Strong cation exchange-type chiral stationary phase for enantioseparation of chiral amines in subcritical fluid chromatography.

PubMed

Wolrab, Denise; Kohout, Michal; Boras, Mario; Lindner, Wolfgang

2013-05-10

A new strong cation exchange type chiral stationary phase (SCX CSP) based on a syringic acid amide derivative of trans-(R, R)-2-aminocyclohexanesulfonic acid was applied to subcritical fluid chromatography (SFC) for separation of various chiral basic drugs and their analogues. Mobile phase systems consisting of aliphatic alcohols as polar modifiers and a broad range of amines with different substitution patterns and lipophilicity were employed to evaluate the impact on the SFC retention and selectivity characteristics. The observed results point to the existence of carbonic and carbamic acid salts formed as a consequence of reactions occurring between carbon dioxide, the alcoholic modifiers and the amine species present in the sub/supercritical fluid medium, respectively. Evidence is provided that these species are essential for affecting ion exchange between the strongly acidic chiral selector units and the basic analytes, following the well-established stoichiometric displacement mechanisms. Specific trends were observed when different types of amines were used as basic additives. While ammonia gave rise to the formation of the most strongly eluting carbonic and carbamic salt species, simple tertiary amines consistently provided superior levels of enantioselectivity. Furthermore, trends in the chiral SFC separation characteristics were investigated by the systematic variation of the modifier content and temperature. Different effects of additives are interpreted in terms of changes in the relative concentration of the transient ionic species contributing to analyte elution, with ammonia-derived carbamic salts being depleted at elevated temperatures by decomposition. Additionally, in an effort to optimize SFC enantiomer separation conditions for selected analytes, the impact of the type of the organic modifier, temperature, flow rate and active back pressure were also investigated. Copyright © 2013 Elsevier B.V. All rights reserved.

High-performance liquid chromatographic enantioseparation of unusual isoxazoline-fused 2-aminocyclopentanecarboxylic acids on macrocyclic glycopeptide-based chiral stationary phases.

PubMed

Sipos, László; Ilisz, István; Nonn, Melinda; Fülöp, Ferenc; Pataj, Zoltán; Armstrong, Daniel W; Péter, Antal

2012-04-06

The enantiomers of four unusual isoxazoline-fused 2-aminocyclopentanecarboxylic acids were directly separated on chiral stationary phases containing macrocyclic glycopeptide antibiotics teicoplanin (Astec Chirobiotic T and T2), teicoplanin aglycone (Chirobiotic TAG), vancomycin (Chirobiotic V) and vancomycin aglycone (Chirobiotic VAG) as chiral selectors. The effects of the mobile phase composition, the structure of the analytes and temperature on the separations were investigated. Experiments were performed at constant mobile phase compositions in the temperature range 5-45 °C to study the effects of temperature, and thermodynamic parameters were calculated from plots of lnk or lnα versus 1/T. Some mechanistic aspects of the chiral recognition process are discussed with respect to the structures of the analytes. It was found that the enantiomeric separations were in most cases enthalpy-driven. The sequence of elution of the enantiomers was determined in all cases. Copyright © 2011 Elsevier B.V. All rights reserved.

Enantioseparation of novel chiral sulfoxides on chlorinated polysaccharide stationary phases in supercritical fluid chromatography.

PubMed

West, Caroline; Konjaria, Mari-Luiza; Shashviashvili, Natia; Lemasson, Elise; Bonnet, Pascal; Kakava, Rusudan; Volonterio, Alessandro; Chankvetadze, Bezhan

2017-05-26

Asymmetric sulfoxides is a particular case of chirality that may be found in natural as well as synthetic products. Twenty-four original molecules containing a sulfur atom as a centre of chirality were analyzed in supercritical fluid chromatography on seven polysaccharide-based chiral stationary phases (CSP) with carbon dioxide - methanol mobile phases. While all the tested CSP provided enantioseparation for a large part of the racemates, chlorinated cellulosic phases proved to be both highly retentive and highly enantioselective towards these species. Favourable structural features were determined by careful comparison of the enantioseparation of the probe molecules. Molecular modelling studies indicate that U-shaped (folded) conformations were most favorable to achieve high enantioresolution on these CSP, while linear (extended) conformations were not so clearly discriminated. For a subset of these species adopting different conformations, a broad range of mobile phase compositions, ranging from 20 to 100% methanol in carbon dioxide, were investigated. While retention decreased continuously in this range, enantioseparation varied in a non-monotonous fashion. Abrupt changes in the tendency curves of retention and selectivity were observed when methanol proportion reaches about 60%, suggesting that a change in the conformation of the analytes and/or chiral selector is occurring at this point. Copyright © 2017 Elsevier B.V. All rights reserved.

HOT ELUENT CAPILLARY LIQUID CHROMATOGRAPHY USING ZIRCONIA AND TITANIA BASED STATIONARY PHASES. (R825344)

EPA Science Inventory

Abstract

High speed capillary liquid chromatographic separations using a simple home made system constructed from readily available inexpensive components have been studied. Using thermally stable zirconia and titania based packing, the separation of eight alkylbenzene...

Normal and polar-organic-phase high-performance liquid chromatographic enantioresolution of omeprazole, rabeprazole, lansoprazole and pantoprazole using monochloro-methylated cellulose-based chiral stationary phase and determination of dexrabeprazole.

PubMed

Dixit, Shuchi; Dubey, Rituraj; Bhushan, Ravi

2014-01-01

Enantioresolution of four anti-ulcer drugs (chiral sulfoxides), namely, omeprazole, rabeprazole, lansoprazole and pantoprazole, was carried out by high-performance liquid chromatography using a polysaccharide-based chiral stationary phase consisting of monochloromethylated cellulose (Lux cellulose-2) under normal and polar-organic-phase conditions with ultraviolet detection at 285 nm. The method was validated for linearity, accuracy, precision, robustness and limit of detection. The optimized enantioresolution method was compared for both the elution modes. The optimized method was further utilized to check the enantiomeric purity of dexrabeprazole. Copyright © 2013 John Wiley & Sons, Ltd.

Two Synthetic Methods for Preparation of Chiral Stationary Phases Using Crystalline Degradation Products of Vancomycin: Column Performance for Enantioseparation of Acidic and Basic Drugs.

PubMed

Abdollahpour, Assem; Heydari, Rouhollah; Shamsipur, Mojtaba

2017-07-01

Two chiral stationary phases (CSPs) based on crystalline degradation products (CDPs) of vancomycin by using different synthetic methods were prepared and compared. Crystalline degradation products of vancomycin were produced by hydrolytic loss of ammonia from vancomycin molecules. Performances of two chiral columns prepared with these degradation products were investigated using several acidic and basic drugs as model analytes. Retention and resolution of these analytes on the prepared columns, as two main parameters, in enantioseparation were studied. The results demonstrated that the stationary phase preparation procedure has a significant effect on the column performance. The resolving powers of prepared columns for enantiomers resolution were changed with the variation in vancomycin-CDP coverage on the silica support. Elemental analysis was used to monitor the surface coverage of silica support by vancomycin-CDP. The results showed that both columns can be successfully applied to chiral separation studies.

Approaches for enantioselective resolution of pharmaceuticals by miniaturised separation techniques with new chiral phases based on nanoparticles and monolithis.

PubMed

Sierra, Isabel; Marina, Maria Luisa; Pérez-Quintanilla, Damián; Morante-Zarcero, Sonia; Silva, Mariana

2016-10-01

This article discusses new developments in the preparation of nanoparticles and monoliths with emphasis upon their application as the stationary and pseudo-stationary phases for miniaturised liquid phase separation techniques, which have occurred in the last 10 years (from 2006 to the actuality). References included in this review represent current trends and state of the art in the application of these materials to the analysis, by EKC, CEC and miniaturised chromatography, of chiral compounds with environmental interest such as pharmaceuticals. Due to their extraordinary properties, columns prepared with these new chiral stationary or pseudo-stationary phases, based on materials such as gold nanoparticles, metal-organic frameworks, ordered mesoporous silicas, carbonaceous materials, polymeric-based and silica-based monoliths or molecularly imprinted materials, can usually show some improvements in the separation selectivity, column efficiency and chemical stability in comparison with conventional chiral columns available commercially. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Preparation of L-phenylalanine chiral ligand-exchange chromatographic stationary phase by atom transfer radical polymerization and resolution of racemates].

PubMed

Sun, Yang; Xu, Fei; Gong, Bolin

2011-09-01

A novel stationary phase was synthesized for chiral ligand-exchange chromatography via atom transfer radical polymerization (ATRP). Glycidyl methacrylate (GMA) was grafted onto the surface of the silica by ATRP using bromoisobutyryl bromide as an initiator, and the organic metal compound formed in the CuCl/2,2'-bipyridine(Bpy) system as a catalyst at room temperature. The chiral stationary phase was then synthesized by grafting L-phenylalanine on the surface of the silica. The stationary phase was characterized by means of elementary analysis and evaluated in detail to determine its separability. The amount of L-phenylalanine on the surface of silica was calculated to be 4.32 mg/m2. The results showed that the good enantioseparations of some DL-amino acids were obtained using ligand-exchange chromatography on the synthesized chiral stationary phase (50 degrees C) with 0.05 mol/L KH2PO4 and 0.1 mmol/L Cu(Ac)2 solution (pH 4.5) as the mobile phase at a flow rate of 1.0 mL/min and a wavelength of 223 nm. The influences of the mobile phase pH, concentration of Cu (II), and temperature of column on the resolution of DL-amino acids by ligand-exchange chromatography were investigated. The results showed that these conditions could affect the resolution of racemates. Compared with the column prepared by radical method using L-phenylalanine directly bonded onto the surface of the silica, the synthesized stationary phase showed a better separation ability, and the DL-aspartic acids and DL-asparagines could be separated at baseline.

Response surface methodology for the determination of the design space of enantiomeric separations on cinchona-based zwitterionic chiral stationary phases by high performance liquid chromatography.

PubMed

Hanafi, Rasha Sayed; Lämmerhofer, Michael

2018-01-26

Quality-by-Design approach for enantioselective HPLC method development surpasses Quality-by-Testing in offering the optimal separation conditions with the least number of experiments and in its ability to describe the method's Design Space visually which helps to determine enantiorecognition to a significant extent. Although some schemes exist for enantiomeric separations on Cinchona-based zwitterionic stationary phases, the exact design space and the weights by which each of the chromatographic parameters influences the separation have not yet been statistically studied. In the current work, a screening design followed by a Response Surface Methodology optimization design were adopted for enantioseparation optimization of 3 model drugs namely the acidic Fmoc leucine, the amphoteric tryptophan and the basic salbutamol. The screening design proved that the acid/base additives are of utmost importance for the 3 chiral drugs, and that among 3 different pairs of acids and bases, acetic acid and diethylamine is the couple able to provide acceptable resolution at variable conditions. Visualization of the response surface of the retention factor, separation factor and resolution helped describe accurately the magnitude by which each chromatographic factor (% MeOH, concentration and ratio of acid base modifiers) affects the separation while interacting with other parameters. The global optima compromising highest enantioresolution with the least run time for the 3 chiral model drugs varied extremely, where it was best to set low % methanol with equal ratio of acid-base modifiers for the acidic drug, very high % methanol and 10-fold higher concentration of the acid for the amphoteric drug while 20 folds of the base modifier with moderate %methanol were needed for the basic drug. Considering the selected drugs as models for many series of structurally related compounds, the design space defined and the optimum conditions computed are the key for method development on

Construction of a hydrazone-linked chiral covalent organic framework-silica composite as the stationary phase for high performance liquid chromatography.

PubMed

Zhang, Kai; Cai, Song-Liang; Yan, Yi-Lun; He, Zi-Hao; Lin, Hui-Mei; Huang, Xiao-Ling; Zheng, Sheng-Run; Fan, Jun; Zhang, Wei-Guang

2017-10-13

Covalent organic frameworks (COFs), as an emerging class of crystalline porous organic polymers, have great potential for applications in chromatographic separation owning to their fascinating crystalline structures and outstanding properties. However, development of COF materials as novel stationary phases in high performance liquid chromatography (HPLC) is just in its infancy. Herein, we report the design and construction of a new hydrazone-linked chiral COF, termed BtaMth COF, from a chiral hydrazide building block (Mth) and present a one-pot synthetic method for the fabrication of BtaMth@SiO 2 composite for HPLC separation of isomers. The as-synthesized BtaMth chiral COF displays good crystallinity, high porosity, as well as excellent chemical stability. Meanwhile, the fabricated HPLC column by using BtaMth@SiO 2 composite as the new stationary phase exhibits high resolution performances for the separation of positional isomers including nitrotoluene and nitrochlorobenzene, as well as cis-trans isomers including beta-cypermethrin and metconazole. Additionally, some effects such as the composition of the mobile phase and column temperature for HPLC separations on the BtaMth@SiO 2 packed column also have been studied in detail. The successful applications indicate the great potentials of hydrazone-linked chiral COF-silica composite as novel stationary phase for the efficient HPLC separation. Copyright © 2017 Elsevier B.V. All rights reserved.

Bidentate urea-based chiral selectors for enantioselective high performance liquid chromatography: synthesis and evaluation of "Crab-like" stationary phases.

PubMed

Kotoni, Dorina; Villani, Claudio; Bell, David S; Capitani, Donatella; Campiglia, Pietro; Gasparrini, Francesco

2013-07-05

A rational approach for the design and preparation of two new "Crab-like" totally synthetic, brush-type chiral stationary phases is presented. Enantiopure diamines, namely 1,2-diaminocyclohexane and 1,2-diphenyl-1,2-ethylene-diamine were treated with 3-(triethoxysilyl)propyl isocyanate, to yield reactive ureido selectors that were eventually attached to unmodified silica particles through a stable, bidentate tether, through a facile two-step one-pot procedure. A full chemical characterization of the new materials has been obtained through solid-state NMR (both (29)Si and (13)C CPMAS) spectroscopy. Columns packed with the two Crab-like chiral stationary phases allow for different mechanisms of separation: normal phase liquid chromatography, reversed phase liquid chromatography and polar organic mode and show a high stability at basic pH values. In particular, the Crab-like column containing the 1,2-diphenyl-1,2-ethylene-diamine selector proved a promising candidate for the resolution of a wide range of racemates (including benzodiazepines, N-derivatized amino acids, and free carboxylic acids) both in normal phase and polar organic mode. An Hmin of 9.57 at a μsf of 0.80mm/s (corresponding to 0.8mL/min) was obtained through van Deemter analysis, based on toluene, for the Crab-like column with the 1,2-diphenyl-1,2-ethylene-diamine selector (250mm×4.6mm I.D.), with a calculated reduced height equivalent to a theoretical plate (h) of only 1.91. Finally, comparative studies were performed with a polymeric commercially available P-CAP-DP column in order to evaluate enantioselectivity and resolution of the Crab-like columns. Copyright © 2013 Elsevier B.V. All rights reserved.

Proline-based chiral stationary phases: a molecular dynamics study of the interfacial structure.

PubMed

Ashtari, M; Cann, N M

2011-09-16

Proline chains have generated considerable interest as a possible basis for new selectors in chiral chromatography. In this article, we employ molecular dynamics simulations to examine the interfacial structure of two diproline chiral selectors, one with a terminal trimethylacetyl group and one with a terminal t-butyl carbamate group. The solvents consist of a relatively apolar n-hexane/2-propanol and a polar water/methanol mixture. We begin with electronic structure calculations for the two chiral selectors to assess the energetics of conformational changes, particularly along the backbone where the amide bonds can alternate between cis and trans conformations. Force fields have been developed for the two selectors, based on these ab initio calculations. Molecular dynamics simulations of the selective interfaces are performed to examine the preferred backbone conformations, as a function of end-group and solvent. The full chiral surface includes the diproline selectors, trimethylsilyl end-caps, and silanol groups. Connection is made with selectivity measurements on these interfaces, where significant differences are observed between these two very similar selectors. Copyright © 2011 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-09-15

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

Adsorption of ibuprofen enantiomers on a chiral stationary phase with a grafted antibiotic eremomycin

NASA Astrophysics Data System (ADS)

Reshetova, E. N.; Asnin, L. D.

2015-02-01

The adsorption of ibuprofen enantiomers on a chiral stationary phase Nautilus-E with a grafted antibiotic eremomycin from aqueous ethanol acetate buffer solutions was studied by chromatography. The ethanol concentration in the mobile phase was varied from 40 to 60 vol %. The adsorption isotherms of both enantiomers had a complex shape characterized by non-Langmuir type curvature and the presence of an inflection point. This is explained by two factors: the energy heterogeneity of the surface of the stationary phase and the dissociation of ibuprofen in the liquid phase. The effect of the system peak on the shape of the chromatograms of the target component was investigated. The temperature effect on the adsorption equilibrium was discussed.

Rapid purification of diastereoisomers from Piper kadsura using supercritical fluid chromatography with chiral stationary phases.

PubMed

Xin, Huaxia; Dai, Zhuoshun; Cai, Jianfeng; Ke, Yanxiong; Shi, Hui; Fu, Qing; Jin, Yu; Liang, Xinmiao

2017-08-04

Supercritical fluid chromatography (SFC) with chiral stationary phases (CSPs) is an advanced solution for the separation of achiral compounds in Piper kadsura. Analogues and stereoisomers are abundant in natural products, but there are obstacles in separation using conventional method. In this paper, four lignan diastereoisomers, (-)-Galbelgin, (-)-Ganschisandrin, Galgravin and (-)-Veraguensin, from Piper kadsura were separated and purified by chiral SFC. Purification strategy was designed, considering of the compound enrichment, sample purity and purification throughput. Two-step achiral purification method on chiral preparative columns with stacked automated injections was developed. Unconventional mobile phase modifier dichloromethane (DCM) was applied to improve the sample solubility. Four diastereoisomers was prepared at the respective weight of 103.1mg, 10.0mg, 152.3mg and 178.6mg from 710mg extract with the purity of greater than 98%. Copyright © 2017 Elsevier B.V. All rights reserved.

Enantiodifferentiation of whisky and cognac lactones using gas chromatography with different cyclodextrin chiral stationary phases.

PubMed

Schmarr, Hans-Georg; Mathes, Maximilian; Wall, Kristina; Metzner, Frank; Fraefel, Marius

2017-09-22

The chiral lactone 5-butyl-4-methyloxolan-2-one or 5-butyl-4-methyldihydro-2(3H)-furanone, often named whisky lactone, is found in oak wood, then contributing to the appreciated flavor of beverages stored in such wooden barrels. Its next higher homologue is named cognac lactone (5-pentyl-4-methyloxolan-2-one or 5-pentyl-4-methyldihydro-2(3H)-furanone), however is much less known, probably due to its minor concentration level. In order to study the direct enantioseparation of both lactones by gas chromatography on chiral stationary phases, individual enantiomers, particularly for cognac lactone were made available. This was achieved by baker's yeast reduction of synthesized ethyl 3-methyl-4-oxononanoate or, after hydrolysis, of the corresponding 4-ketoacid, that gave access to individual enantiomers of cognac lactone. Good enantioseparation was achieved for both whisky and cognac lactone with high values for the chiral resolution with 6-O-tert. butyl dimethylsilyl-2,3-dialkylated or 6-O-tert. butyl dimethylsilyl-2,3-diacylated cyclodextrin derivatives as chiral selectors. The influence of the nature and position of derivatization of the cyclodextrin moiety revealed a strong impact on the chiral recognition mechanism, as the investigated alkylated derivatives heptakis-(2,6-di-O-iso-pentyl-3-O-allyl)-β-cyclodextrin and octakis-(2,3-di-O-pentyl-6-O-methyl)-γ-cyclodextrin did not provide any or only minor chiral selectivity for the two lactones. Copyright © 2017 Elsevier B.V. All rights reserved.

Thiol-ene click chemistry derived cationic cyclodextrin chiral stationary phase and its enhanced separation performance in liquid chromatography.

PubMed

Yao, Xiaobin; Tan, Timothy Thatt Yang; Wang, Yong

2014-01-24

This work is the first demonstration of a simple thiol-ene click chemistry to anchor vinyl imidazolium β-CD onto thiol silica to form a novel cationic native cyclodextrin (CD) chiral stationary phase (CSP). The CSP afforded high enantioseparation ability towards dansyl (Dns) amino acids, carboxylic aryl compounds and flavonoids in chiral HPLC. The current CSP demonstrates the highest resolving ability (selectivity >1.1, resolution >1.5) towards Dns amino acids in a mobile phase buffered at pH=6.5, with the resolution of Dns-dl-leucine as high as 6.97. 2,4-dichloride propionic acid (2,4-ClPOPA) was well resolved with the selectivity and resolution of 1.37 and 4.88, respectively. Compared to a previously reported native CD-CSP based on a triazole linkage, the current cationic CD-CSP shows a stronger retention and higher resolution towards acidic chiral compounds, ascribed to the propitious strong electrostatic attraction. Stability evaluation results indicated that thiol-ene reaction can provide a facile and robust approach for the preparation of positively charged CD CSPs. Copyright © 2013 Elsevier B.V. All rights reserved.

A 3-D open-framework material with intrinsic chiral topology used as a stationary phase in gas chromatography.

PubMed

Xie, Sheng-Ming; Zhang, Xin-Huan; Zhang, Ze-Jun; Zhang, Mei; Jia, Jia; Yuan, Li-Ming

2013-04-01

Compared with liquid chromatography and capillary electrophoresis, the diversity of gas chromatography chiral stationary phases is rather limited. Here, we report the fabrication of Co(D-Cam)1/2(bdc)1/2(tmdpy) (D-Cam = D-camphoric acid; bdc = 1,4-benzenedicarboxylate; tmdpy = 4,4'-trimethylenedipyridine)-coated open tubular columns for high-resolution gas chromatographic separation of compounds. The Co(D-Cam)1/2(bdc)1/2(tmdpy) compound possesses a 3-D framework containing enantiopure building blocks embedded in intrinsically chiral topological nets. In this study, two fused-silica open tubular columns with different inner diameters and lengths, including column A (30 m × 530 μm i.d.) and column B (2 m × 75 μm i.d.), were prepared by a dynamic coating method using Co-(D-Cam)1/2(bdc)1/2(tmdpy) as the stationary phase. The chromatographic properties of the two columns were investigated using n-dodecane as the test compound at 120 °C. The number of theoretical plates (plates/m) of the two metal-organic framework columns was 1,450 and 3,100, respectively. The separation properties were evaluated using racemates, isomers, alkanes, alcohols, and Grob's test mixture. The limit of detection and limit of quantification were found to be 0.125 and 0.417 ng for citronellal enantiomers, respectively. Repeatability (n = 6) showed lower than 0.25 % relative standard deviation (RSD) for retention times and lower than 2.2 % RSD for corrected peak areas. The experimental results showed that the stationary phase has excellent selectivity and also possesses good recognition ability toward these organic compounds, especially chiral compounds.

Self-assembled cyclodextrin-modified gold nanoparticles on silica beads as stationary phase for chiral liquid chromatography and hydrophilic interaction chromatography.

PubMed

Li, Yuanyuan; Wei, Manman; Chen, Tong; Zhu, Nan; Ma, Yulong

2016-11-01

A facile strategy based on self-assembly of Au nanoparticles (AuNPs) (60±10nm in size) on the surfaces of amino-functionalized porous silica spheres under mild conditions was proposed. The resulting material possessed a core-shell structure in which AuNPs were the shell and silica spheres were the core. Then, thiolated-β-cyclodextrin (SH-β-CD) was covalently attached onto the AuNPs as chiral selector for the enantioseparation. The resultant packing material was evaluated by high-performance liquid chromatography (HPLC). The separations of nine pairs of enantiomers were achieved by using the new chiral stationary phase (CSP) in the reversed-phase liquid chromatography (RPLC) mode, respectively. The results showed the new CSP have more sufficient interaction with the analytes due to the existence of AuNPs on silica surfaces, resulting in faster mass transfer rate, compared with β-CD modified silica column. The result shed light on potential usage of chemical modified NPs as chiral selector for enantioseparation based on HPLC. In addition, the new phase was also used in hydrophilic interaction liquid chromatography (HILIC) to separate polar compounds and highly hydrophilic compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Green synthesis of a typical chiral stationary phase of cellulose-tris(3, 5-dimethylphenylcarbamate)

PubMed Central

2013-01-01

Background At present, the study on the homogeneous-phase derivatization of cellulose in ionic liquid is mainly focused on its acetylation. To the best of our knowledge, there has been no such report on the preparation of cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) with ionic liquid 1-allyl-3-methyl-imidazolium chloride (AmimCl) so far. Results With ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a reaction solvent, cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) was synthesized by the reaction of 3,5-dimethylphenyl isocyanate and soluble microcrystalline cellulose in a homogeneous phase. The synthesized CDMPC was then coated onto the surfaces of aminopropyl silica gel to prepare a chiral stationary phase (CSP). The prepared CSP was successfully used in chiral separation of seven racemic pesticides by high performance liquid chromatography (HPLC). Good chiral separation was obtained using n-hexane and different modifiers as the mobile phases under the optimal percentage and column temperature, with the resolution of metalaxyl, diniconazole, flutriafol, paclobutrazol, hexaconazole, myclobutanil and hexythiazox of 1.73, 1.56, 1.26, 1.00, 1.18, 1.14 and 1.51, respectively. The experimental results suggested it was a good choice using a green solvent of AmimCl for cellulose functionalization. Conclusion CDMPC was successfully synthesized as the chiral selector by reacting 3, 5-dimethylphenyl isocyanate with dissolved microcrystalline cellulose in a green ionic liquid of AmimCl. PMID:23890199

Effects of supercritical fluid chromatography conditions on enantioselectivity and performance of polyproline-derived chiral stationary phases.

PubMed

Novell, Arnau; Méndez, Alberto; Minguillón, Cristina

2015-07-17

The chromatographic behaviour and performance of four polyproline-derived chiral stationary phases (CSPs) were tested using supercritical fluid chromatography (SFC). A series of structurally related racemic compounds, whose enantioseparation was proved to be sensitive to the type of mobile phase used in NP-HPLC, were chosen to be tested in the SFC conditions. Good enantioselection ability was shown by the CSPs for the analytes tested in the new conditions. Resolution, efficiency and analysis time, were considerably improved with respect to NP-HPLC when CO2/alcohol mobile phases were used. Monolithic columns clearly show enhanced chromatographic parameters and improved performance respect to their bead-based counterparts. Copyright © 2015 Elsevier B.V. All rights reserved.

Analytical and semipreparative chiral separation of cis-itraconazole on cellulose stationary phases by high-performance liquid chromatography.

PubMed

Kurka, Ondřej; Kučera, Lukáš; Bednář, Petr

2016-07-01

cis-Itraconazole is a chiral antifungal drug administered as a racemate. The knowledge of properties of individual cis-itraconazole stereoisomers is vital information for medicine and biosciences as different stereoisomers of cis-itraconazole may possess different affinity to certain biological pathways in the human body. For this purpose, either chiral synthesis of enantiomers or chiral separation of racemate can be used. This paper presents a two-step high-performance liquid chromatography approach for the semipreparative isolation of four stereoisomers (two enantiomeric pairs) of itraconazole using polysaccharide stationary phases and volatile organic mobile phases without additives in isocratic mode. The approach used involves the separation of the racemate into three fractions (i.e. two pure stereoisomers and one mixed fraction containing the remaining two stereoisomers) in the first run and consequent separation of the collected mixed fraction in the second one. For this purpose, combination of cellulose tris-(4-methylbenzoate) and cellulose tris-(3,5-dimehylphenylcarbamate) columns with complementary selectivity for cis-itraconazole provided full separation of all four stereoisomers (with purity of each isomer > 97%). The stereoisomers were collected, their optical rotation determined and their identity confirmed based on the results of a previously published study. Pure separated stereoisomers are subjected to further biological studies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Innovations in bonding to zirconia-based materials: Part I.

PubMed

Aboushelib, Moustafa N; Matinlinna, Jukka P; Salameh, Ziad; Ounsi, Hani

2008-09-01

Establishing a reliable bond to zirconia-based materials has proven to be difficult which is the major limitation against fabricating adhesive zirconia restorations. This bond could be improved using novel selective infiltration etching conditioning in combination with engineered zirconia primers. Aim of the work was to evaluate resin-to-zirconia bond strength using selective infiltration etching and novel silane-based zirconia primers. Zirconia discs (Procera Zirconia) received selective infiltration etching surface treatment followed by coating with either of five especially engineered experimental zirconia primers. Pre-aged resin-composite discs (Tetric Ivo Ceram) were bonded to the treated surface using an MDP-containing resin-composite (Panavia F 2.0). The bilayered specimens were cut into microbars and the microtensile bond strength (MTBS) was evaluated. 'As-sintered' zirconia discs served as a control (alpha=0.05). The broken microbars were examined using a scanning electron microscope (SEM). The combination of selective infiltration etching with experimental zirconia primers significantly improved (F=3805, P<0.0001) the MTBS values (41+/-5.8 MPa) compared to the 'as-sintered' surface using the same primers which demonstrated spontaneous failure and very low bond strength values (2.6+/-3.1 MPa). SEM analysis revealed that selective infiltration etching surface treatment resulted in a nano-retentive surface where the zirconia primers were able to penetrate and interlock which explained the higher MTBS values observed for the treated specimens.

[Preparation and performance characterization of gold nanoparticles modified chiral capillary electrochromatography stationary phase].

PubMed

Xiong, Lele; Li, Ruijun; Ji, Yibing

2017-07-08

Gold nanoparticles (GNPs, 15 nm) were prepared and introduced to amino groups derived silica monolithic column. Bovine serum albumin (BSA) was immobilized via covalent modification method onto the carboxylic functionalized GNPs to afford chiral stationary phase (CSP) for enantioseparation. GNPs were well dispersed and successfully incorporated onto the columns with the contents as high as 17.18% by characterization method such as transmission electron microscopy (TEM), ultraviolet (UV)-visible absorption spectra and scanning electron microscopy (SEM). The preparation conditions of the BSA modified CSP were optimized and 10% (v/v) 3-aminopropyltriethoxysilane (APTES) and 15 g/L BSA were selected as appropriate reaction conditions. The enantioseparation performance of the BSA modified CSP has been investigated by capillary electrochromatography (CEC). Enantiomers of tryptophan, ephedrine and atenolol were resolved, and the baseline separation of tryptophan was achieved. Meanwhile, the influences of pH value, buffer concentrations and applied voltages used on the chiral separation were studied, and the optimal separation conditions were 10 mmol/L phosphate buffer at pH 7.4 and 15 kV applied voltages. In comparison with the BSA modified CSP prepared by physical adsorption, the CSP prepared by covalent modification method had better separation results, and the analytes could be separated directly without pre-column derivatization. In addition, the prepared BSA modified CSP exhibited good run to run repeatability with relative standard deviations (RSDs) of the migration times and selectivity factors not more than 2.3% and 0.96%, respectively. This work offers a good thinking for modification with other proteins or other types of chiral selectors.

Cellulose tris-(3,5-dimethylphenylcarbamate)-based chiral stationary phase for the enantioseparation of drugs in supercritical fluid chromatography: comparison with HPLC.

PubMed

Kalíková, Květa; Martínková, Monika; Schmid, Martin G; Tesařová, Eva

2018-03-01

A cellulose tris-(3,5-dimethylphenylcarbamate)-based chiral stationary phase was studied as a tool for the enantioselective separation of 21 selected analytes with different pharmaceutical and physicochemical properties. The enantioseparations were performed using supercritical fluid chromatography. The effect of the mobile phase composition was studied. Four different additives (diethylamine, triethylamine, isopropylamine, and trifluoroacetic acid) and isopropylamine combined with trifluoroacetic acid were tested and their influence on enantioseparation was compared. The influence of two different mobile phase co-solvents (methanol and propan-2-ol) combined with all the additives was also evaluated. The best mobile phase compositions for the separation of the majority of enantiomers were CO 2 /methanol/isopropylamine 80:20:0.1 v/v/v or CO 2 /propan-2-ol/isopropylamine/trifluoroacetic acid 80:20:0.05:0.05 v/v/v/v. The best results were obtained from the group of basic β-blockers. A high-performance liquid chromatography separation system composed of the same stationary phase and mobile phase of similar properties prepared as a mixture of hexane/propan-2-ol/additive 80:20:0.1 v/v/v was considered for comparison. Supercritical fluid chromatography was found to yield better results, i.e. better enantioresolution for shorter analysis times than high-performance liquid chromatography. However, examples of enantiomers better resolved under the optimized conditions in high-performance liquid chromatography were also found. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Influence of mobile phase composition on chiral separation of organic selenium racemates].

PubMed

Han, Xiao-qian; Qi, Bang-feng; Dun, Hui-juan; Zhu, Xin-yi; Na, Peng-jun; Jiang, Sheng-xiang; Chen, Li-ren

2002-05-01

The chiral separation of some chiral compounds with similar structure on the cellulose tris (3,5-dimethylphenylcarbamate) chiral stationary phase prepared by us was obtained. Ternary mobile phases influencing chiral recognition were investigated. A mode of interaction between the structural character of samples and chiral stationary phase is discussed. The results indicated that the retention and chiral separation of the analytes had a bigger change with minute addition of alcohols or acetonitrile as modifier in n-hexane/2-propanol (80/20, volume ratio) binary mobile phase.

Synthesis of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) in an ionic liquid and its chiral separation efficiency as stationary phase.

PubMed

Liu, Runqiang; Zhang, Yijun; Bai, Lianyang; Huang, Mingxian; Chen, Jun; Zhang, Yuping

2014-04-11

A chiral selector of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) (CBDMPC) was synthesized by reacting 3,5-dimethylphenyl isocyanate with microcrystalline cellulose dissolved in an ionic liquid of 1-allyl-3-methyl-imidazolium chloride (AMIMCl). The obtained chiral selector was effectively characterized by infrared spectroscopy, elemental analysis and 1H NMR. The selector was reacted with 3-aminopropylsilanized silica gel and the CBDMPC bonded chiral stationary phase (CSP) was obtained. Chromatographic evaluation of the prepared CSPs was conducted by high performance liquid chromatographic (HPLC) and baseline separation of three typical fungicides including hexaconazole, metalaxyl and myclobutanil was achieved using n-hexane/isopropanol as the mobile phase with a flow rate 1.0 mL/min. Experimental results also showed that AMIMCl could be recycled easily and reused in the preparation of CSPs as an effective reaction media.

Synthesis of Cellulose-2,3-bis(3,5-dimethylphenylcarbamate) in an Ionic Liquid and Its Chiral Separation Efficiency as Stationary Phase

PubMed Central

Liu, Runqiang; Zhang, Yijun; Bai, Lianyang; Huang, Mingxian; Chen, Jun; Zhang, Yuping

2014-01-01

A chiral selector of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) (CBDMPC) was synthesized by reacting 3,5-dimethylphenyl isocyanate with microcrystalline cellulose dissolved in an ionic liquid of 1-allyl-3-methyl-imidazolium chloride (AMIMCl). The obtained chiral selector was effectively characterized by infrared spectroscopy, elemental analysis and 1H NMR. The selector was reacted with 3-aminopropylsilanized silica gel and the CBDMPC bonded chiral stationary phase (CSP) was obtained. Chromatographic evaluation of the prepared CSPs was conducted by high performance liquid chromatographic (HPLC) and baseline separation of three typical fungicides including hexaconazole, metalaxyl and myclobutanil was achieved using n-hexane/isopropanol as the mobile phase with a flow rate 1.0 mL/min. Experimental results also showed that AMIMCl could be recycled easily and reused in the preparation of CSPs as an effective reaction media. PMID:24733066

Enantiomeric Profiling of Chiral Pharmacologically Active Compounds in the Environment with the Usage of Chiral Liquid Chromatography 
Coupled with Tandem Mass Spectrometry

PubMed Central

Camacho-Muñoz, Dolores; Petrie, Bruce; Castrignanò, Erika; Kasprzyk-Hordern, Barbara

2016-01-01

The issue of drug chirality is attracting increasing attention among the scientific community. The phenomenon of chirality has been overlooked in environmental research (environmental occurrence, fate and toxicity) despite the great impact that chiral pharmacologically active compounds (cPACs) can provoke on ecosystems. The aim of this paper is to introduce the topic of chirality and its implications in environmental contamination. Special attention has been paid to the most recent advances in chiral analysis based on liquid chromatography coupled with mass spectrometry and the most popular protein based chiral stationary phases. Several groups of cPACs of environmental relevance, such as illicit drugs, human and veterinary medicines were discussed. The increase in the number of papers published in the area of chiral environmental analysis indicates that researchers are actively pursuing new opportunities to provide better understanding of environmental impacts resulting from the enantiomerism of cPACs. PMID:27713682

Amino acid ionic liquids as chiral ligands in ligand-exchange chiral separations.

PubMed

Liu, Qian; Wu, Kangkang; Tang, Fei; Yao, Lihua; Yang, Fei; Nie, Zhou; Yao, Shouzhuo

2009-09-28

Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1-alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers-dl-phenylalanine (dl-Phe), dl-histidine (dl-His), dl-tryptophane (dl-Trp), and dl-tyrosine (dl-Tyr)-were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (R(s))=3.26-10.81 for HPLC; R(s)=1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the stationary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the dl-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.

HPLC SEPARATION OF CHIRAL ORGANOPHOSPHORUS PESTICIDES ON POLYSACCHARIDE CHIRAL STATIONARY PHASES

EPA Science Inventory

High-performance liquid chromatographic separation of the individual enantiomers of 12 organophosphorus pesticides (OPs) were obtained on polysaccharide chiral HPLC columns using an alkane-alcohol mobile phase. The OP pesticides were crotoxyphos, dialifor, dyfonate, fenamiphos, ...

Zirconia based dental ceramics: structure, mechanical properties, biocompatibility and applications.

PubMed

Gautam, Chandkiram; Joyner, Jarin; Gautam, Amarendra; Rao, Jitendra; Vajtai, Robert

2016-12-06

Zirconia (ZrO 2 ) based dental ceramics have been considered to be advantageous materials with adequate mechanical properties for the manufacturing of medical devices. Due to its very high compression strength of 2000 MPa, ZrO 2 can resist differing mechanical environments. During the crack propagation on the application of stress on the surface of ZrO 2 , a crystalline modification diminishes the propagation of cracks. In addition, zirconia's biocompatibility has been studied in vivo, leading to the observation of no adverse response upon the insertion of ZrO 2 samples into the bone or muscle. In vitro experimentation has exhibited the absence of mutations and good viability of cells cultured on this material leading to the use of ZrO 2 in the manufacturing of hip head prostheses. The mechanical properties of zirconia fixed partial dentures (FPDs) have proven to be superior to other ceramic/composite restorations and hence leading to their significant applications in implant supported rehabilitations. Recent developments were focused on the synthesis of zirconia based dental materials. More recently, zirconia has been introduced in prosthetic dentistry for the fabrication of crowns and fixed partial dentures in combination with computer aided design/computer aided manufacturing (CAD/CAM) techniques. This systematic review covers the results of past as well as recent scientific studies on the properties of zirconia based ceramics such as their specific compositions, microstructures, mechanical strength, biocompatibility and other applications in dentistry.

Enantiomeric separation of volatile organics by gas chromatography for the in situ analysis of extraterrestrial materials: kinetics and thermodynamics investigation of various chiral stationary phases.

PubMed

Freissinet, C; Buch, A; Szopa, C; Sternberg, R

2013-09-06

The performances of several commercial chiral capillary columns have been evaluated with the aim of determining the one most suitable for enantiomeric separation in a gas chromatograph onboard a space probe. We compared the GC-MS response of three capillary columns coated with different chiral stationary phases (CSP) using volatile chiral organic molecules which are potential markers of a prebiotic organic chemistry. The three different chiral capillary columns are Chirasil-Val, with an amino acid derivative CSP, ChiralDex-β-PM, with a CSP composed of dissolved permethylated β-cyclodextrins in polysiloxane, and Chirasil-Dex, with a CSP made of modified cyclodextrins chemically bonded to the polysiloxane backbone. Both kinetics and thermodynamics studies have been carried out to evaluate the chiral recognition potential in these different types of columns. The thermodynamic parameters also allow a better understanding of the driving forces affecting the retention and separation of the enantiomers. The Chirasil-Dex-CSP displays the best characteristics for an optimal resolution of the chiral compounds, without preliminary derivatization. This CSP had been chosen to be the only chiral column in the Sample Analysis at Mars (SAM) experiment onboard the current Mars Science Laboratory (MSL) mission, and is also part of the Mars Organic Molecules Analyzer (MOMA) gas chromatograph onboard the next Martian mission ExoMars. The use of this column could also be extended to all space missions aimed at studying chirality in space. Copyright © 2013 Elsevier B.V. All rights reserved.

Development of a composite chiral stationary phase from BSA and β-cyclodextrin-bonded silica.

PubMed

Yao, Bixia; Yang, Xinmei; Guo, Lizhen; Kang, Shanshan; Weng, Wen

2014-01-01

A composite chiral stationary phase (CSP) derived from bovine serum albumin (BSA) and β-cyclodextrin (CD)-bonded silica was prepared. 2,4,6-Trichloro-1,3,5-triazine was used as a cross-linker. The obtained CSP was applied to the enantioseparation of tryptophan, hydrobenzoin, phenylalanine and mandelic acid. The influences of eluent pH value, organic modifier and column temperature on the retention and enantioseparation were discussed. Tryptophan and hydrobenzoin achieved excellent resolution on the composite CSP. For tryptophan, the highest selectivity, 2.79, was achieved with 1% of methanol at pH 8.0. For hydrobenzoin, the selectivity could reach 1.42. The chromatographic results were compared with that on β-CD-bonded or BSA-immobilized CSP. © The Author [2014]. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Internal coating of zirconia restoration with silica-based ceramic improves bonding of resin cement to dental zirconia ceramic.

PubMed

Kitayama, Shuzo; Nikaido, Toru; Ikeda, Masaomi; Alireza, Sadr; Miura, Hiroyuki; Tagami, Junji

2010-01-01

Resin bonding to zirconia ceramic cannot be established by standard methods that are utilized for conventional silica-based dental ceramics. This study was aimed to examine the tensile bond strength of resin cement to zirconia ceramic using a new laboratory technique. Sixty-four zirconia ceramic specimens were air-abraded using Al2O3 particles and divided into two groups; the control group with no pretreatment (Control), and the group pretreated using the internal coating technique (INT), in which the surface of the zirconia specimens were thinly coated by fusing silica-based ceramic and air-abraded in the same manner. The specimens in each group were further divided into two subgroups according to the silane coupling agents applied; a mixture of dentin primer/silane coupling agent (Clearfil SE Bond Primer/Porcelain Bond Activator) or a newly developed single-component silane coupling agent (Clearfil Ceramic Primer). After bonding with dual-cured resin cement (Panavia F 2.0), they were stored in water for 24 h and half of them were additionally subjected to thermal cycling. The tensile bond strengths were tested using a universal testing machine. ANOVAs revealed significant influence of ceramic surface pretreatment (p<0.001), silane coupling agent (p<0.001) and thermal cycling (p<0.001); the INT coating technique significantly increased the bond strengths of resin cement to zirconia ceramic, whereas thermal cycling significantly decreased the bond strengths. The use of a single-component silane coupling agent demonstrated significantly higher bond strengths than that of a mixture of dentin primer/silane coupling agent. The internal coating of zirconia dental restorations with silica-based ceramic followed by silanization may be indicated in order to achieve better bonding for the clinical success.

Zirconia in dentistry: part 2. Evidence-based clinical breakthrough.

PubMed

Koutayas, Spiridon Oumvertos; Vagkopoulou, Thaleia; Pelekanos, Stavros; Koidis, Petros; Strub, Jörg Rudolf

2009-01-01

An ideal all-ceramic restoration that conforms well and demonstrates enhanced biocompatibility, strength, fit, and esthetics has always been desirable in clinical dentistry. However, the inherent brittleness, low flexural strength, and fracture toughness of conventional glass and alumina ceramics have been the main obstacles for extensive use. The recent introduction of zirconia-based ceramics as a restorative dental material has generated considerable interest in the dental community, which has been expressed with extensive industrial, clinical, and research activity. Contemporary zirconia powder technology contributes to the fabrication of new biocompatible all-ceramic restorations with improved physical properties for a wide range of promising clinical applications. Especially with the development of computer-aided design (CAD)/computer-aided manufacturing (CAM) systems, high-strength zirconia frameworks can be viable for the fabrication of full and partial coverage crowns, fixed partial dentures, veneers, posts and/or cores, primary double crowns, implant abutments, and implants. Data from laboratory and clinical studies are promising regarding their performance and survival. However, clinical data are considered insufficient and the identified premature complications should guide future research. In addition, different zirconia-based dental auxiliary components (i.e., cutting burs and surgical drills, extra-coronal attachments and orthodontic brackets) can also be technologically feasible. This review aims to present and discuss zirconia manufacturing methods and their potential for successful clinical application in dentistry.

Alumina additions may improve the damage tolerance of soft machined zirconia-based ceramics.

PubMed

Oilo, Marit; Tvinnereim, Helene M; Gjerdet, Nils Roar

2011-01-01

The aim of this study was to evaluate the damage tolerance of different zirconia-based materials. Bars of one hard machined and one soft machined dental zirconia and an experimental 95% zirconia 5% alumina ceramic were subjected to 100,000 stress cycles (n = 10), indented to provoke cracks on the tensile stress side (n = 10), and left untreated as controls (n = 10). The experimental material demonstrated a higher relative damage tolerance, with a 40% reduction compared to 68% for the hard machined zirconia and 84% for the soft machined zirconia.

Chiral quantum dot based materials

NASA Astrophysics Data System (ADS)

Govan, Joseph; Loudon, Alexander; Baranov, Alexander V.; Fedorov, Anatoly V.; Gun'ko, Yurii

2014-05-01

Recently, the use of stereospecific chiral stabilising molecules has also opened another avenue of interest in the area of quantum dot (QD) research. The main goal of our research is to develop new types of technologically important quantum dot materials containing chiral defects, study their properties and explore their applications. The utilisation of chiral penicillamine stabilisers allowed the preparation of new water soluble white emitting CdS quantum nanostructures which demonstrated circular dichroism in the band-edge region of the spectrum. It was also demonstrated that all three types of QDs (D-, L-, and Rac penicillamine stabilised) show very broad emission bands between 400 and 700 nm due to defects or trap states on the surfaces of the nanocrystals. In this work the chiral CdS based quantum nanostructures have also been doped by copper metal ions and new chiral penicilamine stabilized CuS nanoparticles have been prepared and investigated. It was found that copper doping had a strong effect at low levels in the synthesis of chiral CdS nanostructures. We expect that this research will open new horizons in the chemistry of chiral nanomaterials and their application in biotechnology, sensing and asymmetric synthesis.

Enantioseparation of α-Hydroxyallylphosphonates and Phosphonoallylic Carbonate Derivatives on Chiral Stationary Phases Using Sequential UV, Polarimetric, and Refractive Index Detection.

PubMed

Hamper, Bruce C; Mannino, Michael P; Mueller, Melissa E; Harrison, Liam T; Spilling, Christopher D

2016-09-01

Chromatographic separation of the enantiomers of parent compounds dimethyl α-hydroxyallyl phosphonate and 1-(dimethoxyphosphoryl) allyl methyl carbonate was demonstrated by high-performance liquid chromatography (HPLC) using Chiralpak AS-H and ad-H chiral stationary phases (CSP), respectively, using a combination of UV, polarimetric, and refractive index detectors. A comparison was made of the separation efficiency and elution order of enantiomeric α-hydroxyallyl phosphonates and their carbonate derivatives on commercially available polysaccharide AS, ad, OD, IC-3, and Whelk-O 1 CSPs. In general, the α-hydroxyallyl phosphonates were resolved on the AS-H CSP, whereas the carbonate derivatives and were preferentially resolved on the ad-H CSP. The impact of aryl substitution on the resolution of analytes and was evaluated. Thermodynamic parameters determined for enantioselective adsorption hydroxyphosphonates and on the AS-H CSP and carbonate on the ad-H CSP demonstrated enthalpic control for separation of the enantiomers. Chirality 28:656-662, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality.

PubMed

Arthurs, Ross A; Ismail, Muhammad; Prior, Christopher C; Oganesyan, Vasily S; Horton, Peter N; Coles, Simon J; Richards, Christopher J

2016-02-24

Reaction of [IrCp*Cl2 ]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6 H4 ) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp *,RIr *. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc ,Sp ,RIr . Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enantioseparation of racemic 4-aryl-3,4-dihydro-2(1H)-pyrimidones on chiral stationary phases based on 3,5-dimethylanilides of N-(4-alkylamino-3,5-dinitro)benzoyl L-alpha-amino acids.

PubMed

Kontrec, Darko; Vinković, Vladimir; Sunjić, Vitomir; Schuiki, Birgit; Fabian, Walter M F; Kappe, C Oliver

2003-06-01

Three novel chiral packing materials for high-performance liquid chromatography were prepared by covalently binding of (2S)-N-(3,5-dimethylphenyl)-2-[(4-chloro-3,5-dinitrophenyl)carbonylamino]propan-amide (7), (2S)-N-(3,5-dimethylphenyl)-2-[(4-chloro-3,5-dinitrophenyl)carbonylamino]-4-methylpentanamide (8), and (2S)-N-(3,5-dimethylphenyl)-2-[(4-chloro-3,5-dinitrophenyl)carbonyl-amino]-2-phenylacetamide (9) to aminopropyl silica. The resulting chiral stationary phases (CSPs 1-3) proved effective for the resolution of racemic 4-aryl-3,4-dihydro-2(1H)-pyrimidone derivatives (TR 1-14). The mechanism of their enantioselection, supported by the elution order of (S)-TR 13 and (R)-TR 13 and molecular modeling of the complex of the slower running (S)-TR 13 with CSP 1 is discussed. Copyright 2003 Wiley-Liss, Inc.

Chiral ionic liquids in chromatographic and electrophoretic separations.

PubMed

Kapnissi-Christodoulou, Constantina P; Stavrou, Ioannis J; Mavroudi, Maria C

2014-10-10

This report provides an overview of the application of chiral ionic liquids (CILs) in separation technology, and particularly in capillary electrophoresis and both gas and liquid chromatography. There is a large number of CILs that have been synthesized and designed as chiral agents. However, only a few have successfully been applied in separation technology. Even though this application of CILs is still in its early stages, the scientific interest is increasing dramatically. This article is focused on the use of CILs as chiral selectors, background electrolyte additives, chiral ligands and chiral stationary phases in electrophoretic and chromatographic techniques. Different examples of CILs, which contain either a chiral cation, a chiral anion or both, are presented in this review article, and their major advantages along with their potential applications in chiral electrophoretic and chromatographic recognition are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

DEVELOPMENT OF AN AFFINITY SILICA MONOLITH CONTAINING HUMAN SERUM ALBUMIN FOR CHIRAL SEPARATIONS

PubMed Central

Mallik, Rangan; Hage, David S.

2008-01-01

An affinity monolith based on silica and containing immobilized human serum albumin (HSA) was developed and evaluated in terms of its binding, efficiency and selectivity in chiral separations. The results were compared with data obtained for the same protein when used as a chiral stationary phase with HPLC-grade silica particles or a monolith based on a copolymer of glycidyl methacrylate (GMA) and ethylene dimethacrylate (EDMA). The surface coverage of HSA in the silica monolith was similar to values obtained with silica particles and a GMA/EDMA monolith. However, the higher surface area of the silica monolith gave a material that contained 1.3- to 2.2-times more immobilized HSA per unit volume when compared to silica particles or a GMA/EDMA monolith. The retention, efficiency and resolving power of the HSA silica monolith were evaluated using two chiral analytes: D/L-tryptophan and R/S-warfarin. The separation of R- and S-ibuprofen was also considered. The HSA silica monolith gave higher retention and higher or comparable resolution and efficiency when compared with HSA columns that contained silica particles or a GMA/EDMA monolith. The silica monolith also gave lower back pressures and separation impedances than these other materials. It was concluded that silica monoliths can be valuable alternatives to silica particles or GMA/EDMA monoliths when used with immobilized HSA as a chiral stationary phase. PMID:17475436

Zirconia in fixed prosthesis. A literature review

PubMed Central

Román-Rodríguez, Juan L.; Ferreiroa, Alberto; Solá-Ruíz, María F.; Fons-Font, Antonio

2014-01-01

Statement of problem: Evidence is limited on the efficacy of zirconia-based fixed dental prostheses. Objective: To carry out a literature review of the behavior of zirconium oxide dental restorations. Material and Methods: This literature review searched the Pubmed, Scopus, Medline and Cochrane Library databases using key search words “zirconium oxide,” “zirconia,” “non-metal restorations,” “ceramic oxides,” “veneering ceramic,” “zirconia-based fixed dental prostheses”. Both in vivo and in vitro studies into zirconia-based prosthodontic restoration behavior were included. Results: Clinical studies have revealed a high rate of fracture for porcelain-veneered zirconia-based restorations that varies between 6% and 15% over a 3- to 5-year period, while for ceramo-metallic restorations the fracture rate ranges between 4 and 10% over ten years. These results provoke uncertainty as to the long-term prognosis for this material in the oral medium. The cause of veneering porcelain fractures is unknown but hypothetically they could be associated with bond failure between the veneer material and the zirconia sub-structure. Key words:Veneering ceramic, zirconia-based ceramic restoration, crown, zirconia, tooth-supported fixed prosthesis. PMID:24596638

Fracture resistance of zirconia-based implant abutments after artificial long-term aging.

PubMed

Alsahhaf, Abdulaziz; Spies, Benedikt Christopher; Vach, Kirstin; Kohal, Ralf-Joachim

2017-02-01

To investigate the survival rate, fracture strength, bending moments, loading to fracture and fracture modes of different designs of zirconia abutments after dynamic loading with thermocycling, and compare these values to titanium abutments. A total of 80 abutment samples were divided into 5 test groups of 16 samples in each group. The study included the following groups, "Group 1" CAD/CAM produced all-zirconia abutments, "Group 2" titanium abutments, "Group 3" zirconia-abutments adhesively luted to a titanium base, "Group 4" prefabricated all-zirconia abutments and "Group 5" zirconia-abutments glass soldered to a titanium base. Half the number of samples in each group was exposed to 1.2 million loading cycles (5-years simulation) in the chewing simulator. The samples that survived the artificial aging were later tested for fracture strength in a universal testing machine. The remaining 8 samples of the group were directly tested for fracture strength. All samples exposed to the 5-years artificial aging survived except of six samples in one group (Group 1). The surviving samples were later fracture tested in the universal testing machine. The bending moments (Ncm) values were as follow: Exposed groups: "Group 1" 94.5Ncm; "Group 2" 599.2Ncm; "Group 3" 477.5Ncm; "Group 4" 314.4Ncm; "Group 5" 509.4Ncm. Non-exposed groups: "Group 1" 269.3Ncm; "Group 2" 474.2Ncm; "Group 3" 377.6Ncm; "Group 4" 265.4Ncm; "Group 5" 372.4Ncm. Except in Group 1, the values were higher in the exposed groups, although, statistically there was no difference (p>0.05). The one-piece ZrO2-abutment group (Group 1 and Group 4) exhibited lower values, while the two-piece ZrO2-abutment groups (Group 3 and Group 5) showed similar values and fracture modes like the titanium abutment group. The titanium abutment group showed the highest values of bending moments among all groups. The implant-abutment connection area appeared to influence the bending moment value and the fracture mode of the tested

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation

PubMed Central

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-01-01

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3, 5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. PMID:23891368

Chiral magnetic microspheres purified by centrifugal field flow fractionation and microspheres magnetic chiral chromatography for benzoin racemate separation.

PubMed

Tian, Ailin; Qi, Jing; Liu, Yating; Wang, Fengkang; Ito, Yoichiro; Wei, Yun

2013-08-30

Separation of enantiomers still remains a challenge due to their identical physical and chemical properties in a chiral environment, and the research on specific chiral selector along with separation techniques continues to be conducted to resolve individual enantiomers. In our laboratory the promising magnetic chiral microspheres Fe3O4@SiO2@cellulose-2, 3-bis (3,5-dimethylphenylcarbamate) have been developed to facilitate the resolution using both its magnetic property and chiral recognition ability. In our present studies this magnetic chiral selector was first purified by centrifuge field flow fractionation, and then used to separate benzoin racemate by a chromatographic method. Uniform-sized and masking-impurity-removed magnetic chiral selector was first obtained by field flow fractionation with ethanol through a spiral column mounted on the type-J planetary centrifuge, and using the purified magnetic chiral selector, the final chromatographic separation of benzoin racemate was successfully performed by eluting with ethanol through a coiled tube (wound around the cylindrical magnet to retain the magnetic chiral selector as a stationary phase) submerged in dry ice. In addition, an external magnetic field facilitates the recycling of the magnetic chiral selector. Copyright © 2013 Elsevier B.V. All rights reserved.

Enantiomeric separation of six chiral pesticides that contain chiral sulfur/phosphorus atoms by supercritical fluid chromatography.

PubMed

Zhang, Lijun; Miao, Yelong; Lin, Chunmian

2018-03-01

Six chiral pesticides containing chiral sulfur/phosphorus atoms were separated by supercritical fluid chromatography with supercritical CO 2 as the main mobile phase component. The effect of the chiral stationary phase, different type and concentration of modifiers, column temperature, and backpressure on the separation efficiency was investigated to obtain the appropriate separation condition. Five chiral pesticides (isofenphos-methyl, isocarbophos, flufiprole, fipronil, and ethiprole) were baseline separated under experimental conditions, while isofenphos only obtained partial separation. The Chiralpak AD-3 column showed a better chiral separation ability than others for chiral pesticides containing chiral sulfur/phosphorus atoms. When different modifiers at the same concentration were used, the retention factor of pesticides except flufiprole decreased in the order of isopropanol, ethanol, methanol; meanwhile, the retention factor of flufiprole increased in the order of isopropanol, ethanol, methanol. For a given modifier, the retention factor and resolution decreased on the whole with the increase of its concentration. The enantiomer separation of five chiral pesticides was an "enthalpy-driven" process, and the separation factor decreased as the temperature increased. The backpressure of the mobile phase had little effect on the separation factor and resolution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of molindone enantiomers in human plasma by high-performance liquid chromatography-tandem mass spectrometry using macrocyclic antibiotic chiral stationary phases.

PubMed

Jiang, Hongliang; Li, Yinghe; Pelzer, Mary; Cannon, Michelle J; Randlett, Christopher; Junga, Heiko; Jiang, Xiangyu; Ji, Qin C

2008-05-30

A sensitive and selective bioanalytical assay was developed and validated for the determination of enantiomeric molindone in human plasma using high-performance liquid chromatography-tandem mass spectrometry along with supported liquid extraction procedures. The chiral separation was evaluated and optimized on macrocyclic antibiotic type chiral stationary phases (CSPs) based on teicoplanin aglycone (Chirobiotic TAG) in polar organic, polar ionic, and reversed-phase mode chromatography, respectively. Complete baseline separation was achieved on a Chirobiotic TAG column under isocratic condition in reversed-phase chromatography. The method validation was conducted using a Chirobiotic TAG column (100 mm x 2.1 mm) over the curve range 0.100-100 ng/ml for each molindone enantiomer using 0.0500 ml of plasma sample. The flow rate was 0.8 ml/min and the total run time was 9 min. Supported liquid extraction in a 96-well plate format was used for sample preparation. Parameters including recovery, matrix effect, linearity, sensitivity, specificity, carryover, precision, accuracy, dilution integrity, and stability were evaluated. The intra- and inter-day precision and accuracy of the quality control samples at low, medium, and high concentration levels were RSD

In vitro comparison of fracture load of implant-supported, zirconia-based, porcelain- and composite-layered restorations after artificial aging.

PubMed

Komine, Futoshi; Taguchi, Kohei; Fushiki, Ryosuke; Kamio, Shingo; Iwasaki, Taro; Matsumura, Hideo

2014-01-01

This study evaluated fracture load of single-tooth, implant-supported, zirconia-based, porcelain- and indirect composite-layered restorations after artificial aging. Forty-four zirconia-based molar restorations were fabricated on implant abutments and divided into four groups, namely, zirconia-based all-ceramic restorations (ZAC group) and three types of zirconia-based composite-layered restorations (ZIC-P, ZIC-E, and ZIC groups). Before layering an indirect composite material, the zirconia copings in the ZIC-P and ZIC-E groups were primed with Clearfil Photo Bond and Estenia Opaque Primer, respectively. All restorations were cemented on the abutments with glass-ionomer cement and then subjected to thermal cycling and cyclic loading. All specimens survived thermal cycling and cyclic loading. The fracture load of the ZIC-P group (2.72 kN) was not significantly different from that of the ZAC group (3.05 kN). The fracture load of the zirconia-based composite-layered restoration primed with Clearfil Photo Bond (ZIC-P) was comparable to that of the zirconia-based all-ceramic restoration (ZAC) after artificial aging.

Zirconia in biomedical applications.

PubMed

Chen, Yen-Wei; Moussi, Joelle; Drury, Jeanie L; Wataha, John C

2016-10-01

The use of zirconia in medicine and dentistry has rapidly expanded over the past decade, driven by its advantageous physical, biological, esthetic, and corrosion properties. Zirconia orthopedic hip replacements have shown superior wear-resistance over other systems; however, risk of catastrophic fracture remains a concern. In dentistry, zirconia has been widely adopted for endosseous implants, implant abutments, and all-ceramic crowns. Because of an increasing demand for esthetically pleasing dental restorations, zirconia-based ceramic restorations have become one of the dominant restorative choices. Areas covered: This review provides an updated overview of the applications of zirconia in medicine and dentistry with a focus on dental applications. The MEDLINE electronic database (via PubMed) was searched, and relevant original and review articles from 2010 to 2016 were included. Expert commentary: Recent data suggest that zirconia performs favorably in both orthopedic and dental applications, but quality long-term clinical data remain scarce. Concerns about the effects of wear, crystalline degradation, crack propagation, and catastrophic fracture are still debated. The future of zirconia in biomedical applications will depend on the generation of these data to resolve concerns.

Fabrication and Characterization of Dense Zirconia and Zirconia-Silica Ceramic Nanofibers

PubMed Central

Guo, Guangqing; Fan, Yuwei

2011-01-01

The objective of this study was to prepare dense zirconia-yttria (ZY), zirconia-silica (ZS) and zirconia-yttria-silica (ZYS) nanofibers as reinforcing elements for dental composites. Zirconium (IV) propoxide, yttrium nitrate hexahydrate, and tetraethyl orthosilicate (TEOS) were used as precursors for the preparation of zirconia, yttria, and silica sols. A small amount (1–1.5 wt%) of polyethylene oxide (PEO) was used as a carry polymer. The sols were preheated at 70 °C before electrospinning and their viscosity was measured with a viscometer at different heating time. The gel point was determined by viscosity–time (η–t) curve. The ZY, ZS and ZYS gel nanofibers were prepared using a special reactive electrospinning device under the conditions near the gel point. The as-prepared gel nanofibers had diameters between 200 and 400 nm. Dense (nonporous) ceramic nanofibers of zirconia-yttria (96/4), zirconia-silica (80/20) and zirconia-yttria-silica (76.8/3.2/20) with diameter of 100–300 nm were obtained by subsequent calcinations at different temperatures. The gel and ceramic nanofibers obtained were characterized by scanning electron microscope (SEM), high-resolution field-emission scanning electron microscope (FE-SEM), thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), Fourier transform infrared spectrometer (FT-IR), and X-ray diffraction (XRD). SEM micrograph revealed that ceramic ZY nanofibers had grained structure, while ceramic ZS and ZYS nanofibers had smooth surfaces, both showing no visible porosity under FE-SEM. Complete removal of the polymer PEO was confirmed by TGA/DSC and FT-IR. The formation of tetragonal phase of zirconia and amorphous silica was proved by XRD. In conclusion, dense zirconia-based ceramic nanofibers can be fabricated using the new reactive sol–gel electrospinning technology with minimum organic polymer additives. PMID:21133090

Chiral Drug Analysis in Forensic Chemistry: An Overview.

PubMed

Ribeiro, Cláudia; Santos, Cristiana; Gonçalves, Valter; Ramos, Ana; Afonso, Carlos; Tiritan, Maria Elizabeth

2018-01-28

Many substances of forensic interest are chiral and available either as racemates or pure enantiomers. Application of chiral analysis in biological samples can be useful for the determination of legal or illicit drugs consumption or interpretation of unexpected toxicological effects. Chiral substances can also be found in environmental samples and revealed to be useful for determination of community drug usage (sewage epidemiology), identification of illicit drug manufacturing locations, illegal discharge of sewage and in environmental risk assessment. Thus, the purpose of this paper is to provide an overview of the application of chiral analysis in biological and environmental samples and their relevance in the forensic field. Most frequently analytical methods used to quantify the enantiomers are liquid and gas chromatography using both indirect, with enantiomerically pure derivatizing reagents, and direct methods recurring to chiral stationary phases.

On the interfacial fracture resistance of resin-bonded zirconia and glass-infiltrated graded zirconia

PubMed Central

Chai, Herzl; Kaizer, Marina; Chughtai, Asima; Tong, Hui; Tanaka, Carina; Zhang, Yu

2015-01-01

Objective A major limiting factor for the widespread use of zirconia in prosthetic dentistry is its poor resin-cement bonding capabilities. We show that this deficiency can be overcome by infiltrating the zirconia cementation surface with glass. Current methods for assessing the fracture resistance of resin-ceramic bonds are marred by uneven stress distribution at the interface, which may result in erroneous interfacial fracture resistance values. We have applied a wedge-loaded double-cantilever-beam testing approach to accurately measure the interfacial fracture resistance of adhesively bonded zirconia-based restorative materials. Methods The interfacial fracture energy GC was determined for adhesively bonded zirconia, graded zirconia and feldspathic ceramic bars. The bonding surfaces were subjected to sandblasting or acid etching treatments. Baseline GC was measured for bonded specimens subjected to 7 days hydration at 37 °C. Long-term GC was determined for specimens exposed to 20,000 thermal cycles between 5 and 55 °C followed by 2-month aging at 37 °C in water. The test data were interpreted with the aid of a 2D finite element fracture analysis. Results The baseline and long-term GC for graded zirconia was 2–3 and 8 times that for zirconia, respectively. More significantly, both the baseline and long-term GC of graded zirconia were similar to those for feldspathic ceramic. Significance The interfacial fracture energy of feldspathic ceramic and graded zirconia was controlled by the fracture energy of the resin cement while that of zirconia by the interface. GC for the graded zirconia was as large as for feldspathic ceramic, making it an attractive material for use in dentistry. PMID:26365987

Substituent effects on the enantioselective retention of anti-HIV 5-aryl-delta 2-1,2,4-oxadiazolines on R,R-DACH-DNB chiral stationary phase.

PubMed

Altomare, C; Cellamare, S; Carotti, A; Barreca, M L; Chimirri, A; Monforte, A M; Gasparrini, F; Villani, C; Cirilli, M; Mazza, F

1996-01-01

A series of racemic 3-phenyl-4-(1-adamantyl)-5-X-phenyl- delta 2-1,2,4-oxadiazo lines (PAdOx) were directly resolved by HPLC using a Pirkle-type stationary phase containing N,N'-(3,5-dinitrobenzoyl)-1(R),2(R)-diaminocyclohexane as chiral selector. The more retained enantiomers have S configuration, as demonstrated by X-ray crystallography and circular dichroism measurements. The influence of aromatic ring substituents on enantioselective retention was quantitatively assessed by traditional linear free energy-related (LFER) equations and comparative molecular field analysis (CoMFA). In good agreement with previous findings, the results from this study indicate that the increase in retention (k') is favoured mainly by the phi-basicity and the hydrophilicity of solute, whereas enantioselectivity (alpha) can be satisfactorily modeled by electronic and bulk parameters or CoMFA descriptors. The LFER equations and CoMFA models gave helpful insights into chiral recognition mechanisms.

No-Drag Frame for Anomalous Chiral Fluid

DOE PAGES

Stephanov, Mikhail A.; Yee, Ho-Ung

2016-03-24

For an anomalous fluid carrying dissipationless chiral magnetic and/or vortical currents we show that there is a frame in which a stationary obstacle experiences no drag, but energy and charge currents do not vanish, resembling superfluidity. Unlike ordinary superfluid flow, the anomalous chiral currents can transport entropy in this frame. Moreover, we show that the second law of thermodynamics completely determines the amounts of these anomalous nondissipative currents in the “no-drag frame” as polynomials in temperature and chemical potential with known anomaly coefficients. These general results are illustrated and confirmed by a calculation in the chiral kinetic theory and inmore » the quark-gluon plasma at high temperature.« less

A direct HPLC method for the resolution and quantitation of the R-(-)- and S-(+)-enantiomers of vigabatrin (gamma-vinyl-GABA) in pharmaceutical dosage forms using teicoplanin aglycone chiral stationary phase.

PubMed

Al-Majed, Abdulrahman A

2009-08-15

A direct chiral high-performance liquid chromatography (HPLC) method was developed and validated for the resolution and quantification of antiepileptic drug enantiomers, R-(-)- and S-(+)-vigabatrin (gamma-vinyl-gamma-aminobutyric acid) in pharmaceutical products. The separation was optimized on a macrocyclic glycopeptide antibiotic chiral stationary phase (CSP) based on teicoplanin aglycone, chirobiotic (TAG), using a mobile phase system containing ethanol-water (80:20, v/v), at a flow rate of 0.4ml/min and UV detection set at 210nm. The stability of vigabatrin enantiomers under different degrees of temperature was also studied. The enantiomers of vigabatrin were separated from each other. The calibration curves were linear over a range of 100-1600microg/ml (r=0.999) for both enantiomers. The overall recoveries of R-(-)- and S-(+)-vigabatrin enantiomers from pharmaceutical products were in the range of 98.3-99.8% with %RSD ranged from 0.48 to 0.52%. The limit of quantification (LOQ) and limit of detection (LOD) for each enantiomer were 100 and 25microg/ml, respectively. No interferences were found from commonly co-formulated excipients.

On the effect of basic and acidic additives on the separation of the enantiomers of some basic drugs with polysaccharide-based chiral selectors and polar organic mobile phases.

PubMed

Mosiashvili, L; Chankvetadze, L; Farkas, T; Chankvetadze, B

2013-11-22

This article reports the systematic study of the effect of basic and acidic additives on HPLC separation of enantiomers of some basic chiral drugs on polysaccharide-based chiral columns under polar organic mobile-phase conditions. In contrary to generally accepted opinion that the basic additives improve the separation of enantiomers of basic compounds, the multiple scenarios were observed including the increase, decrease, disappearance and appearance of separation, as well as the reversal of the enantiomer elution order of studied basic compounds induced by the acidic additives. These effects were observed on most of the studied 6 chiral columns in 2-propanol and acetonitrile as mobile phases and diethylamine as a basic additive. As acidic additives formic acid was used systematically and acetic acid and trifluoroacetic acid were applied for comparative purposes. This study illustrates that the minor acidic additives to the mobile phase can be used as for the adjustment of separation selectivity and the enantiomer elution order of basic compounds, as well as for study of chiral recognition mechanisms with polysaccharide-based chiral stationary phases. Copyright © 2013 Elsevier B.V. All rights reserved.

Evaluation of translucency of monolithic zirconia and framework zirconia materials

PubMed Central

Tuncel, İlkin; Üşümez, Aslıhan

2016-01-01

PURPOSE The opacity of zirconia is an esthetic disadvantage that hinders achieving natural and shade-matched restorations. The aim of this study was to evaluate the translucency of non-colored and colored framework zirconia and monolithic zirconia. MATERIALS AND METHODS The three groups tested were: non-colored framework zirconia, colored framework zirconia with the A3 shade according to Vita Classic Scale, and monolithic zirconia (n=5). The specimens were fabricated in the dimensions of 15×12×0.5 mm. A spectrophotometer was used to measure the contrast ratio, which is indicative of translucency. Three measurements were made to obtain the contrast ratios of the materials over a white background (L*w) and a black background (L*b). The data were analyzed using the one-way analysis of variance and Tukey HSD tests. One specimen from each group was chosen for scanning electron microscope analysis. The determined areas of the SEM images were divided by the number of grains in order to calculate the mean grain size. RESULTS Statistically significant differences were observed among all groups (P<.05). Non-colored zirconia had the highest translucency with a contrast ratio of 0.75, while monolithic zirconia had the lowest translucency with a contrast ratio of 0.8. The mean grain sizes of the non-colored, colored, and monolithic zirconia were 233, 256, and 361 nm, respectively. CONCLUSION The translucency of the zirconia was affected by the coloring procedure and the grain size. Although monolithic zirconia may not be the best esthetic material for the anterior region, it may serve as an alternative in the posterior region for the bilayered zirconia restorations. PMID:27350851

Influence of different resin cements and surface treatments on microshear bond strength of zirconia-based ceramics

PubMed Central

Petrauskas, Anderson; Novaes Olivieri, Karina Andrea; Pupo, Yasmine Mendes; Berger, Guilherme; Gonçalves Betiol, Ederson Áureo

2018-01-01

Aim: This study aims to evaluate the microshear bond strength of zirconia-based ceramics with different resin cement systems and surface treatments. Materials and Methods: Forty blocks of zirconia-based ceramic were prepared and embedded in polyvinyl chloride (PVC) tubes with acrylic resin. After polishing, the samples were washed in an ultrasonic bath and dried in an oven for 10 min. Half of the samples were subjected to sandblasting with aluminum oxide. Blocks were divided into four groups (n = 10) in which two resin cements were used as follows: (1) RelyX™ U100 with surface-polished zirconia; (2) RelyX™ U100 with surface-blasted zirconia; (3) Multilink with surface-polished zirconia; and 4) Multilink with surface-blasted zirconia. After performing these surface treatments, translucent tubes (n = 30 per group) were placed on the zirconia specimens, and resin cement was injected into them and light cured. The PVC tubes were adapted in a universal testing machine; a stiletto blade, which was bolted to the machine, was positioned on the cementation interface. The microshear test was performed at a speed of 0.5 mm/min. Failure mode was analyzed in an optical microscope and classified as adhesive, cohesive, or mixed. Results: The null hypothesis of this study was rejected because there was a difference found between the resin cement and the surface treatment. There was a statistical difference (P < 0.005) in RelyX™ U100 with surface-blasted zirconia, in relation to the other three groups. For Multilink groups, there was no statistical difference between them. Conclusion: Self-adhesive resin cement showed a more significant tendency toward bond strength in the ceramic-based zirconium oxide grit-blasted surfaces. PMID:29674825

Column temperature programming in enantioseparation of dihydropyrimidinone compounds using derivatized cellulose and amylose chiral stationary phases.

PubMed

Wang, Fang; Yeung, David; Han, Jun; Semin, David; McElvain, James S; Cheetham, Janet

2008-03-01

We report the application of column temperature programs as a tool to examine unusual temperature-induced behaviors of polysaccharide chiral stationary phases (CSPs). Using dihydropyrimidinone (DHP) compounds as probes we observed the heating (10-50 degrees C) and cooling (50-10 degrees C) van't Hoff plots of retention factors and/or selectivities of DHP compounds were not superimposable on AD, IA, and AS-H columns solvated with ethanol (EtOH)/n-hexane (n-Hex) mobile phases. The plots were not superimposable on AD, IB, and AS-H columns solvated with 2-propanol (2-PrOH)/n-Hex mobile phases. The thermally induced path-dependant behaviors were caused by slow equilibration as evidenced by the disappearance of the hysteresis in the second heating to cooling cycle and in a cooling to heating cycle. From the step-temperature program (10-50-10 degrees C), only EtOH solvated AD and AS-H phases showed the change of retention factors and/or selectivities with time while only 2-PrOH solvated AS-H phase showed similar behaviors.

Chiral Gold Nanoclusters: Atomic Level Origins of Chirality.

PubMed

Zeng, Chenjie; Jin, Rongchao

2017-08-04

Chiral nanomaterials have received wide interest in many areas, but the exact origin of chirality at the atomic level remains elusive in many cases. With recent significant progress in atomically precise gold nanoclusters (e.g., thiolate-protected Au n (SR) m ), several origins of chirality have been unveiled based upon atomic structures determined by using single-crystal X-ray crystallography. The reported chiral Au n (SR) m structures explicitly reveal a predominant origin of chirality that arises from the Au-S chiral patterns at the metal-ligand interface, as opposed to the chiral arrangement of metal atoms in the inner core (i.e. kernel). In addition, chirality can also be introduced by a chiral ligand, manifested in the circular dichroism response from metal-based electronic transitions other than the ligand's own transition(s). Lastly, the chiral arrangement of carbon tails of the ligands has also been discovered in a very recent work on chiral Au 133 (SR) 52 and Au 246 (SR) 80 nanoclusters. Overall, the origins of chirality discovered in Au n (SR) m nanoclusters may provide models for the understanding of chirality origins in other types of nanomaterials and also constitute the basis for the development of various applications of chiral nanoparticles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of framework design and layering material on fracture strength of implant-supported zirconia-based molar crowns.

PubMed

Kamio, Shingo; Komine, Futoshi; Taguchi, Kohei; Iwasaki, Taro; Blatz, Markus B; Matsumura, Hideo

2015-12-01

To evaluate the effects of framework design and layering material on the fracture strength of implant-supported zirconia-based molar crowns. Sixty-six titanium abutments (GingiHue Post) were tightened onto dental implants (Implant Lab Analog). These abutment-implant complexes were randomly divided into three groups (n = 22) according to the design of the zirconia framework (Katana), namely, uniform-thickness (UNI), anatomic (ANA), and supported anatomic (SUP) designs. The specimens in each design group were further divided into two subgroups (n = 11): zirconia-based all-ceramic restorations (ZAC group) and zirconia-based restorations with an indirect composite material (Estenia C&B) layered onto the zirconia framework (ZIC group). All crowns were cemented on implant abutments, after which the specimens were tested for fracture resistance. The data were analyzed with the Kruskal-Wallis test and the Mann-Whitney U-test with the Bonferroni correction (α = 0.05). The following mean fracture strength values (kN) were obtained in UNI design, ANA design, and SUP design, respectively: Group ZAC, 3.78, 6.01, 6.50 and Group ZIC, 3.15, 5.65, 5.83. In both the ZAC and ZIC groups, fracture strength was significantly lower for the UNI design than the other two framework designs (P = 0.001). Fracture strength did not significantly differ (P > 0.420) between identical framework designs in the ZAC and ZIC groups. A framework design with standardized layer thickness and adequate support of veneer by zirconia frameworks, as in the ANA and SUP designs, increases fracture resistance in implant-supported zirconia-based restorations under conditions of chewing attrition. Indirect composite material and porcelain perform similarly as layering materials on zirconia frameworks. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Zirconia coated carbonyl iron particle-based magnetorheological fluid for polishing

NASA Astrophysics Data System (ADS)

Shafrir, Shai N.; Romanofsky, Henry J.; Skarlinski, Michael; Wang, Mimi; Miao, Chunlin; Salzman, Sivan; Chartier, Taylor; Mici, Joni; Lambropoulos, John C.; Shen, Rui; Yang, Hong; Jacobs, Stephen D.

2009-08-01

Aqueous magnetorheological (MR) polishing fluids used in magnetorheological finishing (MRF) have a high solids concentration consisting of magnetic carbonyl iron particles and nonmagnetic polishing abrasives. The properties of MR polishing fluids are affected over time by corrosion of CI particles. Here we report on MRF spotting experiments performed on optical glasses using a zirconia coated carbonyl iron (CI) particle-based MR fluid. The zirconia coated magnetic CI particles were prepared via sol-gel synthesis in kg quantities. The coating layer was ~50-100 nm thick, faceted in surface structure, and well adhered. Coated particles showed long term stability against aqueous corrosion. "Free" nano-crystalline zirconia polishing abrasives were co-generated in the coating process, resulting in an abrasivecharged powder for MRF. A viable MR fluid was prepared simply by adding water. Spot polishing tests were performed on a variety of optical glasses over a period of 3 weeks with no signs of MR fluid degradation or corrosion. Stable material removal rates and smooth surfaces inside spots were obtained.

Effect of Secondary Equilibria on the Adsorption of Ibuprofen Enantiomers on a Chiral Stationary Phase with a Grafted Antibiotic Eremomycin

NASA Astrophysics Data System (ADS)

Reshetova, E. N.; Asnin, L. D.; Kachmarsky, K.

2018-02-01

The chromatographic separation of ibuprofen enantiomers on a Nautilus-E chiral stationary phase with a grafted eremomycin antibiotic at high column loading is accompanied by distortion of the shape of chromatographic peaks. A model is proposed to explain this phenomenon. A number of factors are considered in the model: the ionization of ibuprofen in the mobile phase, the pH change in the mass transfer zone caused by ionization, and competitive adsorption involving buffer components. Simulations performed using this model within the theory of nonequilibrium chromatography allow the shape of chromatograms for large amounts of S- and R-ibuprofen samples to be predicted. The adsorption mechanism is found to be mainly ion-exchange. The contribution from the molecular adsorption of ibuprofen to the total retention is shown to be several percent.

Features of the adsoprtion of naproxen on the chiral stationary phase (S,S)-Whelk-O1 under reversed-phase conditions

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

Asnin, Leonid; Gritti, Fabrice; Kaczmarski, Krzysztof

Using elution chromatography, we studied the adsorption mechanism of the Naproxen enantiomers on the chiral stationary phase (S,S)-Whelk-O1, from buffered methanol-water solutions. We propose an adsorption mechanism that assumes monolayer adsorption of the more retained enantiomer and the associative adsorption of the less retained one. The effects of the mobile phase composition on the adsorption of Naproxen are discussed. The combination of an elevated column temperature and of the use of an acidic mobile phase led to the degradation of the column and caused a major loss of its separation ability. The use of a moderately acidic mobile phase atmore » temperature slightly above ambient did not produce rapid severe damages but, nevertheless, hampered the experiments and caused a slow gradual deterioration of the column.« less

Using glass-graded zirconia to increase delamination growth resistance in porcelain/zirconia dental structures.

PubMed

Chai, Herzl; Mieleszko, Adam J; Chu, Stephen J; Zhang, Yu

2018-01-01

Porcelain fused to zirconia (PFZ) restorations are widely used in prosthetic dentistry. However, their tendency to delaminate along the P/Z interface remains a practical problem so that assessing and improving the interfacial strength are important design aspects. This work examines the effect of modifying the zirconia veneering surface with an in-house felspathic glass on the interfacial fracture resistance of fused P/Z. Three material systems are studied: porcelain fused to zirconia (control) and porcelain fused to glass-graded zirconia with and without the presence of a glass interlayer. The specimens were loaded in a four-point-bend fixture with the porcelain veneer in tension. The evolution of damage is followed with the aid of a video camera. The interfacial fracture energy G C was determined with the aid of a FEA, taking into account the stress shielding effects due to the presence of adjacent channel cracks. Similarly to a previous study on PFZ specimens, the fracture sequence consisted of unstable growth of channel cracks in the veneer followed by stable cracking along the P/Z interface. However, the value of GC for the graded zirconia was approximately 3 times that of the control zirconia, which is due to the good adhesion between porcelain and the glass network structure on the zirconia surface. Combined with its improved bonding to resin-based cements, increased resistance to surface damage and good esthetic quality, graded zirconia emerges as a viable material concept for dental restorations. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Intelligent chiral sensing based on supramolecular and interfacial concepts.

PubMed

Ariga, Katsuhiko; Richards, Gary J; Ishihara, Shinsuke; Izawa, Hironori; Hill, Jonathan P

2010-01-01

Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized.

Chiral HPLC for a study of the optical purity of new liquid crystalline materials derived from lactic acid

NASA Astrophysics Data System (ADS)

Vojtylová, T.; Kašpar, M.; Hamplová, V.; Novotná, V.; Sýkora, D.

2014-08-01

New liquid crystalline (LC) materials were prepared by derivatization of lactic acid. First compound possesses the lactic acid unit as the only chiral center and the second group of LC materials contains two chiral centers. Mesomorphic properties of both the newly synthesized LC materials were studied and the presence of the SmA*-SmC* or exhibit the twist grain boundary (TGB) phases, namely TGBA and TGBC, in a wide range of temperatures down to the room temperature was established. The potential of high-performance liquid chromatography (HPLC) applying chiral stationary phases to separate enantiomers or diastereoisomers of the synthesized LC compounds was evaluated. Two different brands of commercial chiral sorbents, Lux Amylose-2 and Chiralpak AD-3, both based on modified silica with derivatized polysaccharide, were employed in the development of separation procedures. The optimized chiral HPLC method provided a baseline separation of the individual enantiomers for the LC material containing one chiral center. In the case of the more complex compound with two asymmetric carbon atoms, where four isomers exist, partial separation was reached only using the current chiral HPLC.

Fracture resistance of implant- supported monolithic crowns cemented to zirconia hybrid-abutments: zirconia-based crowns vs. lithium disilicate crowns

PubMed Central

Nawafleh, Noor; Öchsner, Andreas; George, Roy

2018-01-01

PURPOSE The aim of this in vitro study was to investigate the fracture resistance under chewing simulation of implant-supported posterior restorations (crowns cemented to hybrid-abutments) made of different all-ceramic materials. MATERIALS AND METHODS Monolithic zirconia (MZr) and monolithic lithium disilicate (MLD) crowns for mandibular first molar were fabricated using computer-aided design/computer-aided manufacturing technology and then cemented to zirconia hybrid-abutments (Ti-based). Each group was divided into two subgroups (n=10): (A) control group, crowns were subjected to single load to fracture; (B) test group, crowns underwent chewing simulation using multiple loads for 1.2 million cycles at 1.2 Hz with simultaneous thermocycling between 5℃ and 55℃. Data was statistically analyzed with one-way ANOVA and a Post-Hoc test. RESULTS All tested crowns survived chewing simulation resulting in 100% survival rate. However, wear facets were observed on all the crowns at the occlusal contact point. Fracture load of monolithic lithium disilicate crowns was statistically significantly lower than that of monolithic zirconia crowns. Also, fracture load was significantly reduced in both of the all-ceramic materials after exposure to chewing simulation and thermocycling. Crowns of all test groups exhibited cohesive fracture within the monolithic crown structure only, and no abutment fractures or screw loosening were observed. CONCLUSION When supported by implants, monolithic zirconia restorations cemented to hybrid abutments withstand masticatory forces. Also, fatigue loading accompanied by simultaneous thermocycling significantly reduces the strength of both of the all-ceramic materials. Moreover, further research is needed to define potentials, limits, and long-term serviceability of the materials and hybrid abutments. PMID:29503716

Phase Stabilization of Zirconia.

DTIC Science & Technology

1997-01-30

preparing stabilized zirconia pursuant to this disclosure, an insoluble alumina powder is mixed with zirconia powder using a liquid dispersant, such...in a drying oven or a furnace. When mixing the alumina and zirconia powders , it is not necessary to have zirconia in any particular phase to achieve...phase stabilization, as disclosed herein. When mixed with alumina powder, zirconia powder can be in cubic, tetragonal or 20 monoclinic phases

Stationary phase deposition based on onium salts

DOEpatents

Wheeler, David R [Albuquerque, NM; Lewis, Patrick R [Albuquerque, NM; Dirk, Shawn M [Albuquerque, NM; Trudell, Daniel E [Albuquerque, NM

2008-01-01

Onium salt chemistry can be used to deposit very uniform thickness stationary phases on the wall of a gas chromatography column. In particular, the stationary phase can be bonded to non-silicon based columns, especially microfabricated metal columns. Non-silicon microfabricated columns may be manufactured and processed at a fraction of the cost of silicon-based columns. In addition, the method can be used to phase-coat conventional capillary columns or silicon-based microfabricated columns.

Metal-Ion-Mediated Supramolecular Chirality of l-Phenylalanine Based Hydrogels.

PubMed

Wang, Fang; Feng, Chuan-Liang

2018-05-14

For chiral hydrogels and related applications, one of the critical issues is how to control the chirality of supramolecular systems in an efficient way, including easy operation, efficient transfer of chirality, and so on. Herein, supramolecular chirality of l-phenylalanine based hydrogels can be effectively controlled by using a broad range of metal ions. The degree of twisting (twist pitch) and the diameter of the chiral nanostructures can also be efficiently regulated. These are ascribed to the synergic effect of hydrogen bonding and metal ion coordination. This study may develop a method to design a new class of electronically, optically, and biologically active materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Five-year prospective clinical study of posterior three-unit zirconia-based fixed dental prostheses.

PubMed

Sorrentino, Roberto; De Simone, Giorgio; Tetè, Stefano; Russo, Simona; Zarone, Fernando

2012-06-01

This prospective clinical trial aimed at evaluating the clinical performance of three-unit posterior zirconia fixed dental prostheses (FDPs) after 5 years of clinical function. Thirty-seven patients received 48 three-unit zirconia-based FDPs. The restorations replaced either a premolar or a molar. Specific inclusion criteria were needed. Tooth preparation was standardized. Computer-aided design/computer-assisted manufacturing frameworks with a 9-mm(2) cross section of the connector and a 0.6-mm minimum thickness of the retainer were made. The restorations were luted with resin cement. The patients were recalled after 1, 6, 12, 24, 36, 48, and 60 months. The survival and success of the ceramics and zirconia were evaluated. The technical and aesthetic outcomes were examined using the United States Public Health Service criteria. The biologic outcomes were analyzed at abutment and contralateral teeth. Descriptive statistics were performed. All FDPs completed the study, resulting in 100% cumulative survival rate and 91.9% and 95.4% cumulative success rates for patients wearing one and two FDPs, respectively. No losses of retention were recorded. Forty-two restorations were rated alpha in all measured parameters. A minor chipping of the ceramics was detected in three restorations. No significant differences between the periodontal parameters of the test and control teeth were observed. Five-year clinical results proved that three-unit posterior zirconia-based FDPs were successful in the medium term for both function and aesthetic. Zirconia can be considered a promising substitute of metal frameworks for the fabrication of short-span posterior prostheses.

Effects of silane- and MDP-based primers application orders on zirconia-resin adhesion-A ToF-SIMS study.

PubMed

Chuang, Shu-Fen; Kang, Li-Li; Liu, Yi-Chuan; Lin, Jui-Che; Wang, Ching-Cheng; Chen, Hui-Min; Tai, Cheng-Kun

2017-08-01

To evaluate the 3-methacryloyloxypropyltrimethoxysilane (MPS)- and 10-methacryloyloxydecyl-dihydrogen-phosphate (MDP)-base primers, in their single or sequential applications, with regard to modifying zirconia surfaces and improving resin-zirconia adhesion. Zirconia disks received different treatments: without primer (Zr), MPS-base primer (S), MDP-base primer (M), MPS/MDP mixture (SMmix), MPS followed by MDP (SM), and MDP followed by MPS (MS). The compositions and chemical interactions of the coatings to zirconia were analyzed using time-of-flight secondary ion mass spectrometry (ToF-SIMS) and reconstructed 3D ion images. Surface wettability of these coatings to water and resin adhesive was assessed. The shear bond strength (SBS) between resin and the treated zirconia was also examined before and after thermocycling. Groups S and MS presented substantial OH - ions in the coatings and zirconia substrate. PO 2 - and PO 3 - fragments existed in all MDP-treatment groups with various proportions and distributions, while groups M and SM showed higher proportions of PO 3 - and the zirconium phosphate related ions. In 3D ion images, PO 3 - in groups M and SM was denser and segregated to the interface, but was dispersed or overlaid above PO 2 - in SMmix and MS. All the primers increased the surface wettability to water and resin, with M and SM presenting superhydrophilic surfaces. All MDP-treatment groups showed improved SBS before thermocycling, while M and SM retained higher SBS after this. The MDP-base primer shows a relevant function in facilitating POZr bonding and enhancing resin-zirconia bonding. The co-treated MPS impairs the chemical activity of MDP, especially if it is the final coat. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Spontaneous chiral symmetry breaking in metamaterials

NASA Astrophysics Data System (ADS)

Liu, Mingkai; Powell, David A.; Shadrivov, Ilya V.; Lapine, Mikhail; Kivshar, Yuri S.

2014-07-01

Spontaneous chiral symmetry breaking underpins a variety of areas such as subatomic physics and biochemistry, and leads to an impressive range of fundamental phenomena. Here we show that this prominent effect is now available in artificial electromagnetic systems, enabled by the advent of magnetoelastic metamaterials where a mechanical degree of freedom leads to a rich variety of strong nonlinear effects such as bistability and self-oscillations. We report spontaneous symmetry breaking in torsional chiral magnetoelastic structures where two or more meta-molecules with opposite handedness are electromagnetically coupled, modifying the system stability. Importantly, we show that chiral symmetry breaking can be found in the stationary response of the system, and the effect is successfully demonstrated in a microwave pump-probe experiment. Such symmetry breaking can lead to a giant nonlinear polarization change, energy localization and mode splitting, which provides a new possibility for creating an artificial phase transition in metamaterials, analogous to that in ferrimagnetic domains.

Spontaneous chiral symmetry breaking in metamaterials.

PubMed

Liu, Mingkai; Powell, David A; Shadrivov, Ilya V; Lapine, Mikhail; Kivshar, Yuri S

2014-07-18

Spontaneous chiral symmetry breaking underpins a variety of areas such as subatomic physics and biochemistry, and leads to an impressive range of fundamental phenomena. Here we show that this prominent effect is now available in artificial electromagnetic systems, enabled by the advent of magnetoelastic metamaterials where a mechanical degree of freedom leads to a rich variety of strong nonlinear effects such as bistability and self-oscillations. We report spontaneous symmetry breaking in torsional chiral magnetoelastic structures where two or more meta-molecules with opposite handedness are electromagnetically coupled, modifying the system stability. Importantly, we show that chiral symmetry breaking can be found in the stationary response of the system, and the effect is successfully demonstrated in a microwave pump-probe experiment. Such symmetry breaking can lead to a giant nonlinear polarization change, energy localization and mode splitting, which provides a new possibility for creating an artificial phase transition in metamaterials, analogous to that in ferrimagnetic domains.

A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands.

PubMed

Chen, Weiping; Mbafor, William; Roberts, Stanley M; Whittall, John

2006-03-29

A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands has been developed. On the basis of this new methodology, several new families of ferrocene-based phosphine ligands have been prepared coupling chirality at phosphorus with other, more standard stereogenic features. The introduction of P-chirality into ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding Rh catalyst when a matching among the planar chirality, carbon chirality, and the chirality of phosphorus is achieved.

Innovations in bonding to zirconia-based materials. Part II: Focusing on chemical interactions.

PubMed

Aboushelib, Moustafa N; Mirmohamadi, Hesam; Matinlinna, Jukka P; Kukk, Edwin; Ounsi, Hani F; Salameh, Ziad

2009-08-01

The zirconia-resin bond strength was enhanced using novel engineered zirconia primers in combination with selective infiltration etching as a surface pre-treatment. The aim of this study was to evaluate the effect of artificial aging on the chemical stability of the established bond and to understand the activation mechanism of the used primers. Selective infiltration etched zirconia discs (Procera; NobelBiocare) were coated with one of four novel engineered zirconia primers containing reactive monomers and were bonded to resin-composite discs (Panavia F2.0). Fourier transform infrared spectroscopy (FT-IR) was carried out to examine the chemical activation of zirconia primers from mixing time and up to 60min. The bilayered specimens were cut into microbars (1mm(2) in cross-section area) and zirconia-resin microtensile bond strength (MTBS) was evaluated immediately and after 90 days of water storage at 37 degrees C. Scanning electron microscopy (SEM) was used to analyze the fracture surface. There was a significant drop in MTBS values after 90 days of water storage for all tested zirconia primers from ca. 28-41MPa to ca. 15-18MPa after completion of artificial aging. SEM revealed increase in percentage of interfacial failure after water storage. FTIR spectra suggested adequate activation of the experimental zirconia primers within 1h of mixing time. The novel engineered zirconia primers produced initially high bond strength values which were significantly reduced after water storage. Long-term bond stability requires developing more stable primers.

Tailoring the chirality of light emission with spherical Si-based antennas.

PubMed

Zambrana-Puyalto, Xavier; Bonod, Nicolas

2016-05-21

Chirality of light is of fundamental importance in several enabling technologies with growing applications in life sciences, chemistry and photodetection. Recently, some attention has been focused on chiral quantum emitters. Consequently, optical antennas which are able to tailor the chirality of light emission are needed. Spherical nanoresonators such as colloids are of particular interest to design optical antennas since they can be synthesized at a large scale and they exhibit good optical properties. Here, we show that these colloids can be used to tailor the chirality of a chiral emitter. To this purpose, we derive an analytic formalism to model the interaction between a chiral emitter and a spherical resonator. We then compare the performances of metallic and dielectric spherical antennas to tailor the chirality of light emission. It is seen that, due to their strong electric dipolar response, metallic spherical nanoparticles spoil the chirality of light emission by yielding achiral fields. In contrast, thanks to the combined excitation of electric and magnetic modes, dielectric Si-based particles feature the ability to inhibit or to boost the chirality of light emission. Finally, it is shown that dual modes in dielectric antennas preserve the chirality of light emission.

Two-body wear comparison of zirconia crown, gold crown, and enamel against zirconia.

PubMed

Kwon, Min-Seok; Oh, Sang-Yeob; Cho, Sung-Am

2015-07-01

Full zirconia crowns have recently been used for dental restorations because of their mechanical properties. However, there is little information about their wear characteristics against enamel, gold, and full zirconia crowns. The purpose of this study was to compare the wear rate of enamel, gold crowns, and zirconia crowns against zirconia blocks using an in vitro wear test. Upper specimens were divided into three groups: 10 enamels (group 1), 10 gold crowns (group 2, Type III gold), and 10 zirconia crowns (group 3, Prettau(®)Zirkon 9H, Zirkonzahn, Italy). Each of these specimens was wear tested against a zirconia block (40×30×3mm(3)) as a lower specimen (30 total zirconia blocks). Each specimen of the groups was abraded against the zirconia block for 600 cycles at 1Hz with 15mm front-to-back movement on an abrading machine. Moreover, the load applied during the abrading test was 50N, and the test was performed in a normal saline emulsion for 10min. Three-dimensional images were taken before and after the test, and the statistical analysis was performed using the Krushal-Wallis test and Mann-Whitney test (p=0.05). The mean volume loss of group 1 was 0.47mm(3), while that of group 2 and group 3 was 0.01mm(3). The wear volume loss of enamels against zirconia was higher than that of gold and zirconia crowns. Moreover, according to this result, zirconia crowns are not recommended for heavy bruxers. Copyright © 2015 Elsevier Ltd. All rights reserved.

Zirconia-coated carbonyl-iron-particle-based magnetorheological fluid for polishing optical glasses and ceramics.

PubMed

Shafrir, Shai N; Romanofsky, Henry J; Skarlinski, Michael; Wang, Mimi; Miao, Chunlin; Salzman, Sivan; Chartier, Taylor; Mici, Joni; Lambropoulos, John C; Shen, Rui; Yang, Hong; Jacobs, Stephen D

2009-12-10

We report on magnetorheological finishing (MRF) spotting experiments performed on glasses and ceramics using a zirconia-coated carbonyl-iron (CI)-particle-based magnetorheological (MR) fluid. The zirconia-coated magnetic CI particles were prepared via sol-gel synthesis in kilogram quantities. The coating layer was approximately 50-100 nm thick, faceted in surface structure, and well adhered. Coated particles showed long-term stability against aqueous corrosion. "Free" nanocrystalline zirconia polishing abrasives were cogenerated in the coating process, resulting in an abrasive-charged powder for MRF. A viable MR fluid was prepared simply by adding water. Spot polishing tests were performed on a variety of optical glasses and ceramics over a period of nearly three weeks with no signs of MR fluid degradation or corrosion. Stable material removal rates and smooth surfaces inside spots were obtained.

Free-Standing Optically Switchable Chiral Plasmonic Photonic Crystal Based on Self-Assembled Cellulose Nanorods and Gold Nanoparticles.

PubMed

Chu, Guang; Wang, Xuesi; Yin, Hang; Shi, Ying; Jiang, Haijing; Chen, Tianrui; Gao, Jianxiong; Qu, Dan; Xu, Yan; Ding, Dajun

2015-10-07

Photonic crystals incorporating with plasmonic nanoparticles have recently attracted considerable attention due to their novel optical properties and potential applications in future subwavelength optics, biosensing and data storage device. Here we demonstrate a free-standing chiral plasmonic film composed of entropy-driven self-co-assembly of gold nanoparticles (GNPs) and rod-like cellulose nanocrystals (CNCs). The CNCs-GNPs composite films not only preserve the photonic ordering of the CNCs matrix but also retain the plasmonic resonance of GNPs, leading to a distinct plasmon-induced chiroptical activity and a strong resonant plasmonic-photonic coupling that is confirmed by the stationary and ultrafast transient optical response. Switchable optical activity can be obtained by either varying the incidence angle of lights, or by taking advantage of the responsive feature of the CNCs matrix. Notably, an angle-dependent plasmon resonance in chiral nematic hybrid film has been observed for the first time, which differs drastically from that of the GNPs embed in three-dimensional photonic crystals, revealing a close relation with the structure of the host matrix. The current approach for fabricating device-scale, macroscopic chiral plasmonic materials from abundant CNCs with robust chiral nematic matrix may enable the mass production of functional optical metamaterials.

Enantiomeric separation of type I and type II pyrethroid insecticides with different chiral stationary phases by reversed-phase high-performance liquid chromatography.

PubMed

Zhang, Ping; Yu, Qian; He, Xiulong; Qian, Kun; Xiao, Wei; Xu, Zhifeng; Li, Tian; He, Lin

2018-04-01

The enantiomeric separation of type I (bifenthrin, BF) and type II (lambda-cyhalothrin, LCT) pyrethroid insecticides on Lux Cellulose-1, Lux Cellulose-3, and Chiralpak IC chiral columns was investigated by reversed-phase high-performance liquid chromatography. Methanol/water or acetonitrile/water was used as mobile phase at a flow rate of 0.8 mL/min. The effects of chiral stationary phase, mobile phase composition, column temperature, and thermodynamic parameters on enantiomer separation were carefully studied. Bifenthrin got a partial separation on Lux Cellulose-1 column and baseline separation on Lux Cellulose-3 column, while LCT enantiomers could be completely separated on both Lux Cellulose-1 and Lux Cellulose-3 columns. Chiralpak IC provided no separation ability for both BF and LCT. Retention factor (k) and selectivity factor (α) decreased with the column temperature increasing from 10°C to 40°C for both BF and LCT enantiomers. Thermodynamic parameters including ∆H and ∆S were also calculated, and the maximum R s were not always obtained at lowest temperature. Furthermore, the quantitative analysis methods for BF and LCT enantiomers in soil and water were also established. Such results provide a new approach for pyrethroid separation under reversed-phase condition and contribute to environmental risk assessment of pyrethroids at enantiomer level. © 2017 Wiley Periodicals, Inc.

High enantioselective Novozym 435-catalyzed esterification of (R,S)-flurbiprofen monitored with a chiral stationary phase.

PubMed

Siódmiak, Tomasz; Mangelings, Debby; Vander Heyden, Yvan; Ziegler-Borowska, Marta; Marszałł, Michał Piotr

2015-03-01

Lipases form Candida rugosa and Candida antarctica were tested for their application in the enzymatic kinetic resolution of (R,S)-flurbiprofen by enantioselective esterification. Successful chromatographic separation with well-resolved peaks of (R)- and (S)-flurbiprofen and their esters was achieved in one run on chiral stationary phases by high-performance liquid chromatography (HPLC). In this study screening of enzymes was performed, and Novozym 435 was selected as an optimal catalyst for obtaining products with high enantiopurity. Additionally, the influence of organic solvents (dichloromethane, dichloroethane, dichloropropane, and methyl tert-butyl ether), primary alcohols (methanol, ethanol, n-propanol, and n-butanol), reaction time, and temperature on the enantiomeric ratio and conversion was tested. The high values of enantiomeric ratio (E in the range of 51.3-90.5) of the esterification of (R,S)-flurbiprofen were obtained for all tested alcohols using Novozym 435, which have a great significance in the field of biotechnological synthesis of drugs. The optimal temperature range for the performed reactions was from 37 to 45 °C. As a result of the optimization, (R)-flurbiprofen methyl ester was obtained with a high optical purity, eep = 96.3 %, after 96 h of incubation. The enantiomeric ratio of the reaction was E = 90.5 and conversion was C = 35.7 %.

Nanosilica coating for bonding improvements to zirconia.

PubMed

Chen, Chen; Chen, Gang; Xie, Haifeng; Dai, Wenyong; Zhang, Feimin

2013-01-01

Resin bonding to zirconia cannot be established from standard methods that are currently utilized in conventional silica-based dental ceramics. The solution-gelatin (sol-gel) process is a well developed silica-coating technique used to modify the surface of nonsilica-based ceramics. Here, we use this technique to improve resin bonding to zirconia, which we compared to zirconia surfaces treated with alumina sandblasting and tribochemical silica coating. We used the shear bond strength test to examine the effect of the various coatings on the short-term resin bonding of zirconia. Furthermore, we employed field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic force microscopy, and Fourier transform infrared spectroscopy to characterize the zirconia surfaces. Water-mist spraying was used to evaluate the durability of the coatings. To evaluate the biological safety of the experimental sol-gel silica coating, we conducted an in vitro Salmonella typhimurium reverse mutation assay (Ames mutagenicity test), cytotoxicity tests, and in vivo oral mucous membrane irritation tests. When compared to the conventional tribochemical silica coating, the experimental sol-gel silica coating provided the same shear bond strength, higher silicon contents, and better durability. Moreover, we observed no apparent mutagenicity, cytotoxicity, or irritation in this study. Therefore, the sol-gel technique represents a promising method for producing silica coatings on zirconia.

Nanosilica coating for bonding improvements to zirconia

PubMed Central

Chen, Chen; Chen, Gang; Xie, Haifeng; Dai, Wenyong; Zhang, Feimin

2013-01-01

Resin bonding to zirconia cannot be established from standard methods that are currently utilized in conventional silica-based dental ceramics. The solution–gelatin (sol–gel) process is a well developed silica-coating technique used to modify the surface of nonsilica-based ceramics. Here, we use this technique to improve resin bonding to zirconia, which we compared to zirconia surfaces treated with alumina sandblasting and tribochemical silica coating. We used the shear bond strength test to examine the effect of the various coatings on the short-term resin bonding of zirconia. Furthermore, we employed field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, atomic force microscopy, and Fourier transform infrared spectroscopy to characterize the zirconia surfaces. Water–mist spraying was used to evaluate the durability of the coatings. To evaluate the biological safety of the experimental sol–gel silica coating, we conducted an in vitro Salmonella typhimurium reverse mutation assay (Ames mutagenicity test), cytotoxicity tests, and in vivo oral mucous membrane irritation tests. When compared to the conventional tribochemical silica coating, the experimental sol–gel silica coating provided the same shear bond strength, higher silicon contents, and better durability. Moreover, we observed no apparent mutagenicity, cytotoxicity, or irritation in this study. Therefore, the sol–gel technique represents a promising method for producing silica coatings on zirconia. PMID:24179333

Metallocorroles as inherently chiral chromophores: resolution and electronic circular dichroism spectroscopy of a tungsten biscorrole.

PubMed

Schies, Christine; Alemayehu, Abraham B; Vazquez-Lima, Hugo; Thomas, Kolle E; Bruhn, Torsten; Bringmann, Gerhard; Ghosh, Abhik

2017-06-01

An inherently chiral metallocorrole has been resolved for the first time by means of HPLC on a chiral stationary phase. For the compound in question, a homoleptic tungsten biscorrole, the absolute configurations of the enantiomers were assigned using online HPLC-ECD measurements in conjunction with time-dependent CAM-B3LYP calculations, which provided accurate simulations of the ECD spectra.

A chiroptical switch based on supramolecular chirality transfer through alkyl chain entanglement and dynamic covalent bonding.

PubMed

Lv, Kai; Qin, Long; Wang, Xiufeng; Zhang, Li; Liu, Minghua

2013-12-14

Chirality transfer is an interesting phenomenon in Nature, which represents an important step to understand the evolution of chiral bias and the amplification of the chirality. In this paper, we report the chirality transfer via the entanglement of the alkyl chains between chiral gelator molecules and achiral amphiphilic Schiff base. We have found that although an achiral Schiff base amphiphile could not form organogels in any kind of organic solvents, it formed co-organogels when mixed with a chiral gelator molecule. Interestingly, the chirality of the gelator molecules was transferred to the Schiff base chromophore in the mixed co-gels and there was a maximum mixing ratio for the chirality transfer. Furthermore, the supramolecular chirality was also produced based on a dynamic covalent chemistry of an imine formed by the reaction between an aldehyde and an amine. Such a covalent bond of imine was formed reversibly depending on the pH variation. When the covalent bond was formed the chirality transfer occurred, when it was destroyed, the transfer stopped. Thus, a supramolecular chiroptical switch is obtained based on supramolecular chirality transfer and dynamic covalent chemistry.

Chiral Recognition with Macrocyclic Glycopeptides: Mechanisms and Applications

NASA Astrophysics Data System (ADS)

Berthod, Alain; Qiu, Hai Xiao; Staroverov, Sergey M.; Kuznestov, Mikhail A.; Armstrong, Daniel W.

The macrocyclic glycopeptide chiral selectors are natural molecules produced by bacterial fermentation. Purified and bonded to silica particles, they make very useful chiral stationary phases (CSP) with a broad spectrum of applicability in enantiomeric separation. The macrocyclic glycopeptide CSPs are multimodal, the same column being able to work in normal phase mode with apolar mobile phase, in reversed-phase mode, or in polar ionic mode with 100% alcoholic mobile phase of adjusted pH. The role of the carbohydrate units is described as well as the critical charge-charge docking interaction responsible for the amino acid enantiomer recognition. The complimentary phenomenon is also exposed.

Marginal and Internal Discrepancies of Posterior Zirconia-Based Crowns Fabricated with Three Different CAD/CAM Systems Versus Metal-Ceramic.

PubMed

Ortega, Rocio; Gonzalo, Esther; Gomez-Polo, Miguel; Suárez, María J

2015-01-01

The aim of this study was to analyze the marginal and internal fit of metalceramic and zirconia-based crowns. Forty standardized steel specimens were prepared to receive posterior crowns and randomly divided into four groups (n = 10): (1) metal-ceramic, (2) NobelProcera Zirconia, (3) Lava Zirconia, and (4) VITA In-Ceram YZ. All crowns were cemented with glass-ionomer agent and sectioned buccolingually. A scanning electron microscope was used for measurements. Kruskal-Wallis and Wilcoxon signed rank test (α = .05) statistical analyses were conducted. Significant differences (P < .0001) in marginal discrepancies were observed between metal-ceramic and zirconia groups. No differences were found for the axial wall fit (P = .057). Significant differences were shown among the groups in discrepancies at the occlusal cusp (P = .0012) and at the fossa (P = .0062). No differences were observed between surfaces. All zirconia groups showed better values of marginal discrepancies than the metal-ceramic group. Procera Zirconia showed the lowest gaps.

Distribution of chirality in the quantum walk: Markov process and entanglement

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

Romanelli, Alejandro

The asymptotic behavior of the quantum walk on the line is investigated, focusing on the probability distribution of chirality independently of position. It is shown analytically that this distribution has a longtime limit that is stationary and depends on the initial conditions. This result is unexpected in the context of the unitary evolution of the quantum walk as it is usually linked to a Markovian process. The asymptotic value of the entanglement between the coin and the position is determined by the chirality distribution. For given asymptotic values of both the entanglement and the chirality distribution, it is possible tomore » find the corresponding initial conditions within a particular class of spatially extended Gaussian distributions.« less

Zirconia-coated carbonyl-iron-particle-based magnetorheological fluid for polishing optical glasses and ceramics

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

Shafrir, Shai N.; Romanofsky, Henry J.; Skarlinski, Michael

2009-12-10

We report on magnetorheological finishing (MRF) spotting experiments performed on glasses and ceramics using a zirconia-coated carbonyl-iron (CI)-particle-based magnetorheological (MR) fluid. The zirconia-coated magnetic CI particles were prepared via sol-gel synthesis in kilogram quantities. The coating layer was {approx}50-100 nm thick, faceted in surface structure, and well adhered. Coated particles showed long-term stability against aqueous corrosion. ''Free'' nanocrystalline zirconia polishing abrasives were cogenerated in the coating process, resulting in an abrasive-charged powder for MRF. A viable MR fluid was prepared simply by adding water. Spot polishing tests were performed on a variety of optical glasses and ceramics over a periodmore » of nearly three weeks with no signs of MR fluid degradation or corrosion. Stable material removal rates and smooth surfaces inside spots were obtained.« less

Translucency of zirconia-based pressable ceramics with different core and veneer thicknesses.

PubMed

Jeong, Il-Do; Bae, So-Yeon; Kim, Dong-Yeon; Kim, Ji-Hwan; Kim, Woong-Chul

2016-06-01

Little information is available on the translucency of zirconia-based pressable ceramic restorations with a pressed ceramic veneer and zirconia core in various thickness combinations. The purpose of this in vitro study was to assess the translucency of 3 types of zirconia-based pressable ceramics for different core-veneer thickness combinations. A bilayered ceramic specimen was prepared with a pressable ceramic (IPS e.max Zirpress, Initial IQ, Rosetta UltraPress) veneer over a zirconia core (Zenostar Zr). Three groups of specimens (n=7) were formed with the following core+veneer thicknesses: 1 +0.5 mm, 0.7 +0.8 mm, and 0.5 +1 mm. To obtain consistent thickness and high translucency, all specimens were subjected to surface grinding with a grinding machine. To eliminate the effect of differences in roughness on the translucency, the surface roughness of the ground specimens was measured with a scanning profiler, and the consistency of these measured values was verified through statistical analysis. The luminous transmittance of the specimens was measured with a spectrophotometer. The effects of the pressable ceramic type and core-veneer thickness combination on transmittance were assessed using a 2-way ANOVA (α=.05). The consistency of the surface roughness among the tested specimens was confirmed using a 1-way ANOVA and the Tukey HSD post hoc test (P<.05). The luminous transmittance exhibited a statistically significant dependence on both the type of pressable ceramic and the core-veneer thickness combination (P<.05). The type of pressable ceramic and core-veneer thickness combination affected the translucency of the restoration. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Phonon anharmonicity of monoclinic zirconia and yttrium-stabilized zirconia

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

Li, Chen W.; Smith, Hillary L.; Lan, Tian

2015-04-13

Inelastic neutron scattering measurements on monoclinic zirconia (ZrO 2) and 8 mol% yttrium-stabilized zirconia were performed at temperatures from 300 to 1373 ωK. We reported temperature-dependent phonon densities of states (DOS) and Raman spectra obtained at elevated temperatures. First-principles lattice dynamics calculations with density functional theory gave total and partial phonon DOS curves and mode Grüneisen parameters. These mode Grüneisen parameters were used to predict the experimental temperature dependence of the phonon DOS with partial success. However, substantial anharmonicity was found at elevated temperatures, especially for phonon modes dominated by the motions of oxygen atoms. Yttrium-stabilized zirconia (YSZ) was somewhatmore » more anharmonic and had a broader phonon spectrum at low temperatures, owing in part to defects in its structure. YSZ also has a larger vibrational entropy than monoclinic zirconia.« less

Structural and Chemical Analysis of the Zirconia-Veneering Ceramic Interface.

PubMed

Inokoshi, M; Yoshihara, K; Nagaoka, N; Nakanishi, M; De Munck, J; Minakuchi, S; Vanmeensel, K; Zhang, F; Yoshida, Y; Vleugels, J; Naert, I; Van Meerbeek, B

2016-01-01

The interfacial interaction of veneering ceramic with zirconia is still not fully understood. This study aimed to characterize morphologically and chemically the zirconia-veneering ceramic interface. Three zirconia-veneering conditions were investigated: 1) zirconia-veneering ceramic fired on sandblasted zirconia, 2) zirconia-veneering ceramic on as-sintered zirconia, and 3) alumina-veneering ceramic (lower coefficient of thermal expansion [CTE]) on as-sintered zirconia. Polished cross-sectioned ceramic-veneered zirconia specimens were examined using field emission gun scanning electron microscopy (Feg-SEM). In addition, argon-ion thinned zirconia-veneering ceramic interface cross sections were examined using scanning transmission electron microscopy (STEM)-energy dispersive X-ray spectrometry (EDS) at high resolution. Finally, the zirconia-veneering ceramic interface was quantitatively analyzed for tetragonal-to-monoclinic phase transformation and residual stress using micro-Raman spectroscopy (µRaman). Feg-SEM revealed tight interfaces for all 3 veneering conditions. High-resolution transmission electron microscopy (HRTEM) disclosed an approximately 1.0-µm transformed zone at sandblasted zirconia, in which distinct zirconia grains were no longer observable. Straight grain boundaries and angular grain corners were detected up to the interface of zirconia- and alumina-veneering ceramic with as-sintered zirconia. EDS mapping disclosed within the zirconia-veneering ceramic a few nanometers thick calcium/aluminum-rich layer, touching the as-sintered zirconia base, with an equally thick silicon-rich/aluminum-poor layer on top. µRaman revealed t-ZrO2-to-m-ZrO2 phase transformation and residual compressive stress at the sandblasted zirconia surface. The difference in CTE between zirconia- and the alumina-veneering ceramic resulted in residual tensile stress within the zirconia immediately adjacent to its interface with the veneering ceramic. The rather minor chemical

A facile and efficient single-step approach for the fabrication of vancomycin functionalized polymer-based monolith as chiral stationary phase for nano-liquid chromatography.

PubMed

Xu, Dongsheng; Shao, Huikai; Luo, Rongying; Wang, Qiqin; Sánchez-López, Elena; Fanali, Salvatore; Marina, Maria Luisa; Jiang, Zhengjin

2018-07-06

A facile single-step preparation strategy for fabricating vancomycin functionalized organic polymer-based monolith within 100μm fused-silica capillary was developed. The synthetic chiral functional monomer, i.e 2-isocyanatoethyl methacrylate (ICNEML) derivative of vancomycin, was co-polymerized with the cross-linker ethylene dimethacrylate (EDMA) in the presence of methanol and dimethyl sulfoxide as the selected porogens. The co-polymerization conditions were systematically optimized in order to obtain satisfactory column performance. Adequate permeability, stability and column morphology were observed for the optimized poly(ICNEML-vancomycin-co-EDMA) monolith. A series of chiral drugs were evaluated on the monolith in either polar organic-phase or reversed-phase modes. After the optimization of separation conditions, baseline or partial enantioseparation were obtained for series of drugs including thalidomide, colchicine, carteolol, salbutamol, clenbuterol and several other β-blockers. The proposed single-step approach not only resulted in a vancomycin functionalized organic polymer-based monolith with acceptable performance, but also significantly simplified the preparation procedure by reducing time and labor. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of the shades of background substructures on the overall color of zirconia-based all-ceramic crowns

PubMed Central

Tulapornchai, Chantana; Mamani, Jatuphol; Kamchatphai, Wannaporn; Thongpun, Noparat

2013-01-01

PURPOSE The objective of this study was to determine the effect of the color of a background substructure on the overall color of a zirconia-based all-ceramic crown. MATERIALS AND METHODS Twenty one posterior zirconia crowns were made for twenty subjects. Seven premolar crowns and six molar crowns were cemented onto abutments with metal post and core in the first and second group. In the third group, eight molar crowns were cemented onto abutments with a prefabricated post and composite core build-up. The color measurements of all-ceramic crowns were made before try-in, before and after cementation. A repeated measure ANOVA was used for a statistical analysis of a color change of all-ceramic crowns at α=.05. Twenty four zirconia specimens, with different core thicknesses (0.4-1 mm) were also prepared to obtain the contrast ratio of zirconia materials after veneering. RESULTS L*, a*, and b* values of all-ceramic crowns cemented either on a metal cast post and core or on a prefabricated post did not show significant changes (P>.05). However, the slight color changes of zirconia crowns were detected and represented by ΔE*ab values, ranging from 1.2 to 3.1. The contrast ratios of zirconia specimens were 0.92-0.95 after veneering. CONCLUSION No significant differences were observed between the L*, a*, and b* values of zirconia crowns cemented either on a metal cast post and core or a prefabricated post and composite core. However, the color of a background substructure could affect the overall color of posterior zirconia restorations with clinically recommended core thickness according to ΔE*ab values. PMID:24049574

Chiral Antioxidant-based Gold Nanoclusters Reprogram DNA Epigenetic Patterns

PubMed Central

Ma, Yue; Fu, Hualin; Zhang, Chunlei; Cheng, Shangli; Gao, Jie; Wang, Zhen; Jin, Weilin; Conde, João; Cui, Daxiang

2016-01-01

Epigenetic modifications sit ‘on top of’ the genome and influence DNA transcription, which can force a significant impact on cellular behavior and phenotype and, consequently human development and disease. Conventional methods for evaluating epigenetic modifications have inherent limitations and, hence, new methods based on nanoscale devices are needed. Here, we found that antioxidant (glutathione) chiral gold nanoclusters induce a decrease of 5-hydroxymethylcytosine (5hmC), which is an important epigenetic marker that associates with gene transcription regulation. This epigenetic change was triggered partially through ROS activation and oxidation generated by the treatment with glutathione chiral gold nanoclusters, which may inhibit the activity of TET proteins catalyzing the conversion of 5-methylcytosine (5mC) to 5hmC. In addition, these chiral gold nanoclusters can downregulate TET1 and TET2 mRNA expression. Alteration of TET-5hmC signaling will then affect several downstream targets and be involved in many aspects of cell behavior. We demonstrate for the first time that antioxidant-based chiral gold nanomaterials have a direct effect on epigenetic process of TET-5hmC pathways and reveal critical DNA demethylation patterns. PMID:27633378

Optical activity via Kerr nonlinearity in a spinning chiral medium

NASA Astrophysics Data System (ADS)

Khan, Anwar Ali; Bacha, Bakht Amin; Khan, Rahmat Ali

2016-11-01

Optical activity is investigated in a chiral medium by employing the four level cascade atomic model, in which the optical responses of the atomic medium are studied with Kerr nonlinearity. Light entering into a chiral medium splits into circular birefringent beams. The angle of divergence between the circular birefringent beams and the polarization states of the two light beams is manipulated with Kerr nonlinearity. In the stationary chiral medium the angle of divergence between the circular birefringent beams is calculated to be 1.3 radian. Furthermore, circular birefringence is optically controlled in a spinning chiral medium, where the maximum rotary photon drag angle for left (right) circularly polarized beam is ±1.1 (±1.5) microradian. The change in the angle of divergence between circular birefringent beams by rotary photon drag is calculated to be 0.4 microradian. The numerical results may help to understand image designing, image coding, discovery of photonic crystals and optical sensing technology.

Natural terpene derivatives as new structural task-specific ionic liquids to enhance the enantiorecognition of acidic enantiomers on teicoplanin-based stationary phase by high-performance liquid chromatography.

PubMed

Flieger, Jolanta; Feder-Kubis, Joanna; Tatarczak-Michalewska, Małgorzata; Płazińska, Anita; Madejska, Anna; Swatko-Ossor, Marta

2017-06-01

We present the specific cooperative effect of a semisynthetic glycopeptide antibiotic teicoplanin and chiral ionic liquids containing the (1R,2S,5R)-(-)-menthol moiety on the chiral recognition of enantiomers of mandelic acid, vanilmandelic acid, and phenyllactic acid. Experiments were performed chromatographically on an Astec Chirobiotic T chiral stationary phase applying the mobile phase with the addition of the chiral ionic liquids. The stereoselective binding of enantiomers to teicoplanin in presence of new chiral ionic liquids were evaluated applying thermodynamic measurements and the docking simulations. Both the experimental and theoretical methods revealed that the chiral recognition of enantiomers in the presence of new chiral ionic liquids was enthalpy driven. The changes of the teicoplanin conformation occurring upon binding of the chiral ionic liquids are responsible for the differences in the standard changes in Gibbs energy (ΔG 0 ) values obtained for complexes formed by the R and S enantiomers and teicoplanin. Docking simulations revealed the steric adjustment between the chiral ionic liquids cyclohexane ring (chair conformation) and the β-d-glucosamine ring of teicoplanin and additionally hydrophobic interactions between the decanoic aliphatic chain of teicoplanin and the alkyl group of the tested salts. The obtained terpene derivatives can be considered as "structural task-specific ionic liquids" responsible for enhancing the chiral resolution in synergistic systems with two chiral selectors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-performance liquid chromatography study of the enantiomer separation of chrysanthemic acid and its analogous compounds on a terguride-based stationary phase.

PubMed

Dondi, M; Flieger, M; Olsovska, J; Polcaro, C M; Sinibaldi, M

1999-10-29

The direct enantioseparation of chrysanthemic acid [2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylic acid] and its halogen-substituted analogues was systematically studied by HPLC using a terguride-based chiral stationary phase in combination with a UV diode array and chiroptical detectors. Isomers with (1R) configuration always eluted before those with (IS) configuration. The elution sequence of cis- and trans-isomers was strongly affected by mobile phase pH, whereas the enantioselectivity remained the same. Conditions for the separation of all the enantiomers were also examined. This method was used for monitor the hydrolytic degradation products of Cyfluthrin (Baythroid) in soil under laboratory conditions.

The bending stress distribution in bilayered and graded zirconia-based dental ceramics

PubMed Central

Fabris, Douglas; Souza, Júlio C.M.; Silva, Filipe S.; Fredel, Márcio; Mesquita-Guimarães, Joana; Zhang, Yu; Henriques, Bruno

2016-01-01

The purpose of this study was to evaluate the biaxial flexural stresses in classic bilayered and in graded zirconia-feldspathic porcelain composites. A finite element method and an analytical model were used to simulate the piston-on-ring test and to predict the biaxial stress distributions across the thickness of the bilayer and graded zirconia-feldspathic porcelain discs. An axisymmetric model and a flexure formula of Hsueh et al. were used in the FEM and analytical analysis, respectively. Four porcelain thicknesses were tested in the bilayered discs. In graded discs, continuous and stepwise transitions from the bottom zirconia layer to the top porcelain layer were studied. The resulting stresses across the thickness, measured along the central axis of the disc, for the bilayered and graded discs were compared. In bilayered discs, the maximum tensile stress decreased while the stress mismatch (at the interface) increased with the porcelain layer thickness. The optimized balance between both variables is achieved for a porcelain thickness ratio in the range of 0.30–0.35. In graded discs, the highest tensile stresses were registered for porcelain rich interlayers (p=0.25) whereas the zirconia rich ones (p=8) yield the lowest tensile stresses. In addition, the maximum stresses in a graded structure can be tailored by altering compositional gradients. A decrease in maximum stresses with increasing values of p (a scaling exponent in the power law function) was observed. Our findings showed a good agreement between the analytical and simulated models, particularly in the tensile region of the disc. Graded zirconia-feldspathic porcelain composites exhibited a more favourable stress distribution relative to conventional bilayered systems. This fact can significantly impact the clinical performance of zirconia-feldspathic porcelain prostheses, namely reducing the fracture incidence of zirconia and the chipping and delamination of porcelain. PMID:28104926

Zirconia ceramics for excess weapons plutonium waste

NASA Astrophysics Data System (ADS)

Gong, W. L.; Lutze, W.; Ewing, R. C.

2000-01-01

We synthesized a zirconia (ZrO 2)-based single-phase ceramic containing simulated excess weapons plutonium waste. ZrO 2 has large solubility for other metallic oxides. More than 20 binary systems A xO y-ZrO 2 have been reported in the literature, including PuO 2, rare-earth oxides, and oxides of metals contained in weapons plutonium wastes. We show that significant amounts of gadolinium (neutron absorber) and yttrium (additional stabilizer of the cubic modification) can be dissolved in ZrO 2, together with plutonium (simulated by Ce 4+, U 4+ or Th 4+) and impurities (e.g., Ca, Mg, Fe, Si). Sol-gel and powder methods were applied to make homogeneous, single-phase zirconia solid solutions. Pu waste impurities were completely dissolved in the solid solutions. In contrast to other phases, e.g., zirconolite and pyrochlore, zirconia is extremely radiation resistant and does not undergo amorphization. Baddeleyite (ZrO 2) is suggested as the natural analogue to study long-term radiation resistance and chemical durability of zirconia-based waste forms.

Chromatographic enantioseparation by poly(biphenylylacetylene) derivatives with memory of both axial chirality and macromolecular helicity.

PubMed

Ishidate, Ryoma; Ikai, Tomoyuki; Kanoh, Shigeyoshi; Yashima, Eiji; Maeda, Katsuhiro

2017-03-01

Novel poly(biphenylylacetylene) derivatives bearing two acetyloxy groups at the 2- and 2'-positions and an alkoxycarbonyl group at the 4'-position of the biphenyl pendants (poly-Ac's) were synthesized by the polymerization of the corresponding biphenylylacetylenes using a rhodium catalyst. The obtained stereoregular (cis-transoidal) poly-Ac's folded into a predominantly one-handed helical conformation accompanied by a preferred-handed axially twisted conformation of the biphenyl pendants through noncovalent interactions with a chiral alcohol and both the induced main-chain helicity and the pendant axial chirality were maintained, that is, memorized, after complete removal of the chiral alcohol. The stability of the helicity memory of the poly-Ac's in a solution was lower than that of the analogous poly(biphenylylacetylene)s bearing two methoxymethoxy groups at the 2- and 2'-positions of the biphenyl pendants (poly-MOM's). In the solid state, however, the helicity memory of the poly-Ac's was much more stable and showed a better chiral recognition ability toward several racemates than that of the previously reported poly-MOM when used as a chiral stationary phase for high-performance liquid chromatography. In particular, the poly-Ac-based CSP with a helicity memory efficiently separated racemic benzoin derivatives into enantiomers. © 2017 Wiley Periodicals, Inc.

[[Chiral separation of five arylpropionic acid drugs and determination of their enantiomers in pharmaceutical preparations by reversed-phase high performance liquid chromatography with cellulose-tris-(4-methylbenzoate) stationary phase

PubMed

Luo, An; Wan, Qiang; Fan, Huajun; Chen, Zhi; Wu, Xuehao; Huang, Xiaowen; Zang, Linquan

2014-09-01

Chromatographic behaviors for enantiomeric separation of arylpropionic acid drugs were systematically developed by reversed phase-high performance liquid chromatography (RP-HPLC) using cellulose-tris-(4-methylbenzoate) (CTMB) as chiral stationary phase (CSP). The effects of the composition of the mobile phase, additives and temperature on chiral separation of flurbiprofen, pranoprofen, naproxen, ibuprofen and loxoprofen were further investigated. The enantiomers had been successfully separated on CSP of CTMB by the mobile phase of methanol-0.1% (v/v) formic acid except naproxen by acetonitrile-0.1% (v/v) formic acid at 25 °C. The mechanisms of the racemic resolution for the above mentioned five drugs are discussed thermodynamically and structurally. The resolutions between respective enantiomers for arylpropionic acid drugs on CTMB had significant differences due to their chromatographic behaviors. The order of resolutions ranked pranoprofen, loxoprofen, flurbiprofen, ibuprofen and naproxen. The method established has been successfully applied to the determination of the enantiomers of the five drugs in commercial preparations under the optimized conditions. It proved that the method is simple, reliable and accurate.

High-performance liquid chromatographic separations of stereoisomers of chiral basic agrochemicals with polysaccharide-based chiral columns and polar organic mobile phases.

PubMed

Matarashvili, Iza; Shvangiradze, Iamze; Chankvetadze, Lali; Sidamonidze, Shota; Takaishvili, Nino; Farkas, Tivadar; Chankvetadze, Bezhan

2015-12-01

The separation of the stereoisomers of 23 chiral basic agrochemicals was studied on six different polysaccharide-based chiral columns in high-performance liquid chromatography with various polar organic mobile phases. Along with the successful separation of analyte stereoisomers, emphasis was placed on the effect of the chiral selector and mobile phase composition on the elution order of stereoisomers. The interesting phenomenon of reversal of enantiomer/stereoisomer elution order function of the polysaccharide backbone (cellulose or amylose), type of derivative (carbamate or benzoate), nature, and position of the substituent(s) in the phenylcarbamate moiety (methyl or chloro) and the nature of the mobile phase was observed. For several of the analytes containing two chiral centers all four stereoisomers were resolved with at least one chiral selector/mobile phase combination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards long lasting zirconia-based composites for dental implants: Transformation induced plasticity and its consequence on ceramic reliability.

PubMed

Reveron, Helen; Fornabaio, Marta; Palmero, Paola; Fürderer, Tobias; Adolfsson, Erik; Lughi, Vanni; Bonifacio, Alois; Sergo, Valter; Montanaro, Laura; Chevalier, Jérôme

2017-01-15

Zirconia-based composites were developed through an innovative processing route able to tune compositional and microstructural features very precisely. Fully-dense ceria-stabilized zirconia ceramics (84vol% Ce-TZP) containing equiaxed alumina (8vol%Al 2 O 3 ) and elongated strontium hexa-aluminate (8vol% SrAl 12 O 19 ) second phases were obtained by conventional sintering. This work deals with the effect of the zirconia stabilization degree (CeO 2 in the range 10.0-11.5mol%) on the transformability and mechanical properties of Ce-TZP-Al 2 O 3 -SrAl 12 O 19 materials. Vickers hardness, biaxial flexural strength and Single-edge V-notched beam tests revealed a strong influence of ceria content on the mechanical properties. Composites with 11.0mol% CeO 2 or above exhibited the classical behaviour of brittle ceramics, with no apparent plasticity and very low strain to failure. On the contrary, composites with 10.5mol% CeO 2 or less showed large transformation-induced plasticity and almost no dispersion in strength data. Materials with 10.5mol% of ceria showed the highest values in terms of biaxial bending strength (up to 1.1GPa) and fracture toughness (>10MPa√m). In these ceramics, as zirconia transformation precedes failure, the Weibull modulus was exceptionally high and reached a value of 60, which is in the range typically reported for metals. The results achieved demonstrate the high potential of using these new strong, tough and stable zirconia-based composites in structural biomedical applications. Yttria-stabilized (Y-TZP) zirconia ceramics are increasingly used for developing metal-free restorations and dental implants. Despite their success related to their excellent mechanical resistance, Y-TZP can undergo Low Temperature Degradation which could be responsible for restoration damage or even worst the failure of the implant. Current research is focusing on strategies to improve the LTD resistance of Y-TZP or to develop alternative composites with better

Fractographic features of glass-ceramic and zirconia-based dental restorations fractured during clinical function.

PubMed

Oilo, Marit; Hardang, Anne D; Ulsund, Amanda H; Gjerdet, Nils R

2014-06-01

Fractures during clinical function have been reported as the major concern associated with all-ceramic dental restorations. The aim of this study was to analyze the fracture features of glass-ceramic and zirconia-based restorations fractured during clinical use. Twenty-seven crowns and onlays were supplied by dentists and dental technicians with information about type of cement and time in function, if available. Fourteen lithium disilicate glass-ceramic restorations and 13 zirconia-based restorations were retrieved and analyzed. Fractographic features were examined using optical microscopy to determine crack initiation and crack propagation of the restorations. The material comprised fractured restorations from one canine, 10 incisors, four premolars, and 11 molars. One crown was not categorized because of difficulty in orientation of the fragments. The results revealed that all core and veneer fractures initiated in the cervical margin and usually from the approximal area close to the most coronally placed curvature of the margin. Three cases of occlusal chipping were found. The margin of dental all-ceramic single-tooth restorations was the area of fracture origin. The fracture features were similar for zirconia, glass-ceramic, and alumina single-tooth restorations. Design features seem to be of great importance for fracture initiation. © 2014 Eur J Oral Sci.

Analysis of carvedilol enantiomers in human plasma using chiral stationary phase column and liquid chromatography with tandem mass spectrometry.

PubMed

Poggi, Josiane Cristófani; Da Silva, Flávia Garcez; Coelho, Eduardo Barbosa; Marques, Maria Paula; Bertucci, Carlo; Lanchote, Vera Lucia

2012-03-01

Carvedilol is an antihypertensive drug available as a racemic mixture. (-)-(S)-carvedilol is responsible for the nonselective β-blocker activity but both enantiomers present similar activity on α(1)-adrenergic receptor. To our knowledge, this is the first study of carvedilol enantiomers in human plasma using a chiral stationary phase column and liquid chromatography with tandem mass spectrometry. The method involves plasma extraction with diisopropyl ether using metoprolol as internal standard and direct separation of the carvedilol enantiomers on a Chirobiotic T® (Teicoplanin) column. Protonated ions [M + H](+) and their respective ion products were monitored at transitions of 407 > 100 for the carvedilol enantiomers and 268 > 116 for the internal standard. The quantification limit was 0.2 ng ml(-1) for both enantiomers in plasma. The method was applied to study enantioselectivity in the pharmacokinetics of carvedilol administered as a single dose of 25 mg to a hypertensive patient. The results showed a higher plasma concentration of (+)-(R)-carvedilol (AUC(0-∞) 205.52 vs. 82.61 (ng h) ml(-1)), with an enantiomer ratio of 2.48. Copyright © 2012 Wiley Periodicals, Inc.

Silver Films with Hierarchical Chirality.

PubMed

Ma, Liguo; Cao, Yuanyuan; Duan, Yingying; Han, Lu; Che, Shunai

2017-07-17

Physical fabrication of chiral metallic films usually results in singular or large-sized chirality, restricting the optical asymmetric responses to long electromagnetic wavelengths. The chiral molecule-induced formation of silver films prepared chemically on a copper substrate through a redox reaction is presented. Three levels of chirality were identified: primary twisted nanoflakes with atomic crystal lattices, secondary helical stacking of these nanoflakes to form nanoplates, and tertiary micrometer-sized circinates consisting of chiral arranged nanoplates. The chiral Ag films exhibited multiple plasmonic absorption- and scattering-based optical activities at UV/Vis wavelengths based on their hierarchical chirality. The Ag films showed chiral selectivity for amino acids in catalytic electrochemical reactions, which originated from their primary atomic crystal lattices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polyoxometalates-based chiral frameworks involving helical motifs generated by spontaneous resolution

NASA Astrophysics Data System (ADS)

Li, Ning; Jiang, Dingding; Pan, Qiliang; Zhao, Jianguo; Zhang, Sufang; Xing, Baoyan; Du, Yaqin; Zhang, Zhong; Liu, Shuxia

2018-05-01

Two enantiomerically 3D chiral polyoxometalate frameworks L,D-[K(H2O)]6[H2GeMo2W10O40]3ṡ40H2O (1a and 1b), were conventionally synthesized and characterized by X-ray single-crystal diffraction, IR spectrum, elemental analysis, powder X-ray diffraction, thermogravimetric analysis, UV-Vis spectroscopy, circular dichroism spectra. Structural analysis indicates that 1a and 1b are enantiomers. The terminal O and μ2-O atoms of Keggin-type polyanion [GeMo2W10O40]4- and {K(H2O)}n segments are connected one another to form 1D chiral helical chains, which are further extended by the achiral Keggin-type [GeMo2W10O40]4- anion to construct 3D 4,8-connected chiral frameworks. The enantiomers were isolated by spontaneous resolution during crystallization without any chiral auxiliary. They represent rare examples of enantiomerically pure chiral polyoxometalate-based inorganic porous frameworks.

Chiral magnetic effect without chirality source in asymmetric Weyl semimetals

NASA Astrophysics Data System (ADS)

Kharzeev, Dmitri E.; Kikuchi, Yuta; Meyer, René

2018-05-01

We describe a new type of the chiral magnetic effect (CME) that should occur in Weyl semimetals (WSMs) with an asymmetry in the dispersion relations of the left- and right-handed (LH and RH) chiral Weyl fermions. In such materials, time-dependent pumping of electrons from a non-chiral external source can generate a non-vanishing chiral chemical potential. This is due to the different capacities of the LH and RH chiral Weyl cones arising from the difference in the density of states in the LH and RH cones. The chiral chemical potential then generates, via the chiral anomaly, a current along the direction of an applied magnetic field even in the absence of an external electric field. The source of chirality imbalance in this new setup is thus due to the band structure of the system and the presence of (non-chiral) electron source, and not due to the parallel electric and magnetic fields. We illustrate the effect by an argument based on the effective field theory, and by the chiral kinetic theory calculation for a rotationally invariant WSM with different Fermi velocities in the left and right chiral Weyl cones; we also consider the case of a WSM with Weyl nodes at different energies. We argue that this effect is generically present in WSMs with different dispersion relations for LH and RH chiral Weyl cones, such as SrSi2 recently predicted as a WSM with broken inversion and mirror symmetries, as long as the chiral relaxation time is much longer than the transport scattering time.

pH control of the structure, composition, and catalytic activity of sulfated zirconia

NASA Astrophysics Data System (ADS)

Ivanov, Vladimir K.; Baranchikov, Alexander Ye.; Kopitsa, Gennady P.; Lermontov, Sergey A.; Yurkova, Lyudmila L.; Gubanova, Nadezhda N.; Ivanova, Olga S.; Lermontov, Anatoly S.; Rumyantseva, Marina N.; Vasilyeva, Larisa P.; Sharp, Melissa; Pranzas, P. Klaus; Tretyakov, Yuri D.

2013-02-01

We report a detailed study of structural and chemical transformations of amorphous hydrous zirconia into sulfated zirconia-based superacid catalysts. Precipitation pH is shown to be the key factor governing structure, composition and properties of amorphous sulfated zirconia gels and nanocrystalline sulfated zirconia. Increase in precipitation pH leads to substantial increase of surface fractal dimension (up to ˜2.7) of amorphous sulfated zirconia gels, and consequently to increase in specific surface area (up to ˜80 m2/g) and simultaneously to decrease in sulfate content and total acidity of zirconia catalysts. Complete conversion of hexene-1 over as synthesized sulfated zirconia catalysts was observed even under ambient conditions.

Novel stationary phases based on asphaltenes for gas chromatography.

PubMed

Boczkaj, Grzegorz; Momotko, Malwina; Chruszczyk, Dorota; Przyjazny, Andrzej; Kamiński, Marian

2016-07-01

We present the results of investigations on the possibility of the application of the asphaltene fraction isolated from the oxidized residue from vacuum distillation of crude oil as a stationary phase for gas chromatography. The results of the investigation revealed that the asphaltene stationary phases can find use for the separation of a wide range of volatile organic compounds. The experimental values of Rohrschneider/McReynolds constants characterize the asphaltenes as stationary phases of medium polarity and selectivity similar to commercially available phases based on alkyl phthalates. Isolation of asphaltenes from the material obtained under controlled process conditions allows the production of a stationary phase having reproducible sorption properties and chromatographic columns having the same selectivity. Unique selectivity and high thermal stability make asphaltenes attractive as a material for stationary phases for gas chromatography. A low production cost from a readily available raw material (oxidized petroleum bitumens) is an important economic factor in case of application of the asphaltene stationary phases for preparative and process separations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of cementation surface modifications on fracture resistance of zirconia.

PubMed

Srikanth, Ramanathan; Kosmac, Tomaz; Della Bona, Alvaro; Yin, Ling; Zhang, Yu

2015-04-01

To examine the effects of glass infiltration (GI) and alumina coating (AC) on the indentation flexural load and four-point bending strength of monolithic zirconia. Plate-shaped (12 mm × 12 mm × 1.0 mm or 1.5 or 2.0 mm) and bar-shaped (4 mm × 3 mm × 25 mm) monolithic zirconia specimens were fabricated. In addition to monolithic zirconia (group Z), zirconia monoliths were glass-infiltrated or alumina-coated on their tensile surfaces to form groups ZGI and ZAC, respectively. They were also glass-infiltrated on their upper surfaces, and glass-infiltrated or alumina-coated on their lower (tensile) surfaces to make groups ZGI2 and ZAC2, respectively. For comparison, porcelain-veneered zirconia (group PVZ) and monolithic lithium disilicate glass-ceramic (group LiDi) specimens were also fabricated. The plate-shaped specimens were cemented onto a restorative composite base for Hertzian indentation using a tungsten carbide spherical indenter with a radius of 3.2mm. Critical loads for indentation flexural fracture at the zirconia cementation surface were measured. Strengths of bar-shaped specimens were evaluated in four-point bending. Glass infiltration on zirconia tensile surfaces increased indentation flexural loads by 32% in Hertzian contact and flexural strength by 24% in four-point bending. Alumina coating showed no significant effect on resistance to flexural damage of zirconia. Monolithic zirconia outperformed porcelain-veneered zirconia and monolithic lithium disilicate glass-ceramics in terms of both indentation flexural load and flexural strength. While both alumina coating and glass infiltration can be used to effectively modify the cementation surface of zirconia, glass infiltration can further increase the flexural fracture resistance of zirconia. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effects of cementation surface modifications on fracture resistance of zirconia

PubMed Central

Srikanth, Ramanathan; Kosmac, Tomaz; Bona, Alvaro Della; Yin, Ling; Zhang, Yu

2015-01-01

Objectives To examine the effects of glass infiltration (GI) and alumina coating (AC) on the indentation flexural load and four-point bending strength of monolithic zirconia. Methods Plate-shaped (12 mm × 12 mm × 1.0 mm or 1.5 mm or 2.0 mm) and bar-shaped (4 mm × 3 mm × 25 mm) monolithic zirconia specimens were fabricated. In addition to monolithic zirconia (group Z), zirconia monoliths were glass-infiltrated or alumina-coated on their tensile surfaces to form groups ZGI and ZAC, respectively. They were also glass-infiltrated on their upper surfaces, and glass-infiltrated or alumina-coated on their lower (tensile) surfaces to make groups ZGI2 and ZAC2, respectively. For comparison, porcelain-veneered zirconia (group PVZ) and monolithic lithium disilicate glass-ceramic (group LiDi) specimens were also fabricated. The plate-shaped specimens were cemented onto a restorative composite base for Hertzian indentation using a tungsten carbide spherical indenter with a radius of 3.2 mm. Critical loads for indentation flexural fracture at the zirconia cementation surface were measured. Strengths of bar-shaped specimens were evaluated in four-point bending. Results Glass infiltration on zirconia tensile surfaces increased indentation flexural loads by 32% in Hertzian contact and flexural strength by 24% in four-point bending. Alumina coating showed no significant effect on resistance to flexural damage of zirconia. Monolithic zirconia outperformed porcelain-veneered zirconia and monolithic lithium disilicate glass-ceramics in terms of both indentation flexural load and flexural strength. Significance While both alumina coating and glass infiltration can be used to effectively modify the cementation surface of zirconia, glass infiltration can further increase the flexural fracture resistance of zirconia. PMID:25687628

Evaluation of participants' perception and taste thresholds with a zirconia palatal plate.

PubMed

Wada, Takeshi; Takano, Tomofumi; Tasaka, Akinori; Ueda, Takayuki; Sakurai, Kaoru

2016-10-01

Zirconia and cobalt-chromium can withstand a similar degree of loading. Therefore, using a zirconia base for removable dentures could allow the thickness of the palatal area to be reduced similarly to metal base dentures. We hypothesized that zirconia palatal plate for removable dentures provides a high level of participants' perception without influencing taste thresholds. The purpose of this study was to evaluate the participants' perception and taste thresholds of zirconia palatal plate. Palatal plates fabricated using acrylic resin, zirconia, and cobalt-chromium alloy were inserted into healthy individuals. Taste thresholds were investigated using the whole-mouth gustatory test, and participants' perception was evaluated using the 100-mm visual analog scale to assess the ease of pronunciation, ease of swallowing, sensation of temperature, metallic taste, sensation of foreign body, subjective sensory about weight, adhesiveness of chewing gum, and general satisfaction. For the taste thresholds, no significant differences were noted in sweet, salty, sour, bitter, or umami tastes among participants wearing no plate, or the resin, zirconia, and metal plates. Speech was easier and foreign body sensation was lower with the zirconia plate than with the resin plate. Evaluation of the adhesiveness of chewing gum showed that chewing gum does not readily adhere to the zirconia plate in comparison with the metal plate. The comprehensive participants' perception of the zirconia plate was evaluated as being superior to the resin plate. A zirconia palatal plate provides a high level of participants' perception without influencing taste thresholds. Copyright © 2016 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Zirconia-based dental crown to support a removable partial denture: a three-dimensional finite element analysis using contact elements and micro-CT data.

PubMed

Rocha, Eduardo Passos; Anchieta, Rodolfo Bruniera; de Almeida, Erika Oliveira; Freitas, Amilcar Chagas; Martini, Ana Paula; Sotto-Maior, Bruno Sales; Luersen, Marco Antonio; Ko, Ching Chang

2015-01-01

Veneer fracture is the most common complication in zirconia-based restorations. The aim of this study was to evaluate the mechanical behavior of a zirconia-based crown in a lower canine tooth supporting removable partial denture (RPD) prosthesis, varying the bond quality of the veneer/coping interface. Microtomography (μCT) data of an extracted left lower canine were used to build the finite element model (M) varying the core material (gold core - MAu; zirconia core - MZi) and the quality of the veneer/core interface (complete bonded - MZi; incomplete bonded - MZi-NL). The incomplete bonding condition was only applied for zirconia coping by using contact elements (Target/Contact) with 0.3 frictional coefficients. Stress fields were obtained using Ansys Workbench 10.0. The loading condition (L = 1 N) was vertically applied at the base of the RPD prosthesis metallic support towards the dental apex. Maximum principal (σmax) and von Mises equivalent (σvM) stresses were obtained. The σmax (MPa) for the bonded condition was similar between gold and zirconia cores (MAu, 0.42; MZi, 0.40). The incomplete bonded condition (MZi-NL) raised σmax in the veneer up to 800% (3.23 MPa) in contrast to the bonded condition. The peak of σvM increased up to 270% in the MZi-NL. The incomplete bond condition increasing the stress in the veneer/zirconia interface.

Preparative enantiomer separation of dichlorprop with a cinchona-derived chiral selector employing centrifugal partition chromatography and high-performance liquid chromatography: a comparative study.

PubMed

Gavioli, Elena; Maier, Norbert M; Minguillón, Cristina; Lindner, Wolfgang

2004-10-01

A countercurrent chromatography protocol for support-free preparative enantiomer separation of the herbicidal agent 2-(2,4-dichlorphenoxy)propionic acid (dichlorprop) was developed utilizing a purposefully designed, highly enantioselective chiral stationary-phase additive (CSPA) derived from bis-1,4-(dihydroquinidinyl)phthalazine. Guided by liquid-liquid extraction experiments, a solvent system consisting of 10 mM CSPA in methyl tert-butyl ether and 100 mM sodium phosphate buffer (pH 8.0) was identified as a suitable stationary/mobile-phase combination. This solvent system provided an ideal compromise among stationary-phase retention, enantioselectivity, and well-balanced analyte distribution behavior. Using a commercial centrifugal partition chromatography instrument, complete enantiomer separations of up to 366 mg of racemic dichlorprop could be achieved, corresponding to a sample load being equivalent to the molar amount of CSPA employed. Comparison of the preparative performance characteristics of the CPC protocol with that of a HPLC separation using a silica-supported bis-1,4-(dihydroquinidinyl)phthalazine chiral stationary phase CSP revealed comparable loading capacities for both techniques but a significantly lower solvent consumption for CPC. With respect to productivity, HPLC was found to be superior, mainly due to inherent flow rate restrictions of the CPC instrument. Given that further progress in instrumental design and engineering of dedicated, highly enantioselective CSPAs can be achieved, CPC may offer a viable alternative to CSP-based HPLC for preparative-scale enantiomer separation.

Research on surface modification of nano-zirconia

NASA Astrophysics Data System (ADS)

Chen, Wen; Zhang, Cun-Lin; Yang, Xiao-Yi

2005-02-01

The mechanisms about the aggregation and dispersibility of nano-zirconia were analyzed in detail. And nano-zirconia powders which were surface-modified with silane coupling reagent WD70 were prepared in order to disperse homogeneously in ethanol in this investigation. The grain size and grain phase of nano-zirconia were obtained by XRD. Research and characterization on the structure and surface characteristic of surface-modified nano-zirconia were achieved by XPS, TG-DSC, TEM and FT-IR. The results given by FT-IR and XPS showed WD70 was jointed on the surface of nano-zirconia through both physical adsorption and chemical binding after the de-methanol reaction between the methoxyl groups of WD70 and the hydroxy groups on the surface of nano-zirconia. And the corresponding model of surface-modified nano-zirconia was given. The images provided by TEM presented intuitionistic effect of surface modification on the dispersibility of nano-zirconia in ethanol. And TG-DSC analysis ascertained the amount of WD70 that was jointed on the surface of nano-zirconia and the amount was about 6.21 percent.

Chiral supramolecular organization from a sheet-like achiral gel: a study of chiral photoinduction.

PubMed

Royes, Jorge; Polo, Víctor; Uriel, Santiago; Oriol, Luis; Piñol, Milagros; Tejedor, Rosa M

2017-05-31

Chiral photoinduction in a photoresponsive gel based on an achiral 2D architecture with high geometric anisotropy and low roughness has been investigated. Circularly polarized light (CPL) was used as a chiral source and an azobenzene chromophore was employed as a chiral trigger. The chiral photoinduction was studied by evaluating the preferential excitation of enantiomeric conformers of the azobenzene units. Crystallographic data and density functional theory (DFT) calculations show how chirality is transferred to the achiral azomaterials as a result of the combination of chiral photochemistry and supramolecular interactions. This procedure could be applied to predict and estimate chirality transfer from a chiral physical source to a supramolecular organization using different light-responsive units.

Innovations in bonding to zirconia based ceramics: Part III. Phosphate monomer resin cements.

PubMed

Mirmohammadi, Hesam; Aboushelib, Moustafa N M; Salameh, Ziad; Feilzer, Albert J; Kleverlaan, Cornelis J

2010-08-01

To compare the bond strength values and the ranking order of three phosphate monomer containing resin cements using microtensile (microTBS) and microshear (microSBS) bond strength tests. Zirconia discs (Procera Zirconia) were bonded to resin composite discs (Filtek Z250) using three different cements (Panavia F 2.0, RelyX UniCem, and Multilink). Two bond strength tests were used to determine zirconia resin bond strength; microtensile bond strength test (microTBS) and microshear bond strength test (microSBS). Ten specimens were tested for each group (n=10). Two-way analysis of variance (ANOVA) was used to analyze the data (alpha=0.05). There were statistical significant differences in bond strength values and in the ranking order obtained using the two test methods. microTBS reported significant differences in bond strength values, whereas microSBS failed to detect such effect. Both Multilink and Panavia demonstrated basically cohesive failure in the resin cement while RelyX UniCem demonstrated interfacial failure. Based on the findings of this study, the data obtained using either microTBS or microSBS could not be directly compared. microTBS was more sensitive to material differences compared to microSBS which failed to detect such differences. Copyright 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Mass-Selective Chiral Analysis

NASA Astrophysics Data System (ADS)

Boesl, Ulrich; Kartouzian, Aras

2016-06-01

Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here.

Thin Layer Chromatographic Resolution of Some β-adrenolytics and a β2-Agonist Using Bovine Serum Albumin as Chiral Additive in Stationary Phase.

PubMed

Malik, Poonam; Bhushan, Ravi

2018-01-01

Direct enantiomeric resolution of commonly used five racemic β-adrenolytics, namely, bisoprolol, atenolol, propranolol, salbutamol and carvedilol has been achieved by thin layer chromatography using bovine serum albumin (BSA) as chiral additive in stationary phase. Successful resolution of the enantiomers of all racemic β-adrenolytics was achieved by use of different composition of simple organic solvents having no buffer or inorganic ions. The effect of variation in pH, temperature, amount of BSA as the additive, and composition of mobile phase on resolution was systematically studied. Spots were visualized in iodine vapors. Native enantiomers for each of the five analytes were isolated and identified and their elution order was determined. The limit of detection was found to be 0.7, 1.2, 0.84, 1.6 and 0.9 μg (per spot) for each enantiomer of bisoprolol, atenolol, propranolol, salbutamol and carvedilol, respectively. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Chiral electroweak currents in nuclei

DOE PAGES

Riska, D. O.; Schiavilla, R.

2017-01-10

Here, the development of the chiral dynamics based description of nuclear electroweak currents is reviewed. Gerald E. (Gerry) Brown’s role in basing theoretical nuclear physics on chiral Lagrangians is emphasized. Illustrative examples of the successful description of electroweak observables of light nuclei obtained from chiral effective field theory are presented.

Evaporation rate-based selection of supramolecular chirality.

PubMed

Hattori, Shingo; Vandendriessche, Stefaan; Koeckelberghs, Guy; Verbiest, Thierry; Ishii, Kazuyuki

2017-03-09

We demonstrate the evaporation rate-based selection of supramolecular chirality for the first time. P-type aggregates prepared by fast evaporation, and M-type aggregates prepared by slow evaporation are kinetic and thermodynamic products under dynamic reaction conditions, respectively. These findings provide a novel solution reaction chemistry under the dynamic reaction conditions.

An innovative approach to the analysis of 3-[4-(2-methylpropyl)phenyl]propanoic acid as an impurity of ibuprofen on a carbon-coated zirconia stationary phase.

PubMed

Kalafut, P; Kucera, R; Klimes, J; Sochor, J

2009-07-12

3-[4-(2-Methylpropyl)phenyl]propanoic acid has been introduced as impurity F to the European Pharmacopoeia in its Supplement 4.2. In contrast to other impurities, which are evaluated by HPLC, the content of impurity F is determined by gas chromatography after previous derivatization. Thus a novel reversed-phase HPLC method was developed to simplify the evaluation of pharmacopoeial impurity F of ibuprofen. Favourable properties of zirconia stationary phases were employed for this purpose. The HPLC separation was achieved on a Zr-CARB column (150 mm x 4.6mm i.d., 5 microm) using the mobile phase acetonitrile-phosphate buffer (pH 3.5, 25 mM) (38:62, v/v), temperature 80 degrees C and the flow rate 1.2 ml min(-1). The fluorescence detection was employed to enhance the sensitivity of the method. Optimal detection parameters were chosen on the basis of fluorescence spectra of the analytes. The excitation and emission wavelengths were 220 nm and 285 nm, respectively. The analysis was completed within 25 min. The subsequent validation of the method confirmed the applicability of method for the analytical assay of impurity F.

Synthesis and characterization of mesoporous zirconia and aluminated mesoporous zirconia

NASA Astrophysics Data System (ADS)

Zhao, Elizabeth Sun

Synthesis of mesoporous zirconia has been performed by slowly hydrolyzing zirconium propoxide in the presence of anionic surfactants: namely, dodecyl phosphate or sulfate (P12 and Sf12) and hexadecyl sulfonate (So16) The zirconia. outgassed at 140--150°C has T-plot surface areas higher than 400 M2/g. This outgassing does not remove the surfactant. After calcination in air at 500°C and combustion of the surfactant, the mesoporous volume is reduced by a factor of about 2, whereas the pore wall material crystallizes in the tetragonal phase. The high-resolution electron microscopic study reveals the presence of a disorganized network of polygonal pores structure. It is suggested that the chemistry of the hydrolysis solution is instrumental in determining the pore structure. A schematic model in which the surfactant is a scaffold component is suggested in order to explain these results and the fixation of PO4, or SO4 in the walls may help to preserve the porous structure. It is very different from the templating mechanism. From the density obtained from phase transition temperature, and from the mesoporous volume (N2 adsorption), the thickness of the wall can be calculated as well as the pseudo-length of the pores. From the thickness, the T-plot area can be recalculated and agrees well with the measured T-plot surface area for the sample calcined at 500°C. Around 900°C, the walls become thicker and crystallizes into monoclinic zirconia without pore structure. In order to try to modify, the acidity of the mesoporous sulfated and oxo-phosphated zirconia, they were doped with aluminum. The sulfated zirconia only has a coating layer of amorphous alumina, while the phosphated zirconia has aluminum in the lattice and the alumina coat. A maximum ratio of Al/Zr ˜ 0.04 can be reached in the lattice. The introduction of aluminum into the lattice prevents the crystallization of the oxo-phosphate at 900°C, and helps to preserve the surface area and porosity of the sulfated

Parameter retrieval of chiral metamaterials based on the state-space approach.

PubMed

Zarifi, Davoud; Soleimani, Mohammad; Abdolali, Ali

2013-08-01

This paper deals with the introduction of an approach for the electromagnetic characterization of homogeneous chiral layers. The proposed method is based on the state-space approach and properties of a 4×4 state transition matrix. Based on this, first, the forward problem analysis through the state-space method is reviewed and properties of the state transition matrix of a chiral layer are presented and proved as two theorems. The formulation of a proposed electromagnetic characterization method is then presented. In this method, scattering data for a linearly polarized plane wave incident normally on a homogeneous chiral slab are combined with properties of a state transition matrix and provide a powerful characterization method. The main difference with respect to other well-established retrieval procedures based on the use of the scattering parameters relies on the direct computation of the transfer matrix of the slab as opposed to the conventional calculation of the propagation constant and impedance of the modes supported by the medium. The proposed approach allows avoiding nonlinearity of the problem but requires getting enough equations to fulfill the task which was provided by considering some properties of the state transition matrix. To demonstrate the applicability and validity of the method, the constitutive parameters of two well-known dispersive chiral metamaterial structures at microwave frequencies are retrieved. The results show that the proposed method is robust and reliable.

Fracture strength of zirconia implant abutments on narrow diameter implants with internal and external implant abutment connections: A study on the titanium resin base concept.

PubMed

Sailer, Irena; Asgeirsson, Asgeir G; Thoma, Daniel S; Fehmer, Vincent; Aspelund, Thor; Özcan, Mutlu; Pjetursson, Bjarni E

2018-04-01

There is limited knowledge regarding the strength of zirconia abutments with internal and external implant abutment connections and zirconia abutments supported by a titanium resin base (Variobase, Straumann) for narrow diameter implants. To compare the fracture strength of narrow diameter abutments with different types of implant abutment connections after chewing simulation. Hundred and twenty identical customized abutments with different materials and implant abutment connections were fabricated for five groups: 1-piece zirconia abutment with internal connection (T1, Cares-abutment-Straumann BL-NC implant, Straumann Switzerland), 1-piece zirconia abutment with external hex connection (T2, Procera abutment-Branemark NP implant, Nobel Biocare, Sweden), 2-piece zirconia abutments with metallic insert for internal connection (T3, Procera abutment-Replace NP implant, Nobel Biocare), 2-piece zirconia abutment on titanium resin base (T4, LavaPlus abutment-VarioBase-Straumann BL-NC implant, 3M ESPE, Germany) and 1-piece titanium abutment with internal connection (C, Cares-abutment-Straumann BL-NC implant, Straumann, Switzerland). All implants had a narrow diameter ranging from 3.3 to 3.5 mm. Sixty un-restored abutments and 60 abutments restored with glass-ceramic crowns were tested. Mean bending moments were compared using ANOVA with p-values adjusted for multiple comparisons using Tukey's procedure. The mean bending moments were 521 ± 33 Ncm (T4), 404 ± 36 Ncm (C), 311 ± 106 Ncm (T1) 265 ± 22 Ncm (T3) and 225 ± 29 (T2) for un-restored abutments and 278 ± 84 Ncm (T4), 302 ± 170 Ncm (C), 190 ± 55 Ncm (T1) 80 ± 102 Ncm (T3) and 125 ± 57 (T2) for restored abutments. For un-restored abutments, C and T4 had similar mean bending moments, significantly higher than those of the three other groups (p < .05). Titanium abutments (C) had significantly higher bending moments than identical zirconia abutments (T1) (p < .05). Zirconia

Bulky melamine-based Zn-porphyrin tweezer as a CD probe of molecular chirality.

PubMed

Petrovic, Ana G; Vantomme, Ghislaine; Negrón-Abril, Yashira L; Lubian, Elisa; Saielli, Giacomo; Menegazzo, Ileana; Cordero, Roselynn; Proni, Gloria; Nakanishi, Koji; Carofiglio, Tommaso; Berova, Nina

2011-10-01

The transfer of chirality from a guest molecule to an achiral host is the subject of significant interest especially when, upon chiral induction, the chiroptical response of the host/guest complex can effectively report the absolute configuration (AC) of the guest. For more than a decade, dimeric metalloporphyrin hosts (tweezers) have been successfully applied as chirality probes for determination of the AC for a wide variety of chiral synthetic compounds and natural products. The objective of this study is to investigate the utility of a new class of melamine-bridged Zn-porphyrin tweezers as sensitive AC reporters. A combined approach based on an experimental CD analysis and a theoretical prediction of the prevailing interporphyrin helicity demonstrates that these tweezers display favorable properties for chiral recognition. Herein, we discuss the application of the melamine-bridged tweezer to the chiral recognition of a diverse set of chiral guests, such as 1,2-diamines, α-amino-esters and amides, secondary alcohols, and 1,2-amino-alcohols. The bulky periphery and the presence of a rigid porphyrin linkage lead, in some cases, to a more enhanced CD sensitivity than that reported earlier with other tweezers. Copyright © 2011 Wiley-Liss, Inc.

Assessment and comparison of retention of zirconia copings luted with different cements onto zirconia and titanium abutments: An in vitro study

PubMed Central

Menon, Neelima Sreekumar; Kumar, G. P. Surendra; Jnanadev, K. R.; Satish Babu, C. L.; Shetty, Shilpa

2016-01-01

Aim: The purpose of this in vitro study was to assess and compare the retention of zirconia copings luted with different luting agents onto zirconia and titanium abutments. Materials and Methods: Titanium and zirconia abutments were torqued at 35 N/cm onto implant analogs. The samples were divided into two groups: Group A consisted of four titanium abutments and 32 zirconia copings and Group B consisted of four zirconia abutments and 32 zirconia copings and four luting agents were used. The cemented copings were subjected to tensile dislodgement forces and subjected to ANOVA test. Results: Zirconia abutments recorded a higher mean force compared to titanium. Among the luting agents, resin cement recorded the highest mean force followed by zinc phosphate, glass ionomer, and noneugenol zinc oxide cement, respectively. Conclusion: Highest mean retention was recorded for zirconia implant abutments compared to titanium abutments when luted with zirconia copings. PMID:27141162

Photoremovable chiral auxiliary.

PubMed

Kammath, Viju Balachandran; Sebej, Peter; Slanina, Tomáš; Kříž, Zdeněk; Klán, Petr

2012-03-01

A new concept of a photoremovable chiral auxiliary (PCA), based on the chiral benzoin chromophore, is introduced. This moiety can control the asymmetric formation of a Diels-Alder adduct, and then be removed in a subsequent photochemical step in high chemical and quantum yields. Selective formation of the products at up to 96% ee was observed in the presence of a Lewis acid catalyst in the case of a 2-methoxybenzoinyl chiral auxiliary.

Geophysics-based method of locating a stationary earth object

DOEpatents

Daily, Michael R [Albuquerque, NM; Rohde, Steven B [Corrales, NM; Novak, James L [Albuquerque, NM

2008-05-20

A geophysics-based method for determining the position of a stationary earth object uses the periodic changes in the gravity vector of the earth caused by the sun- and moon-orbits. Because the local gravity field is highly irregular over a global scale, a model of local tidal accelerations can be compared to actual accelerometer measurements to determine the latitude and longitude of the stationary object.

Chiral EFT based nuclear forces: achievements and challenges

NASA Astrophysics Data System (ADS)

Machleidt, R.; Sammarruca, F.

2016-08-01

During the past two decades, chiral effective field theory has become a popular tool to derive nuclear forces from first principles. Two-nucleon interactions have been worked out up to sixth order of chiral perturbation theory and three-nucleon forces up to fifth order. Applications of some of these forces have been conducted in nuclear few- and many-body systems—with a certain degree of success. But in spite of these achievements, we are still faced with great challenges. Among them is the issue of a proper uncertainty quantification of predictions obtained when applying these forces in ab initio calculations of nuclear structure and reactions. A related problem is the order by order convergence of the chiral expansion. We start this review with a pedagogical introduction and then present the current status of the field of chiral nuclear forces. This is followed by a discussion of representative examples for the application of chiral two- and three-body forces in the nuclear many-body system including convergence issues.

Densification of Zirconia with Borates.

DTIC Science & Technology

1980-01-24

solid electrolytes for fuel cell and oxygen sensor applications.1 ’ 2 The sintering temperatures for commercial quality stabilized zirconia powders are...in the temperature range 1450-1500C). A few studies were also made using a much coarser particle size (- 1-2 pm ave.) cubic stabilized zirconia ... powder , "Zircoa B" [Zirconia Corp. of America]. The additives used as sintering aids were reagent grade horic anhydride, calcium metaborate and calcium

Influence of CAD/CAM systems and cement selection on marginal discrepancy of zirconia-based ceramic crowns.

PubMed

Martínez-Rus, Francisco; Suárez, María J; Rivera, Begoña; Pradíes, Guillermo

2012-04-01

To analyze the effect of ceramic manufacturing technique and luting cement selection on the marginal adaptation of zirconium oxide-based all-ceramic crowns. An extracted mandibular first premolar was prepared for a complete coverage restoration and subsequently duplicated 40 times in a liquid crystal polymer (LCP). All-ceramic crowns (n = 10) were fabricated on LCP models using the following systems: glass-infiltrated zirconia-toughened alumina (In-Ceram Zirconia) and yttrium cation-doped tetragonal zirconia polycrystals (In-Ceram YZ, Cercon, and Procera Zirconia). The restorations (n = 5) were cemented on their respective dies with glass-ionomer cement (Ketac Cem Aplicap) and resin cement (Panavia 21). The absolute marginal discrepancy of the crowns was measured before and after cementation by scanning electronic microscopy at 160 points along the circumferential margin. The data were analyzed using one-way ANOVA for repeated measures and for independent samples, Scheffé's multiple range post hoc test, and Student's t-test (alpha = 0.05). There were statistical differences in the mean marginal openings among the four all-ceramic systems before and after luting (P < 0.0001). The Procera restorations had the lowest pre- and post-cementation values (P < 0.0001). A significant increase in the marginal gap size caused by luting media occurred in all tested groups (P < 0.0001). Resin cement resulted in larger marginal discrepancies than glass-ionomer cement (P < 0.0001).

Immobilized-type chiral packing materials for HPLC based on polysaccharide derivatives.

PubMed

Ikai, Tomoyuki; Yamamoto, Chiyo; Kamigaito, Masami; Okamoto, Yoshio

2008-11-01

The polysaccharide-based chiral packing materials (CPMs) for high-performance liquid chromatography (HPLC) have been recognized as the most powerful ones for the analyzing and preparative separating of the chiral compounds. These CPMs have been conventionally prepared by coating polysaccharide derivatives on a silica gel support. This means that the solvents, which swell or dissolve the derivatives on the silica gel and reduce the performance of the chiral columns, do not allow to be applied as components of the eluents. Therefore, the polysaccharide-based CPMs can be used with a rather limited number of eluents. In order to enhance the versatility of the eluent selection for more practical and economical chromatographic enantioseparations, the polysaccharide derivatives must be immobilized onto the silica gel. This review summarizes our latest studies on the development of the immobilized-type CPMs via the radical copolymerization and the polycondensation of the polysaccharide derivatives bearing small amounts of vinyl groups and alkoxysilyl groups, respectively.

Competitive chiral induction in a 2D molecular assembly: Intrinsic chirality versus coadsorber-induced chirality.

PubMed

Chen, Ting; Li, Shu-Ying; Wang, Dong; Wan, Li-Jun

2017-11-01

Noncovalently introducing stereogenic information is a promising approach to embed chirality in achiral molecular systems. However, the interplay of the noncovalently introduced chirality with the intrinsic chirality of molecules or molecular aggregations has rarely been addressed. We report a competitive chiral expression of the noncovalent interaction-mediated chirality induction and the intrinsic stereogenic center-controlled chirality induction in a two-dimensional (2D) molecular assembly at the liquid/solid interface. Two enantiomorphous honeycomb networks are formed by the coassembly of an achiral 5-(benzyloxy)isophthalic acid (BIC) derivative and 1-octanol at the liquid/solid interface. The preferential formation of the globally homochiral assembly can be achieved either by using the chiral analog of 1-octanol, ( S )-6-methyl-1-octanol, as a chiral coadsorber to induce chirality to the BIC assembly via noncovalent hydrogen bonding or by covalently linking a chiral center in the side chain of BIC. Both the chiral coadsorber and the intrinsically chiral BIC derivative can act as a chiral seeds to induce a preferred handedness in the assembly of the achiral BIC derivatives. Furthermore, the noncovalent interaction-mediated chirality induction can restrain or even overrule the manifestation of the intrinsic chirality of the BIC molecule and dominate the handedness of the 2D molecular coassembly. This study provides insight into the interplay of intrinsically chiral centers and external chiral coadsorbers in the chiral induction, transfer, and amplification processes of 2D molecular assembly.

Competitive chiral induction in a 2D molecular assembly: Intrinsic chirality versus coadsorber-induced chirality

PubMed Central

Chen, Ting; Li, Shu-Ying; Wang, Dong; Wan, Li-Jun

2017-01-01

Noncovalently introducing stereogenic information is a promising approach to embed chirality in achiral molecular systems. However, the interplay of the noncovalently introduced chirality with the intrinsic chirality of molecules or molecular aggregations has rarely been addressed. We report a competitive chiral expression of the noncovalent interaction–mediated chirality induction and the intrinsic stereogenic center–controlled chirality induction in a two-dimensional (2D) molecular assembly at the liquid/solid interface. Two enantiomorphous honeycomb networks are formed by the coassembly of an achiral 5-(benzyloxy)isophthalic acid (BIC) derivative and 1-octanol at the liquid/solid interface. The preferential formation of the globally homochiral assembly can be achieved either by using the chiral analog of 1-octanol, (S)-6-methyl-1-octanol, as a chiral coadsorber to induce chirality to the BIC assembly via noncovalent hydrogen bonding or by covalently linking a chiral center in the side chain of BIC. Both the chiral coadsorber and the intrinsically chiral BIC derivative can act as a chiral seeds to induce a preferred handedness in the assembly of the achiral BIC derivatives. Furthermore, the noncovalent interaction–mediated chirality induction can restrain or even overrule the manifestation of the intrinsic chirality of the BIC molecule and dominate the handedness of the 2D molecular coassembly. This study provides insight into the interplay of intrinsically chiral centers and external chiral coadsorbers in the chiral induction, transfer, and amplification processes of 2D molecular assembly. PMID:29119137

Synthesis and chromatographic characterization of dextran-coated zirconia high-performance liquid chromatographic stationary phases.

PubMed

Dunlap, C J; Carr, P W

1996-10-11

Porous zirconia particles made by the oil emulsion (OE) method and the polymerization-induced colloid aggregation (PICA) method have been coated with a small, carboxymethylated (approximately 5%) dextran polymer and crosslinked in place. The parameters of the coating process (dextran concentration, adsorption time and crosslinker concentration) have all been examined and an optimum value for each determined. The coated and uncoated materials were characterized by nitrogen sorptometry and size-exclusion chromatography (SEC) using solutes (polystyrenes and dextrans) of well-defined molecular masses. Nitrogen sorptometry results show that the PICA material has a much lower pore volume and smaller pore diameter than do the OE materials. Despite this, the elution volumes of the SEC probes change very little upon polymer coating the PICA material while the OE material shows a very large change upon coating.

Biological and nano-indentation properties of polybenzoxazine-based composites reinforced with zirconia particles as a novel biomaterial.

PubMed

Lotfi, L; Javadpour, J; Naimi-Jamal, M R

2018-01-01

The biological and mechanical properties of substances are relevant to their application as biomaterials and there are many efforts to enhance biocompatibility and mechanical properties of bio-medical materials. In this study, to achieve a low rate of shrinkage during polymerization, good mechanical properties, and excellent biocompatibility, benzoxazine based composites were synthesized. Benzoxazine monomer was synthesized using a solventless method. FTIR and DSC analysis were carried out to determine the appropriate polymerization temperature. The low viscosity of the benzoxazine monomer at 70°C attract us to use in situ polymerization after high speed ball milling of the benzoxazine and it mixture with different weight fractions of zirconia particles. Dispersion and adhesion between the ceramic and polymer components were evaluate by SEM. To evaluate the biological properties and toxicity of the polybenzoxazine-based composite samples reinforced with zirconia particles, 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide assay was conducted. The micromechanical properties of each composite were evaluated by more than 20 nanoindentation tests and 3 nanoscratching tests. Surface topography of scratched regions was investigated using Atomic Force Microscopy. Shrinkage was simulated by Materials Studio software. SEM images showed good dispersion and adhesion between the ceramic and polymer components. Biocompatibility assay showed excellent in vitro biocompatibility. Nano-indentation force-displacement curves showed matrix, reinforcement and interphase regions in specimens and excellent homogeneity in mechanical properties. The nanoindentation results showed that the addition of zirconia particles to the polybenzoxazine matrix increased the modulus and hardness of the neat polybenzoxazine; however, by adding more than an optimum level of reinforcement particles, the mechanical properties decreased due to the agglomeration of reinforcement particles and

Stock Versus CAD/CAM Customized Zirconia Implant Abutments - Clinical and Patient-Based Outcomes in a Randomized Controlled Clinical Trial.

PubMed

Schepke, Ulf; Meijer, Henny J A; Kerdijk, Wouter; Raghoebar, Gerry M; Cune, Marco

2017-02-01

Single-tooth replacement often requires a prefabricated dental implant and a customized crown. The benefits of individualization of the abutment remain unclear. This randomized controlled clinical trial aims to study potential benefits of individualization of zirconia implant abutments with respect to preservation of marginal bone level and several clinical and patient-based outcome measures. Fifty participants with a missing premolar were included and randomly assigned to standard (ZirDesign, DentsplySirona Implants, Mölndal, Sweden) or computer aided design/computer aided manufacturing (CAD/CAM) customized (Atlantis, DentsplySirona Implants, Mölndal, Sweden) zirconia abutment therapy. Peri-implant bone level (primary outcome), Plaque-index, calculus formation, bleeding on probing, gingiva index, probing pocket depth, recession, appearance of soft tissues and patients' contentment were assessed shortly after placement and one year later. No implants were lost and no complications related to the abutments were observed. Statistically significant differences between stock and CAD/CAM customized zirconia abutments could not be demonstrated for any of the operationalized variables. The use of a CAD/CAM customized zirconia abutment in single tooth replacement of a premolar is not associated with an improvement in clinical performance or patients' contentment when compared to the use of a stock zirconia abutment. © 2016 The Authors. Clinical Implant Dentistry and Related Research Published by Wiley Periodicals, Inc.

Bolometric-Effect-Based Wavelength-Selective Photodetectors Using Sorted Single Chirality Carbon Nanotubes

PubMed Central

Zhang, Suoming; Cai, Le; Wang, Tongyu; Shi, Rongmei; Miao, Jinshui; Wei, Li; Chen, Yuan; Sepúlveda, Nelson; Wang, Chuan

2015-01-01

This paper exploits the chirality-dependent optical properties of single-wall carbon nanotubes for applications in wavelength-selective photodetectors. We demonstrate that thin-film transistors made with networks of carbon nanotubes work effectively as light sensors under laser illumination. Such photoresponse was attributed to photothermal effect instead of photogenerated carriers and the conclusion is further supported by temperature measurements. Additionally, by using different types of carbon nanotubes, including a single chirality (9,8) nanotube, the devices exhibit wavelength-selective response, which coincides well with the absorption spectra of the corresponding carbon nanotubes. This is one of the first reports of controllable and wavelength-selective bolometric photoresponse in macroscale assemblies of chirality-sorted carbon nanotubes. The results presented here provide a viable route for achieving bolometric-effect-based photodetectors with programmable response spanning from visible to near-infrared by using carbon nanotubes with pre-selected chiralities. PMID:26643777

Origami-Based Reconfigurable Metamaterials for Tunable Chirality.

PubMed

Wang, Zuojia; Jing, Liqiao; Yao, Kan; Yang, Yihao; Zheng, Bin; Soukoulis, Costas M; Chen, Hongsheng; Liu, Yongmin

2017-07-01

Origami is the art of folding two-dimensional (2D) materials, such as a flat sheet of paper, into complex and elaborate three-dimensional (3D) objects. This study reports origami-based metamaterials whose electromagnetic responses are dynamically controllable via switching the folding state of Miura-ori split-ring resonators. The deformation of the Miura-ori unit along the third dimension induces net electric and magnetic dipoles of split-ring resonators parallel or anti-parallel to each other, leading to the strong chiral responses. Circular dichroism as high as 0.6 is experimentally observed while the chirality switching is realized by controlling the deformation direction and kinematics. In addition, the relative density of the origami metamaterials can be dramatically reduced to only 2% of that of the unfolded structure. These results open a new avenue toward lightweight, reconfigurable, and deployable metadevices with simultaneously customized electromagnetic and mechanical properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stock Versus CAD/CAM Customized Zirconia Implant Abutments – Clinical and Patient‐Based Outcomes in a Randomized Controlled Clinical Trial

PubMed Central

Meijer, Henny J.A.; Kerdijk, Wouter; Raghoebar, Gerry M.; Cune, Marco

2016-01-01

Abstract Background Single‐tooth replacement often requires a prefabricated dental implant and a customized crown. The benefits of individualization of the abutment remain unclear. Purpose This randomized controlled clinical trial aims to study potential benefits of individualization of zirconia implant abutments with respect to preservation of marginal bone level and several clinical and patient‐based outcome measures. Material and Methods Fifty participants with a missing premolar were included and randomly assigned to standard (ZirDesign, DentsplySirona Implants, Mölndal, Sweden) or computer aided design/computer aided manufacturing (CAD/CAM) customized (Atlantis, DentsplySirona Implants, Mölndal, Sweden) zirconia abutment therapy. Peri‐implant bone level (primary outcome), Plaque‐index, calculus formation, bleeding on probing, gingiva index, probing pocket depth, recession, appearance of soft tissues and patients' contentment were assessed shortly after placement and one year later. Results No implants were lost and no complications related to the abutments were observed. Statistically significant differences between stock and CAD/CAM customized zirconia abutments could not be demonstrated for any of the operationalized variables. Conclusion The use of a CAD/CAM customized zirconia abutment in single tooth replacement of a premolar is not associated with an improvement in clinical performance or patients' contentment when compared to the use of a stock zirconia abutment. PMID:27476829

Adhesion/cementation to zirconia and other non-silicate ceramics: Where are we now?

PubMed Central

Thompson, Jeffrey Y; Stoner, Brian R.; Piascik, Jeffrey R.; Smith, Robert

2010-01-01

Non-silicate ceramics, especially zirconia, have become a topic of great interest in the field of prosthetic and implant dentistry. A clinical problem with use of zirconia-based components is the difficulty in achieving suitable adhesion with intended synthetic substrates or natural tissues. Traditional adhesive techniques used with silica-based ceramics do not work effectively with zirconia. Currently, several technologies are being utilized clinically to address this problem, and other approaches are under investigation. Most focus on surface modification of the inert surfaces of high strength ceramics. The ability to chemically functionalize the surface of zirconia appears to be critical in achieving adhesive bonding. This review will focus on currently available approaches as well as new advanced technologies to address this problem. PMID:21094526

Preparative supercritical fluid chromatography: A powerful tool for chiral separations.

PubMed

Speybrouck, David; Lipka, Emmanuelle

2016-10-07

In 2012, the 4 biggest pharmaceutical blockbusters were pure enantiomers and separating racemic mixtures is now frequently a key step in the development of a new drug. For a long time, preparative liquid chromatography was the technique of choice for the separation of chiral compounds either during the drug discovery process to get up to a hundred grams of a pure enantiomer or during the clinical trial phases needing kilograms of material. However the advent of supercritical Fluid Chromatography (SFC) in the 1990s has changed things. Indeed, the use of carbon dioxide as the mobile phase in SFC offers many advantages including high flow rate, short equilibration time as well as low solvent consumption. Despite some initial teething troubles, SFC is becoming the primary method for preparative chiral chromatography. This article will cover recent developments in preparative SFC for the separation of enantiomers, reviewing several aspects such as instrumentation, chiral stationary phases, mobile phases or purely preparative considerations including overloading, productivity or large scale chromatography. Copyright © 2016 Elsevier B.V. All rights reserved.

CAD/CAM ZIRCONIA VS. SLIP-CAST GLASS-INFILTRATED ALUMINA/ZIRCONIA ALL-CERAMIC CROWNS: 2-YEAR RESULTS OF A RANDOMIZED CONTROLLED CLINICAL TRIAL

PubMed Central

Çehreli, Murat Cavit; Kökat, Ali Murat; Akça, Kivanç

2009-01-01

The aim of this randomized controlled clinical trial was to compare the early clinical outcome of slip-cast glass-infiltrated Alumina/Zirconia and CAD/CAM Zirconia all-ceramic crowns. A total of 30 InCeram® Zirconia and Cercon® Zirconia crowns were fabricated and cemented with a glass ionomer cement in 20 patients. At baseline, 6-month, 1-year, and 2-year recall appointments, Californian Dental Association (CDA) quality evaluation system was used to evaluate the prosthetic replacements, and plaque and gingival index scores were used to explore the periodontal outcome of the treatments. No clinical sign of marginal discoloration, persistent pain and secondary caries was detected in any of the restorations. All InCeram® Zirconia crowns survived during the 2-year period, although one nonvital tooth experienced root fracture coupled with the fracture of the veneering porcelain of the restoration. One Cercon® Zirconia restoration fractured and was replaced. According to the CDA criteria, marginal integrity was rated excellent for InCeram® Zirconia (73%) and Cercon® Zirconia (80%) restorations, respectively. Slight color mismatch rate was higher for InCeram® Zirconia restorations (66%) than Cercon® Zirconia (26%) restorations. Plaque and gingival index scores were mostly zero and almost constant over time. Time-dependent changes in plaque and gingival index scores within and between groups were statistically similar (p>0.05). This clinical study demonstrates that single-tooth InCeram® Zirconia and Cercon® Zirconia crowns have comparable early clinical outcome, both seem as acceptable treatment modalities, and most importantly, all-ceramic alumina crowns strengthened by 25% zirconia can sufficiently withstand functional load in the posterior zone. PMID:19148406

Biaxial flexural strength of bilayered zirconia using various veneering ceramics

PubMed Central

Chantranikul, Natravee

2015-01-01

PURPOSE The aim of this study was to evaluate the biaxial flexural strength (BFS) of one zirconia-based ceramic used with various veneering ceramics. MATERIALS AND METHODS Zirconia core material (Katana) and five veneering ceramics (Cerabien ZR; CZR, Lava Ceram; LV, Cercon Ceram Kiss; CC, IPS e.max Ceram; EM and VITA VM9; VT) were selected. Using the powder/liquid layering technique, bilayered disk specimens (diameter: 12.50 mm, thickness: 1.50 mm) were prepared to follow ISO standard 6872:2008 into five groups according to veneering ceramics as follows; Katana zirconia veneering with CZR (K/CZR), Katana zirconia veneering with LV (K/LV), Katana zirconia veneering with CC (K/CC), Katana zirconia veneering with EM (K/EM) and Katana zirconia veneering with VT (K/VT). After 20,000 thermocycling, load tests were conducted using a universal testing machine (Instron). The BFS were calculated and analyzed with one-way ANOVA and Tukey HSD (α=0.05). The Weibull analysis was performed for reliability of strength. The mode of fracture and fractured surface were observed by SEM. RESULTS It showed that K/CC had significantly the highest BFS, followed by K/LV. BFS of K/CZR, K/EM and K/VT were not significantly different from each other, but were significantly lower than the other two groups. Weibull distribution reported the same trend of reliability as the BFS results. CONCLUSION From the result of this study, the BFS of the bilayered zirconia/veneer composite did not only depend on the Young's modulus value of the materials. Further studies regarding interfacial strength and sintering factors are necessary to achieve the optimal strength. PMID:26576251

Gelation induced supramolecular chirality: chirality transfer, amplification and application.

PubMed

Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

2014-08-14

Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

Development of zirconia based phosphors for application in lighting and as luminescent bioprobes =

NASA Astrophysics Data System (ADS)

Soares, Maria Rosa Nunes

The strong progress evidenced in photonic and optoelectronic areas, accompanied by an exponential development in the nanoscience and nanotechnology, gave rise to an increasing demand for efficient luminescent materials with more and more exigent characteristics. In this field, wide band gap hosts doped with lanthanide ions represent a class of luminescent materials with a strong technological importance. Within wide band gap material, zirconia owns a combination of physical and chemical properties that potentiate it as an excellent host for the aforementioned ions, envisaging its use in different areas, including in lighting and optical sensors applications, such as pressure sensors and biosensors. Following the demand for outstanding luminescent materials, there is also a request for fast, economic and an easy scale-up process for their production. Regarding these demands, laser floating zone, solution combustion synthesis and pulsed laser ablation in liquid techniques are explored in this thesis for the production of single crystals, nanopowders and nanoparticles of lanthanides doped zirconia based hosts. Simultaneously, a detailed study of the morphological, structural and optical properties of the produced materials is made. The luminescent characteristics of zirconia and yttria stabilized zirconia (YSZ) doped with different lanthanide ions (Ce3+ (4f1), Pr3+ (4f2), Sm3+ (4f5), Eu3+ (4f6), Tb3+ (4f8), Dy3+ (4f9), Er3+ (4f11), Tm3+ (4f12), Yb3+ (4f13)) and co-doped with Er3+,Yb3+ and Tm3+,Yb3+ are analysed. Besides the Stokes luminescence, the anti- Stokes emission upon infrared excitation (upconversion and black body radiation) is also analysed and discussed. The comparison of the luminescence characteristics in materials with different dimensions allowed to analyse the effect of size in the luminescent properties of the dopant lanthanide ions. The potentialities of application of the produced luminescent materials in solid state light, biosensors and pressure

A review of engineered zirconia surfaces in biomedical applications

PubMed Central

Yin, Ling; Nakanishi, Yoshitaka; Alao, Abdur-Rasheed; Song, Xiao-Fei; Abduo, Jaafar; Zhang, Yu

2017-01-01

Zirconia is widely used for load-bearing functional structures in medicine and dentistry. The quality of engineered zirconia surfaces determines not only the fracture and fatigue behaviour but also the low temperature degradation (ageing sensitivity), bacterial colonization and bonding strength of zirconia devices. This paper reviews the current manufacturing techniques for fabrication of zirconia surfaces in biomedical applications, particularly, in tooth and joint replacements, and influences of the zirconia surface quality on their functional behaviours. It discusses emerging manufacturing techniques and challenges for fabrication of zirconia surfaces in biomedical applications. PMID:29130030

Chiral Separations

NASA Astrophysics Data System (ADS)

Stalcup, A. M.

2010-07-01

The main goal of this review is to provide a brief overview of chiral separations to researchers who are versed in the area of analytical separations but unfamiliar with chiral separations. To researchers who are not familiar with this area, there is currently a bewildering array of commercially available chiral columns, chiral derivatizing reagents, and chiral selectors for approaches that span the range of analytical separation platforms (e.g., high-performance liquid chromatography, gas chromatography, supercritical-fluid chromatography, and capillary electrophoresis). This review begins with a brief discussion of chirality before examining the general strategies and commonalities among all of the chiral separation techniques. Rather than exhaustively listing all the chiral selectors and applications, this review highlights significant issues and differences between chiral and achiral separations, providing salient examples from specific classes of chiral selectors where appropriate.

Effect of sandblasting on surface roughness of zirconia-based ceramics and shear bond strength of veneering porcelain.

PubMed

He, Min; Zhang, Zutai; Zheng, Dongxiang; Ding, Ning; Liu, Yan

2014-01-01

This study aims to investigate the effect of sandblasting on the surface roughness of zirconia and the shear bond strength of the veneering porcelain. Pre-sintered zirconia plates were prepared and divided into four groups. Group A were not treated at all; group B were first sandblasted under 0.2 MPa pressure and then densely sintered; group C and D were sintered first, and then sandblasted under 0.2 MPa and 0.4 MPa pressures respectively. Surface roughness was measured and 3D roughness was reconstructed for the specimens, which were also analyzed with X-ray diffractometry. Finally after veneering porcelain sintering, shear bond tests were conducted. Sandblasting zirconia before sintering significantly increased surface roughness and the shear bond strength between zirconia and veneering porcelain (p<0.05). Sandblasting zirconia before sintering is a useful method to increase surface roughness and could successfully improve the bonding strength of veneering porcelain.

Reactions of yttria-stabilized zirconia with oxides and sulfates of various elements

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1978-01-01

The reactions between partially stabilized zirconia, containing 8 weight-percent yttria, and oxides and sulfates of various elements were studied at 1200, 1300, and 1400 C for times to 800, 400, and 200 hours, respectively. These oxides and sulfates represent impurities and additives potentially present in gas turbine fuels or impurities in the turbine combustion air as well as the elements of the substrate alloys in contact with zirconia. Based on the results, these compounds can be classified in four groups: (1) compounds which did not react with zirconia (Na2SO4, K2SO4, Cr2O3, Al2O3 and NiO); (2) compounds that reached completely with both zirconia phases (CaO, BaO, and BaSO4); (3) compounds that reacted preferentially with monoclinic zirconia (Na2O, K2O, CoO, Fe2O3, MgO, SiO2, and ZnO); and (4) compounds that reacted preferentially with cubic zirconia (V2O5, P2O5).

A chiral-based magnetic memory device without a permanent magnet

PubMed Central

Dor, Oren Ben; Yochelis, Shira; Mathew, Shinto P.; Naaman, Ron; Paltiel, Yossi

2013-01-01

Several technologies are currently in use for computer memory devices. However, there is a need for a universal memory device that has high density, high speed and low power requirements. To this end, various types of magnetic-based technologies with a permanent magnet have been proposed. Recent charge-transfer studies indicate that chiral molecules act as an efficient spin filter. Here we utilize this effect to achieve a proof of concept for a new type of chiral-based magnetic-based Si-compatible universal memory device without a permanent magnet. More specifically, we use spin-selective charge transfer through a self-assembled monolayer of polyalanine to magnetize a Ni layer. This magnitude of magnetization corresponds to applying an external magnetic field of 0.4 T to the Ni layer. The readout is achieved using low currents. The presented technology has the potential to overcome the limitations of other magnetic-based memory technologies to allow fabricating inexpensive, high-density universal memory-on-chip devices. PMID:23922081

A chiral-based magnetic memory device without a permanent magnet.

PubMed

Ben Dor, Oren; Yochelis, Shira; Mathew, Shinto P; Naaman, Ron; Paltiel, Yossi

2013-01-01

Several technologies are currently in use for computer memory devices. However, there is a need for a universal memory device that has high density, high speed and low power requirements. To this end, various types of magnetic-based technologies with a permanent magnet have been proposed. Recent charge-transfer studies indicate that chiral molecules act as an efficient spin filter. Here we utilize this effect to achieve a proof of concept for a new type of chiral-based magnetic-based Si-compatible universal memory device without a permanent magnet. More specifically, we use spin-selective charge transfer through a self-assembled monolayer of polyalanine to magnetize a Ni layer. This magnitude of magnetization corresponds to applying an external magnetic field of 0.4 T to the Ni layer. The readout is achieved using low currents. The presented technology has the potential to overcome the limitations of other magnetic-based memory technologies to allow fabricating inexpensive, high-density universal memory-on-chip devices.

Novel electrochemical method for the characterization of the degree of chirality in chiral polyaniline.

PubMed

Feng, Zhang; Li, Ma; Yan, Yang; Jihai, Tang; Xiao, Li; Wanglin, Li

2013-01-01

A novel method to indicate the degree of chirality in polyaniline (PANI) was developed. The (D-camphorsulfonic acid)- and (HCl)-PANI-based electrodes exhibited significantly different electrochemical performances in D- and L-Alanine (Ala) aqueous solution, respectively, which can be used for the characterization the optical activity of chiral PANI. Cyclic voltammogram, tafel, and open circuit potential of PANI-based electrodes were measured within D- and L-Ala electrolyte solution, respectively. The open circuit potentials under different reacting conditions were analyzed by Doblhofer model formula, in which [C(+)](poly1)/[C(+)](poly2) was used as a parameter to characterize the degree of chirality in chiral PANI. The results showed that [C(+)](poly1)/[C(+)](poly2) can be increased with increasing concentrations of (1S)-(+)- and (1R)-(-)-10-camphorsulfonic acid. In addition, we detected that appropriate response time and lower temperature are necessary to improve the degree of chirality. Copyright © 2012 Wiley Periodicals, Inc.

Evaluation of experimental coating to improve the zirconia-veneering ceramic bond strength.

PubMed

Matani, Jay D; Kheur, Mohit; Jambhekar, Shantanu Subhashchandra; Bhargava, Parag; Londhe, Aditya

2014-12-01

To evaluate the shear bond strength (SBS) between zirconia and veneering ceramic following different surface treatments of zirconia. The efficacy of an experimental zirconia coating to improve the bond strength was also evaluated. Zirconia strips were fabricated and were divided into four groups as per their surface treatment: polished (control), airborne-particle abrasion, laser irradiation, and application of the experimental coating. The surface roughness and the residual monoclinic content were evaluated before and after the respective surface treatments. A scanning electron microscope (SEM) analysis of the experimental surfaces was performed. All specimens were subjected to shear force in a universal testing machine. The SBS values were analyzed with one-way ANOVA followed by Bonferroni post hoc for groupwise comparisons. The fractured specimens were examined to observe the failure mode. The SBS (29.17 MPa) and roughness values (0.80) of the experimental coating group were the highest among the groups. The residual monoclinic content was minimal (0.32) when compared to the remaining test groups. SEM analysis revealed a homogenous surface well adhered to an undamaged zirconia base. The other test groups showed destruction of the zirconia surface. The analysis of failure following bond strength testing showed entirely cohesive failures in the veneering ceramic in all study groups. The experimental zirconia surface coating is a simple technique to increase the microroughness of the zirconia surface, and thereby improve the SBS to the veneering ceramic. It results in the least monoclinic content and produces no structural damage to the zirconia substructure. © 2014 by the American College of Prosthodontists.

Versatile ligands for high-performance liquid chromatography: An overview of ionic liquid-functionalized stationary phases.

PubMed

Zhang, Mingliang; Mallik, Abul K; Takafuji, Makoto; Ihara, Hirotaka; Qiu, Hongdeng

2015-08-05

Ionic liquids (ILs), a class of unique substances composed purely by cation and anions, are renowned for their fascinating physical and chemical properties, such as negligible volatility, high dissolution power, high thermal stability, tunable structure and miscibility. They are enjoying ever-growing applications in a great diversity of disciplines. IL-modified silica, transforming the merits of ILs into chromatographic advantages, has endowed the development of high-performance liquid chromatography (HPLC) stationary phase with considerable vitality. In the last decade, IL-functionalized silica stationary phases have evolved into a series of branches to accommodate to different HPLC modes. An up-to-date overview of IL-immobilized stationary phases is presented in this review, and divided into five parts according to application mode, i.e., ion-exchange, normal-phase, reversed-phase, hydrophilic interaction and chiral recognition. Specific attention is channeled to synthetic strategies, chromatographic behavior and separation performance of IL-functionalized silica stationary phases. Copyright © 2015 Elsevier B.V. All rights reserved.

Osseointegration of zirconia implants: an SEM observation of the bone-implant interface.

PubMed

Depprich, Rita; Zipprich, Holger; Ommerborn, Michelle; Mahn, Eduardo; Lammers, Lydia; Handschel, Jörg; Naujoks, Christian; Wiesmann, Hans-Peter; Kübler, Norbert R; Meyer, Ulrich

2008-11-06

The successful use of zirconia ceramics in orthopedic surgery led to a demand for dental zirconium-based implant systems. Because of its excellent biomechanical characteristics, biocompatibility, and bright tooth-like color, zirconia (zirconium dioxide, ZrO2) has the potential to become a substitute for titanium as dental implant material. The present study aimed at investigating the osseointegration of zirconia implants with modified ablative surface at an ultrastructural level. A total of 24 zirconia implants with modified ablative surfaces and 24 titanium implants all of similar shape and surface structure were inserted into the tibia of 12 Göttinger minipigs. Block biopsies were harvested 1 week, 4 weeks or 12 weeks (four animals each) after surgery. Scanning electron microscopy (SEM) analysis was performed at the bone implant interface. Remarkable bone attachment was already seen after 1 week which increased further to intimate bone contact after 4 weeks, observed on both zirconia and titanium implant surfaces. After 12 weeks, osseointegration without interposition of an interfacial layer was detected. At the ultrastructural level, there was no obvious difference between the osseointegration of zirconia implants with modified ablative surfaces and titanium implants with a similar surface topography. The results of this study indicate similar osseointegration of zirconia and titanium implants at the ultrastructural level.

Chirality-controlled crystallization via screw dislocations.

PubMed

Sung, Baeckkyoung; de la Cotte, Alexis; Grelet, Eric

2018-04-11

Chirality plays an important role in science from enantiomeric separation in chemistry to chiral plasmonics in nanotechnology. However, the understanding of chirality amplification from chiral building blocks to ordered helical superstructures remains a challenge. Here, we demonstrate that topological defects, such as screw dislocations, can drive the chirality transfer from particle to supramolecular structure level during the crystallization process. By using a model system of chiral particles, which enables direct imaging of single particle incorporation into growing crystals, we show that the crystallization kinetic pathway is the key parameter for monitoring, via the defects, the chirality amplification of the crystalline structures from racemic to predominantly homohelical. We provide an explanation based on the interplay between geometrical frustration, racemization induced by thermal fluctuations, and particle chirality. Our results demonstrate that screw dislocations not only promote the growth, but also control the chiral morphology and therefore the functionality of crystalline states.

Multilayered thermal insulation formed of zirconia bonded layers of zirconia fibers and metal oxide fibers and method for making same

DOEpatents

Wrenn, Jr., George E.; Holcombe, Jr., Cressie E.

1988-01-01

A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

Multilayered thermal insulation formed of zirconia bonded layers of zirconia fibers and metal oxide fibers and method for making same

DOEpatents

Wrenn, G.E. Jr.; Holcombe, C.E. Jr.

1988-09-13

A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

Structural insights into two inorganic-organic hybrids based on chiral amino acids and polyoxomolybdates

NASA Astrophysics Data System (ADS)

Arefian, Mina; Mirzaei, Masoud; Eshtiagh-Hosseini, Hossein

2018-03-01

A new chiral inorganic-organic hybrid with the formula (L-His)2(H7CoMo6O24)·6H2O (1), based on natural amino acid and Anderson type polyoxomolybdate was synthesized through mild condition. The chiral L-histidine molecules induced chirality to the whole structure through various types of strong and unconventional hydrogen bond (HB) interactions (CH⋯O, NH⋯O and CH···π interactions), as well as bifurcated hydrogen bonds (BHBs) between L-histidine amino acid, hexamer water cluster molecules, and H7CoMo6O24·xH2O. Following, important non-covalent CH⋯O interactions is investigated in another chiral inorganic-organic hybrid structure, (L-Pro)3(PMo12O40).4.5H2O (2), in detail. The CH⋯O hydrogen bonds lead to a chiral network similar to the DNA strands affording a promising candidate to bio-inorganic studies.

An implemented method of asymmetric transmission for arbitrary polarization base in multi-layered chiral meta-surface

NASA Astrophysics Data System (ADS)

Xiao, Zhong-yin; Zou, Huan-ling; Xu, Kai-Kai; Tang, Jing-yao

2018-03-01

Asymmetric transmission of linearly or circularly polarized waves is a well-established property not only for three-layered chiral structures but for multi-layered ones. Here we show a method which can simultaneously implement asymmetric transmission for arbitrary base vector polarized wave in multi-layered chiral meta-surface. We systematically study the implemented method based on a multi-layered chiral structure consisting of a y-shape, a half gammadion and an S-shape in the terahertz gap. A numerical simulation was carried out, followed by an explanation of the asymmetric transmission mechanism in these structures proposed in this work. The simulated results indicate that the multi-layered chiral structure can realize a maximum asymmetric transmission of 0.89 and 0.28 for circularly and linearly polarized waves, respectively, which exhibit magnitude improvement over previous chiral metamaterials. Specifically, the maximum asymmetric transmitted coefficient of the multi-layered chiral structure is insensitivity to the incident angles from 0° to 45° for circularly polarized components. Additionally, we also study the influence of structural parameters on the asymmetric transmission effect for both linearly and circularly polarized waves in detail.

Lewis base catalyzed aldol additions of chiral trichlorosilyl enolates and silyl enol ethers.

PubMed

Denmark, Scott E; Fujimori, Shinji; Pham, Son M

2005-12-23

[structures: see text] The consequences of double diastereodifferentiation in chiral Lewis base catalyzed aldol additions using chiral enoxysilanes derived from lactate, 3-hydroxyisobutyrate, and 3-hydroxybutyrate have been investigated. Trichlorosilyl enolates derived from the chiral methyl and ethyl ketones were subjected to aldolization in the presence of phosphoramides, and the intrinsic selectivity of these enolates and the external stereoinduction from chiral catalyst were studied. In the reactions with the lactate derived enolate, the strong internal stereoinduction dominated the stereochemical outcome of the aldol addition. For the 3-hydroxyisobutyrate- and 3-hydroxybutyrate derived enolates, the catalyst-controlled diastereoselectivities were observed, and the resident stereogenic centers exerted marginal influence. The corresponding trimethylsilyl enol ethers were employed in SiCl4/bisphosphoramide catalyzed aldol additions, and the effect of double diastereodifferentiation was also investigated. The overall diastereoselection of the process was again controlled by the strong external influence of the catalyst.

Optical rotation based chirality detection of enantiomers via weak measurement in frequency domain

NASA Astrophysics Data System (ADS)

Li, Dongmei; Guan, Tian; Liu, Fang; Yang, Anping; He, Yonghong; He, Qinghua; Shen, Zhiyuan; Xin, Meiguo

2018-05-01

A transmission optical rotation detection scheme based on a weak measurement was proposed for the chirality detection of enantiomers. In this transmission weak measurement system in the frequency domain, the optical activity of the chiral liquid sample was estimated with the central wavelength shift, by modifying the preselected polarization state with the optical rotation (OR). The central wavelength shift of output spectra is sensitive to the OR angle but immune to the interference of the refractive index change caused by measuring circumstances. Two isomers of chiral amino acid acquired opposite responses with this system, and a resolution of 2.17 × 10-9 mol/ml for Proline detection could be obtained. Such a resolution is about 2 orders of magnitude higher than that of common methods, which shows a high sensitivity. This proposed weak measurement scenario suggested an approach to polarimetry and provided a way to accurately assess molecular chirality.

Zirconia in dental implantology: A review

PubMed Central

Apratim, Abhishek; Eachempati, Prashanti; Krishnappa Salian, Kiran Kumar; Singh, Vijendra; Chhabra, Saurabh; Shah, Sanket

2015-01-01

Background: Titanium has been the most popular material of choice for dental implantology over the past few decades. Its properties have been found to be most suitable for the success of implant treatment. But recently, zirconia is slowly emerging as one of the materials which might replace the gold standard of dental implant, i.e., titanium. Materials and Methods: Literature was searched to retrieve information about zirconia dental implant and studies were critically analyzed. PubMed database was searched for information about zirconia dental implant regarding mechanical properties, osseointegration, surface roughness, biocompatibility, and soft tissue health around it. The literature search was limited to English language articles published from 1975 to 2015. Results: A total of 45 papers met the inclusion criteria for this review, among the relevant search in the database. Conclusion: Literature search showed that some of the properties of zirconia seem to be suitable for making it an ideal dental implant, such as biocompatibility, osseointegration, favourable soft tissue response and aesthetics due to light transmission and its color. At the same time, some studies also point out its drawbacks. It was also found that most of the studies on zirconia dental implants are short-term studies and there is a need for more long-term clinical trials to prove that zirconia is worth enough to replace titanium as a biomaterial in dental implantology. PMID:26236672

Implant-supported fixed dental prostheses with CAD/CAM-fabricated porcelain crown and zirconia-based framework.

PubMed

Takaba, Masayuki; Tanaka, Shinpei; Ishiura, Yuichi; Baba, Kazuyoshi

2013-07-01

Recently, fixed dental prostheses (FDPs) with a hybrid structure of CAD/CAM porcelain crowns adhered to a CAD/CAM zirconia framework (PAZ) have been developed. The aim of this report was to describe the clinical application of a newly developed implant-supported FDP fabrication system, which uses PAZ, and to evaluate the outcome after a maximum application period of 36 months. Implants were placed in three patients with edentulous areas in either the maxilla or mandible. After the implant fixtures had successfully integrated with bone, gold-platinum alloy or zirconia custom abutments were first fabricated. Zirconia framework wax-up was performed on the custom abutments, and the CAD/CAM zirconia framework was prepared using the CAD/CAM system. Next, wax-up was performed on working models for porcelain crown fabrication, and CAD/CAM porcelain crowns were fabricated. The CAD/CAM zirconia frameworks and CAD/CAM porcelain crowns were bonded using adhesive resin cement, and the PAZ was cemented. Cementation of the implant superstructure improved the esthetics and masticatory efficiency in all patients. No undesirable outcomes, such as superstructure chipping, stomatognathic dysfunction, or periimplant bone resorption, were observed in any of the patients. PAZ may be a potential solution for ceramic-related clinical problems such as chipping and fracture and associated complicated repair procedures in implant-supported FDPs. © 2012 by the American College of Prosthodontists.

Light transmittance of zirconia as a function of thickness and microhardness of resin cements under different thicknesses of zirconia

PubMed Central

Egilmez, Ferhan; Ergun, Gulfem; Kaya, Bekir M.

2013-01-01

Objective: The objective of this study was to compare microhardness of resin cements under different thicknesses of zirconia and the light transmittance of zirconia as a function of thickness. Study design: A total of 126 disc-shaped specimens (2 mm in height and 5 mm in diameter) were prepared from dual-cured resin cements (RelyX Unicem, Panavia F and Clearfil SA cement). Photoactivation was performed by using quartz tungsten halogen and light emitting diode light curing units under different thicknesses of zirconia. Then the specimens (n=7/per group) were stored in dry conditions in total dark at 37°C for 24 h. The Vicker’s hardness test was performed on the resin cement layer with a microhardness tester. Statistical significance was determined using multifactorial analysis of variance (ANOVA) (alpha=.05). Light transmittance of different thicknesses of zirconia (0.3, 0.5 and 0.8 mm) was measured using a hand-held radiometer (Demetron, Kerr). Data were analyzed using one-way ANOVA test (alpha=.05). Results: ANOVA revealed that resin cement and light curing unit had significant effects on microhardness (p < 0.001). Additionally, greater zirconia thickness resulted in lower transmittance. There was no correlation between the amount of light transmitted and microhardness of dual-cured resin cements (r = 0.073, p = 0.295). Conclusion: Although different zirconia thicknesses might result in insufficient light transmission, dual-cured resin cements under zirconia restorations could have adequate microhardness. Key words:Zirconia, microhardness, light transmittance, resin cement. PMID:23385497

Towards long lasting zirconia-based composites for dental implants. Part I: innovative synthesis, microstructural characterization and in vitro stability.

PubMed

Palmero, Paola; Fornabaio, Marta; Montanaro, Laura; Reveron, Helen; Esnouf, Claude; Chevalier, Jérôme

2015-05-01

In order to fulfill the clinical requirements for strong, tough and stable ceramics used in dental applications, we designed and developed innovative zirconia-based composites, in which equiaxial α-Al2O3 and elongated SrAl12O19 phases are dispersed in a ceria-stabilized zirconia matrix. The composite powders were prepared by an innovative surface coating route, in which commercial zirconia powders were coated by inorganic precursors of the second phases, which crystallize on the zirconia particles surface under proper thermal treatment. Samples containing four different ceria contents (in the range 10.0-11.5 mol%) were prepared by carefully tailoring the amount of the cerium precursor during the elaboration process. Slip cast green bodies were sintered at 1450 °C for 1 h, leading to fully dense materials. Characterization of composites by SEM and TEM analyses showed highly homogeneous microstructures with an even distribution of both equiaxial and elongated-shape grains inside a very fine zirconia matrix. Ce content plays a major role on aging kinetics, and should be carefully controlled: sample with 10 mol% of ceria were transformable, whereas above 10.5 mol% there is negligible or no transformation during autoclave treatment. Thus, in this paper we show the potential of the innovative surface coating route, which allows a perfect tailoring of the microstructural, morphological and compositional features of the composites; moreover, its processing costs and environmental impacts are limited, which is beneficial for further scale-up and real use in the biomedical field. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chiral Responsive Liquid Quantum Dots.

PubMed

Zhang, Jin; Ma, Junkai; Shi, Fangdan; Tian, Demei; Li, Haibing

2017-08-01

How to convert the weak chiral-interaction into the macroscopic properties of materials remains a huge challenge. Here, this study develops highly fluorescent, selectively chiral-responsive liquid quantum dots (liquid QDs) based on the hydrophobic interaction between the chiral chains and the oleic acid-stabilized QDs, which have been designated as (S)-1810-QDs. The fluorescence spectrum and liquidity of thermal control demonstrate the fluorescence properties and the fluidic behavior of (S)-1810-QDs in the solvent-free state. Especially, (S)-1810-QDs exhibit a highly chiral-selective response toward (1R, 2S)-2-amino-1,2-diphenyl ethanol. It is anticipated that this study will facilitate the construction of smart chiral fluidic sensors. More importantly, (S)-1810-QDs can become an attractive material for chiral separation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of an internal coating technique on tensile bond strengths of resin cements to zirconia ceramics.

PubMed

Kitayama, Shuzo; Nikaido, Toru; Maruoka, Rena; Zhu, Lei; Ikeda, Masaomi; Watanabe, Akihiko; Foxton, Richard M; Miura, Hiroyuki; Tagami, Junji

2009-07-01

This study was conducted to enhance the tensile bond strengths of resin cements to zirconia ceramics. Fifty-six zirconia ceramic specimens (Cercon Base) and twenty-eight silica-based ceramic specimens (GN-1, GN-1 Ceramic Block) were air-abraded using alumina. Thereafter, the zirconia ceramic specimens were divided into two subgroups of 28 each according to the surface pretreatment; no pretreatment (Zr); and the internal coating technique (INT). For INT, the surface of zirconia was coated by fusing silica-based ceramics (Cercon Ceram Kiss). Ceramic surfaces were conditioned with/without a silane coupling agent followed by bonding with one of two resin cements; Panavia F 2.0 (PF) and Superbond C&B (SB). After 24 hours storage in water, the tensile bond strengths were tested (n=7). For both PF and SB, silanization significantly improved the bond strength to GN-1 and INT (p<0.05). The INT coating followed by silanizaton demonstrated enhancement of bonding to zirconia ceramics.

Synthesis and characterization of thermally stable zirconia based mesoporous nanosilica with metalloporphyrin encapsulation

NASA Astrophysics Data System (ADS)

Nadeem, Saad; Iqbal, Farukh; Mutalib, Mohamed Ibrahim Abdul; Abdullah, Bawadi; Shaharun, Maizatul Shima

2017-10-01

Metal composite materials-48 (MCM-48) with silica zirconia mesoporous matrix (having a Zr/Si ratio of 0.02) has been developed successfully using autogenous conditions and Copper tetra phenyl porphyrin (CuTPP) inclusion via flexible ligand approach. Thermo gravimetric analysis (TGA) was used to study the thermal stability which gives the stability up to 700°C, Fourier transform infrared spectroscopy (FTIR) for the functional group attachment also confirmed the MCM-48 structure and the Zirconia addition and X-Ray photon spectroscopy (XPS) for the binding energies and bonding also revealed the surface Zr4+ states. DRS-UV-Vis study for the photophysical behaviour, visible light activation and band gap reduction which reduced from 5.6 to 2.8 eV. All the characterizations have confirmed that nanoscale mesoporous silica with successful inclusion of zirconia in the matrix and the encapsulation of CuTPP was confirmed via diffuse reflectance (DR Uv-Vis) spectroscopy.

Shear bond strength of veneering porcelain to zirconia: Effect of surface treatment by CNC-milling and composite layer deposition on zirconia.

PubMed

Santos, R L P; Silva, F S; Nascimento, R M; Souza, J C M; Motta, F V; Carvalho, O; Henriques, B

2016-07-01

The purpose of this study was to evaluate the shear bond strength of veneering feldspathic porcelain to zirconia substrates modified by CNC-milling process or by coating zirconia with a composite interlayer. Four types of zirconia-porcelain interface configurations were tested: RZ - porcelain bonded to rough zirconia substrate (n=16); PZ - porcelain bonded to zirconia substrate with surface holes (n=16); RZI - application of a composite interlayer between the veneering porcelain and the rough zirconia substrate (n=16); PZI - application of a composite interlayer between the porcelain and the zirconia substrate treated by CNC-milling (n=16). The composite interlayer was composed of zirconia particles reinforced porcelain (30%, vol%). The mechanical properties of the ceramic composite have been determined. The shear bond strength test was performed at 0.5mm/min using a universal testing machine. The interfaces of fractured and untested specimens were examined by FEG-SEM/EDS. Data was analyzed with Shapiro-Wilk test to test the assumption of normality. The one-way ANOVA followed by Tukey HSD multiple comparison test was used to compare shear bond strength results (α=0.05). The shear bond strength of PZ (100±15MPa) and RZI (96±11MPa) specimens were higher than that recorded for RZ (control group) specimens (89±15MPa), although not significantly (p>0.05). The highest shear bond strength values were recorded for PZI specimens (138±19MPa), yielding a significant improvement of 55% relative to RZ specimens (p<0.05). This study shows that it is possible to highly enhance the zirconia-porcelain bond strength - even by ~55% - by combining surface holes in zirconia frameworks and the application of a proper ceramic composite interlayer. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chirality Differentiation by Diffusion in Chiral Nematic Liquid Crystals

NASA Astrophysics Data System (ADS)

Jiang, Jinghua; Yang, Deng-Ke

2017-01-01

Chirality is of great importance in the living world. It helps differentiate biochemical reactions such as those that take place during digestion. It may also help differentiate physical processes such as diffusion. Aiming to study the latter effect, we investigate the diffusion of guest chiral molecules in chiral nematic (cholesteric) liquid-crystal hosts. We discover that the diffusion dramatically depends on the handedness of the guest and host molecules and the chiral differentiation is greatly enhanced by the proper alignment of the liquid-crystal host. The diffusion of a guest chiral molecule in a chiral host with the same handedness is much faster than in a chiral host with opposite handedness. We also observe that the differentiation of chirality depends on the diffusion direction with respect to the twisting direction (helical axis). These results might be important in understanding effects of chirality on physical processes that take place in biological organisms. In addition, this effect could be utilized for enantiomer separation.

Chiral signs of TPPS co-assemblies with chiral gelators: role of molecular and supramolecular chirality.

PubMed

Wang, Qiuling; Zhang, Li; Yang, Dong; Li, Tiesheng; Liu, Minghua

2016-10-13

A dianionic tetrakis(4-sulfonatophenyl)porphyrin (TPPS) self-assembled into J-aggregates when it co-assembled with a chiral cationic amphiphile via supramolecular gelation. The chiral signs of TPPS J aggregates followed the supramolecular chirality of amphiphilic assemblies rather than the molecular chirality of the amphiphile.

Chiral amplification and sensing of chirality with lyotropic chromonic liquid crystals

NASA Astrophysics Data System (ADS)

Srinivasarao, Mohan; Park, Jung Ok; Fu, Jinxin; Nayani, Karthik; Chang, Rui

Due to the anisotropic elastic properties of lyotropic chromonic liquid crystals (LCLCs), a spontaneously twisted chiral structure has been reported in the achiral LCLCs system under cylindrical confinement. It is found that the handedness of chirality could be biased with a minute amount of a chiral additive. The entire system becomes ``homochiral'' and takes on the handedness of the additive. When 1% by weight of L-glutamic acid was added to LCLCs in a cylinder, the LCLC sbecomes homochiral and possesses giant optical rotation. We explore the mechanism for this based on the ``sergeants-and-soldiers'' and the ``majority-rule'' principles known for organic molecular systems.

Novel fabrication method for zirconia restorations: bonding strength of machinable ceramic to zirconia with resin cements.

PubMed

Kuriyama, Soichi; Terui, Yuichi; Higuchi, Daisuke; Goto, Daisuke; Hotta, Yasuhiro; Manabe, Atsufumi; Miyazaki, Takashi

2011-01-01

A novel method was developed to fabricate all-ceramic restorations which comprised CAD/CAM-fabricated machinable ceramic bonded to CAD/CAM-fabricated zirconia framework using resin cement. The feasibility of this fabrication method was assessed in this study by investigating the bonding strength of a machinable ceramic to zirconia. A machinable ceramic was bonded to a zirconia plate using three kinds of resin cements: ResiCem (RE), Panavia (PA), and Multilink (ML). Conventional porcelain-fused-to-zirconia specimens were also prepared to serve as control. Shear bond strength test (SBT) and Schwickerath crack initiation test (SCT) were carried out. SBT revealed that PA (40.42 MPa) yielded a significantly higher bonding strength than RE (28.01 MPa) and ML (18.89 MPa). SCT revealed that the bonding strengths of test groups using resin cement were significantly higher than those of Control. Notably, the bonding strengths of RE and ML were above 25 MPa even after 10,000 times of thermal cycling -adequately meeting the ISO 9693 standard for metal-ceramic restorations. These results affirmed the feasibility of the novel fabrication method, in that a CAD/CAM-fabricated machinable ceramic is bonded to a CAD/CAM-fabricated zirconia framework using a resin cement.

Bonding of Resin Cement to Zirconia with High Pressure Primer Coating

PubMed Central

Wang, Ying-jie; Jiao, Kai; Liu, Yan; Zhou, Wei; Shen, Li-juan; Fang, Ming; Li, Meng; Zhang, Xiang; Tay, Franklin R.; Chen, Ji-hua

2014-01-01

Objectives To investigate the effect of air-drying pressure during ceramic primer coating on zirconia/resin bonding and the surface characteristics of the primed zirconia. Methods Two ceramic primers (Clearfil Ceramic Primer, CCP, Kuraray Medical Inc. and Z-Prime Plus, ZPP, Bisco Inc.) were applied on the surface of air-abraded zirconia (Katana zirconia, Noritake) and dried at 4 different air pressures (0.1–0.4 MPa). The primed zirconia ceramic specimens were bonded with a resin-based luting agent (SA Luting Cement, Kuraray). Micro-shear bond strengths of the bonded specimens were tested after 3 days of water storage or 5,000× thermocycling (n = 12). Failure modes of the fractured specimens were examined with scanning electron miscopy. The effects of air pressure on the thickness of the primer layers and the surface roughness (Sa) of primed zirconia were evaluated using spectroscopic ellipsometry (n = 6), optical profilometry and environmental scanning electron microscopy (ESEM) (n = 6), respectively. Results Clearfil Ceramic Primer air-dried at 0.3 and 0.4 MPa, yielding significantly higher µSBS than gentle air-drying subgroups (p<0.05). Compared to vigorous drying conditions, Z-Prime Plus air-dried at 0.2 MPa exhibited significantly higher µSBS (p<0.05). Increasing air-drying pressure reduced the film thickness for both primers. Profilometry measurements and ESEM showed rougher surfaces in the high pressure subgroups of CCP and intermediate pressure subgroup of ZPP. Conclusion Air-drying pressure influences resin/zirconia bond strength and durability significantly. Higher air-drying pressure (0.3-0.4 MPa) for CCP and intermediate pressure (0.2 MPa) for ZPP are recommended to produce strong, durable bonds between resin cement and zirconia ceramics. PMID:24992678

Timoshenko beam model for chiral materials

NASA Astrophysics Data System (ADS)

Ma, T. Y.; Wang, Y. N.; Yuan, L.; Wang, J. S.; Qin, Q. H.

2017-12-01

Natural and artificial chiral materials such as deoxyribonucleic acid (DNA), chromatin fibers, flagellar filaments, chiral nanotubes, and chiral lattice materials widely exist. Due to the chirality of intricately helical or twisted microstructures, such materials hold great promise for use in diverse applications in smart sensors and actuators, force probes in biomedical engineering, structural elements for absorption of microwaves and elastic waves, etc. In this paper, a Timoshenko beam model for chiral materials is developed based on noncentrosymmetric micropolar elasticity theory. The governing equations and boundary conditions for a chiral beam problem are derived using the variational method and Hamilton's principle. The static bending and free vibration problem of a chiral beam are investigated using the proposed model. It is found that chirality can significantly affect the mechanical behavior of beams, making materials more flexible compared with nonchiral counterparts, inducing coupled twisting deformation, relatively larger deflection, and lower natural frequency. This study is helpful not only for understanding the mechanical behavior of chiral materials such as DNA and chromatin fibers and characterizing their mechanical properties, but also for the design of hierarchically structured chiral materials.

Timoshenko beam model for chiral materials

NASA Astrophysics Data System (ADS)

Ma, T. Y.; Wang, Y. N.; Yuan, L.; Wang, J. S.; Qin, Q. H.

2018-06-01

Natural and artificial chiral materials such as deoxyribonucleic acid (DNA), chromatin fibers, flagellar filaments, chiral nanotubes, and chiral lattice materials widely exist. Due to the chirality of intricately helical or twisted microstructures, such materials hold great promise for use in diverse applications in smart sensors and actuators, force probes in biomedical engineering, structural elements for absorption of microwaves and elastic waves, etc. In this paper, a Timoshenko beam model for chiral materials is developed based on noncentrosymmetric micropolar elasticity theory. The governing equations and boundary conditions for a chiral beam problem are derived using the variational method and Hamilton's principle. The static bending and free vibration problem of a chiral beam are investigated using the proposed model. It is found that chirality can significantly affect the mechanical behavior of beams, making materials more flexible compared with nonchiral counterparts, inducing coupled twisting deformation, relatively larger deflection, and lower natural frequency. This study is helpful not only for understanding the mechanical behavior of chiral materials such as DNA and chromatin fibers and characterizing their mechanical properties, but also for the design of hierarchically structured chiral materials.

Chiral liquid crystal colloids

NASA Astrophysics Data System (ADS)

Yuan, Ye; Martinez, Angel; Senyuk, Bohdan; Tasinkevych, Mykola; Smalyukh, Ivan I.

2018-01-01

Colloidal particles disturb the alignment of rod-like molecules of liquid crystals, giving rise to long-range interactions that minimize the free energy of distorted regions. Particle shape and topology are known to guide this self-assembly process. However, how chirality of colloidal inclusions affects these long-range interactions is unclear. Here we study the effects of distortions caused by chiral springs and helices on the colloidal self-organization in a nematic liquid crystal using laser tweezers, particle tracking and optical imaging. We show that chirality of colloidal particles interacts with the nematic elasticity to predefine chiral or racemic colloidal superstructures in nematic colloids. These findings are consistent with numerical modelling based on the minimization of Landau-de Gennes free energy. Our study uncovers the role of chirality in defining the mesoscopic order of liquid crystal colloids, suggesting that this feature may be a potential tool to modulate the global orientated self-organization of these systems.

Enantiomeric-Enriched Ferrocenes: Synthesis, Chiral Resolution, and Mathematic Evaluation of CD-chiral Selector Energies with Ferrocene-Conjugates.

PubMed

Snegur, Lubov V; Borisov, Yurii A; Kuzmenko, Yuliya V; Davankov, Vadim A; Ilyin, Mikhail M; Ilyin, Mikhail M; Arhipov, Dmitry E; Korlyukov, Alexander A; Kiselev, Sergey S; Simenel, Alexander A

2017-08-25

Enantiomeric-enriched ferrocene-modified pyrazoles were synthesized via the reaction of the ferrocene alcohol, ( S )-FcCH(OH)CH₃ (Fc = ferrocenyl), with various pyrazoles in acidic conditions at room temperature within several minutes. X-ray structural data for racemic ( R , S )-1 N -(3,5-dimethyl pyrazolyl)ethyl ferrocene ( 1 ) and its ( S )-enantiomer ( S )- 1 were determined. A series of racemic pyrazolylalkyl ferrocenes was separated into enantiomers by analytical HPLC on β- and γ-cyclodextrins (CD) chiral stationary phases. The quantum chemical calculations of interaction energies of β-CD were carried out for both ( R )- and ( S )-enantiomers. A high correlation between experimental HPLC data and calculated interaction energies values was obtained.

Long-Term Effects on Graphene Supercapacitors of Using a Zirconia Bowl and Zirconia Balls for Ball-Mill mixing of Active Materials

NASA Astrophysics Data System (ADS)

Song, Dae-Hoon; Kim, Jin-Young; Kahng, Yung Ho; Cho, Hoonsung; Kim, Eung-Sam

2018-04-01

Improving the energy storage performance of supercapacitor electrodes based on reduced graphene oxide (RGO) is one of the main subjects in this research field. However, when a zirconia bowl and zirconia balls were used for ball-mill mixing of the active materials for RGO supercapacitors, the energy storage performance deteriorated over time. Our study revealed that the source of the problem was the inclusion of zirconia bits from abrasion of the bowl and the balls during the ballmill mixing, which increased during a period of 1 year. We probed two solutions to this problem: 1) hydrofluoric (HF) acid treatment of the RGO supercapacitors and 2) use of a tempered steel bowl and tempered steel balls for the mixing. For both cases, the energy storage performance was restored to near the initial level, showing a specific capacitance ( C sp ) of 200 F/g. Our results should lead to progress in research on RGO supercapacitors.

Supercritical fluid chromatography versus high performance liquid chromatography for enantiomeric and diastereoisomeric separations on coated polysaccharides-based stationary phases: Application to dihydropyridone derivatives.

PubMed

Hoguet, Vanessa; Charton, Julie; Hecquet, Paul-Emile; Lakhmi, Chahinaze; Lipka, Emmanuelle

2018-05-11

For analytical applications, SFC has always remained in the shadow of LC. Analytical enantioseparation of eight dihydropyridone derivatives, was run in both High Performance Liquid Chromatography and Supercritical Fluid Chromatography. Four polysaccharide based chiral stationary phases namely amylose and cellulose tris(3, 5-dimethylphenylcarbamate), amylose tris((S)-α-phenylethylcarbamate) and cellulose tris(4-methylbenzoate) with four mobile phases consisted of either n-hexane/ethanol or propan-2-ol (80:20 v:v) or carbon dioxide/ethanol or propan-2-ol (80:20 v:v) mixtures were investigated under same operatory conditions (temperature and flow-rate). The elution strength, enantioselectivity and resolution were compared in the two methodologies. For these compounds, for most of the conditions, HPLC afforded shorter retention times and a higher resolution than SFC. HPLC appears particularly suitable for the separation of the compounds bearing two chiral centers. For instance compound 7 was baseline resolved on OD-H CSP under n-Hex/EtOH 80/20, with resolution values equal to 2.98, 1.55, 4.52, between the four stereoisomers in less than 17 min, whereas in SFC, this latter is not fully separated in 23 min under similar eluting conditions. After analytical screenings, the best conditions were transposed to semi-preparative scale. Copyright © 2018 Elsevier B.V. All rights reserved.

Operation of Thin-Film Electrolyte Metal-Supported Solid Oxide Fuel Cells in Lightweight and Stationary Stacks: Material and Microstructural Aspects

PubMed Central

Roehrens, Daniel; Packbier, Ute; Fang, Qingping; Blum, Ludger; Sebold, Doris; Bram, Martin; Menzler, Norbert

2016-01-01

In this study we report on the development and operational data of a metal-supported solid oxide fuel cell with a thin film electrolyte under varying conditions. The metal-ceramic structure was developed for a mobile auxiliary power unit and offers power densities of 1 W/cm2 at 800 °C, as well as robustness under mechanical, thermal and chemical stresses. A dense and thin yttria-doped zirconia layer was applied to a nanoporous nickel/zirconia anode using a scalable adapted gas-flow sputter process, which allowed the homogeneous coating of areas up to 100 cm2. The cell performance is presented for single cells and for stack operation, both in lightweight and stationary stack designs. The results from short-term operation indicate that this cell technology may be a very suitable alternative for mobile applications. PMID:28773883

Application of Carbon Nanotubes in Chiral and Achiral Separations of Pharmaceuticals, Biologics and Chemicals

PubMed Central

Hemasa, Ayman L.; Maher, William A.; Ghanem, Ashraf

2017-01-01

Carbon nanotubes (CNTs) possess unique mechanical, physical, electrical and absorbability properties coupled with their nanometer dimensional scale that renders them extremely valuable for applications in many fields including nanotechnology and chromatographic separation. The aim of this review is to provide an updated overview about the applications of CNTs in chiral and achiral separations of pharmaceuticals, biologics and chemicals. Chiral single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) have been directly applied for the enantioseparation of pharmaceuticals and biologicals by using them as stationary or pseudostationary phases in chromatographic separation techniques such as high-performance liquid chromatography (HPLC), capillary electrophoresis (CE) and gas chromatography (GC). Achiral MWCNTs have been used for achiral separations as efficient sorbent objects in solid-phase extraction techniques of biochemicals and drugs. Achiral SWCNTs have been applied in achiral separation of biological samples. Achiral SWCNTs and MWCNTs have been also successfully used to separate achiral mixtures of pharmaceuticals and chemicals. Collectively, functionalized CNTs have been indirectly applied in separation science by enhancing the enantioseparation of different chiral selectors whereas non-functionalized CNTs have shown efficient capabilities for chiral separations by using techniques such as encapsulation or immobilization in polymer monolithic columns. PMID:28718832

Polar stationary phases based on poly(oligo ethylene glycol)diacrylates for capillary gas chromatography

NASA Astrophysics Data System (ADS)

Shiryaeva, V. E.; Popova, T. P.; Korolev, A. A.; Kanat'eva, A. Yu.; Kurganov, A. A.

2017-08-01

New stationary phases for capillary columns in GC are synthesized and studied. The phases are prepared by depositing oligo(ethylene glycol)diacrylates on the column walls and subsequent polymerization (crosslinking) in the presence of peroxide initiators. It is shown that stationary phases based on monomers with molecular weights of 10 kDa or higher exhibit separation properties similar to those of conventional stationary phases based on polyethylene glycol (PEG); however, their thermal stability is higher because they have a higher degree of crosslinking and a more ordered structure of the crosslinked polymers than the respective parameters of phases based on native PEG.

[Influence on mechanical properties and microstructure of nano-zirconia toughened alumina ceramics with nano-zirconia content].

PubMed

Wang, Guang-Kui; Kang, Hong; Bao, Guang-Jie; Lv, Jin-Jun; Gao, Fei

2006-10-01

To investigate the mechanical properties and microstructure of nano -zirconia toughened alumina ceramics with variety of nano-zirconia content in centrifugal infiltrate casting processing of dental all-ceramic. Composite powder with different ethanol-water ratio, obtained serosity from ball milling and centrifugal infiltrate cast processing of green, then sintered at 1 450 degrees C for 8 h. The physical and mechanical properties of the sintered sample after milling and polishing were tested. Microstructures of the surface and fracture of the sintered sample were investigated by SEM. The experimental results showed that there had statistical significience (P < 0.01) on static three-point flexure strength and Vickers Hardness in three kinds of different nano-zirconia content sintered sample. Fracture toughness of 20% group was different from other two groups, while 10% group had not difference from 30% group (P < 0.05). The mechanical properties of this ceramic with 20% nano-zirconia was the best of the three, the static three-point flexure strength was (433 +/- 19) MPa and fracture toughness was (7.50 +/- 0.56) MPa x min 1/2. The intra/inter structure, fracture of intragranular and intergranular on the surface and fracture of sintered sample in microstrucre was also found. Intra/inter structure has strengthen toughness in ceramics. It has better toughness with 20% nano-zirconia, is suitable dental all-ceramic restoratives.

Chiral superconductors.

PubMed

Kallin, Catherine; Berlinsky, John

2016-05-01

Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a chiral triplet p-wave superconductor, and UPt3, which has two low-temperature superconducting phases (in zero magnetic field), the lower of which is believed to be chiral triplet f-wave. Other systems that may exhibit chiral superconductivity are also discussed. Key signatures of chiral superconductivity are surface currents and chiral Majorana modes, Majorana states in vortex cores, and the possibility of half-flux quantum vortices in the case of triplet pairing. Experimental evidence for chiral superconductivity from μSR, NMR, strain, polar Kerr effect and Josephson tunneling experiments are discussed.

Chirality and protein biosynthesis.

PubMed

Banik, Sindrila Dutta; Nandi, Nilashis

2013-01-01

Chirality is present at all levels of structural hierarchy of protein and plays a significant role in protein biosynthesis. The macromolecules involved in protein biosynthesis such as aminoacyl tRNA synthetase and ribosome have chiral subunits. Despite the omnipresence of chirality in the biosynthetic pathway, its origin, role in current pathway, and importance is far from understood. In this review we first present an introduction to biochirality and its relevance to protein biosynthesis. Major propositions about the prebiotic origin of biomolecules are presented with particular reference to proteins and nucleic acids. The problem of the origin of homochirality is unresolved at present. The chiral discrimination by enzymes involved in protein synthesis is essential for keeping the life process going. However, questions remained pertaining to the mechanism of chiral discrimination and concomitant retention of biochirality. We discuss the experimental evidence which shows that it is virtually impossible to incorporate D-amino acids in protein structures in present biosynthetic pathways via any of the two major steps of protein synthesis, namely aminoacylation and peptide bond formation reactions. Molecular level explanations of the stringent chiral specificity in each step are extended based on computational analysis. A detailed account of the current state of understanding of the mechanism of chiral discrimination during aminoacylation in the active site of aminoacyl tRNA synthetase and peptide bond formation in ribosomal peptidyl transferase center is presented. Finally, it is pointed out that the understanding of the mechanism of retention of enantiopurity has implications in developing novel enzyme mimetic systems and biocatalysts and might be useful in chiral drug design.

Molybdenum disilicide composites reinforced with zirconia and silicon carbide

DOEpatents

Petrovic, John J.

1995-01-01

Compositions consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

Chiral Recognition and Separation by Chirality-Enriched Metal-Organic Frameworks.

PubMed

Das, Saikat; Xu, Shixian; Ben, Teng; Qiu, Shilun

2018-05-16

Endowed with chiral channels and pores, chiral metal-organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality-enriched MOFs with accessible pores. The ability of the materials to form host-guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed-matrix membranes (MMMs) composed of chirality-enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral separations of cathinone and amphetamine-derivatives: Comparative study between capillary electrochromatography, supercritical fluid chromatography and three liquid chromatographic modes.

PubMed

Albals, Dima; Heyden, Yvan Vander; Schmid, Martin G; Chankvetadze, Bezhan; Mangelings, Debby

2016-03-20

The screening part of an earlier defined chiral separation strategy in capillary electrochromatography (CEC) was used for the separation of ten cathinone- and amphetamine derivatives. They were analyzed using 4 polysaccharide-based chiral stationary phases (CSPs), containing cellulose tris(3,5-dimethylphenylcarbamate) (ODRH), amylose tris(3,5-dimethylphenylcarbamate) (ADH), amylose tris(5-chloro-2-methylphenylcarbamate) (LA2), and cellulose tris(4-chloro-3-methylphenylcarbamate) (LC4) as chiral selectors. After applying the screening to each compound, ADH and LC4 showed the highest success rate. In a second part of the study, a comparison between CEC and other analytical techniques used for chiral separations i.e., supercritical fluid chromatography (SFC), polar organic solvent chromatography (POSC), reversed-phase (RPLC) and normal-phase liquid chromatography (NPLC), was made. For this purpose, earlier defined screening approaches for each technique were applied to separate the 10 test substances. This allowed an overall comparison of the success rates of the screening steps of the 5 techniques for these compounds. The results showed that CEC had a similar enantioselectivity rate as NPLC and RPLC, producing the highest number of separations (9 out of 10 racemates). SFC resolved 7 compounds, while POSC gave only 2 separations. On the other hand, the baseline separation success rates for NPLC and RPLC was better than for CEC. For a second comparison, the same chiral stationary phases as in the CEC screening were also tested with all techniques at their specific screening conditions, which allowed a direct comparison of the performance of CEC versus the same CSPs in the other techniques. This comparison revealed that RPLC was able to separate all tested compounds, and also produced the highest number of baseline separations on the CSP that were used in the CEC screening step. CEC and NPLC showed the same success rate: nine out of ten substances were separated. When

Energetics of zirconia stabilized by cation and nitrogen substitution

NASA Astrophysics Data System (ADS)

Molodetsky, Irina

Tetragonal and cubic zirconia are used in advanced structural ceramics, fuel cells, oxygen sensors, nuclear waste ceramics and many other applications. These zirconia phases are stabilized at room temperature (relative to monoclinic phase for pure zirconia) by cation and nitrogen substitution. This work is aimed at a better understanding of the mechanisms of stabilization of the high-temperature zirconia. phases. Experimental data are produced on the energetics of zirconia stabilized by yttria and calcia, energetics of nitrogen-oxygen substitution in zirconia and cation doped zirconia, and energetics of x-ray amorphous zirconia. obtained by low-temperature synthesis. High-temperature oxide melt solution enables direct measurement of enthalpies of formation of these refractory oxides. The enthalpy of the monoclinic to cubic phase transition of zirconia is DeltaHm-c = 12.2 +/- 1.2 kJ/mol. For cubic phases of YSZ at low yttria contents, a straight line DeltaH f,YSZ = -(52.4 +/- 3.6)x + (12.2 +/- 1.2) approximates the enthalpy of formation as a function of the yttria content, x (0. 1 < x < 0.3). Use of the quadratic fit DeltaHf,YSZ = 126.36 x 2 - 81.29 x + 12.37 (0.1 ≲ x ≲ 0.53) indicates that yttria stabilizes the cubic phase in enthalpy at low dopant content and destabilizes the cubic phase as yttria content increases. Positive entropy of mixing in YSZ and small enthalpy of long range ordering in 0.47ZrO2-0.53YO1.5, DeltaHord = -2.4 +/- 3.0 kJ/mol, indicate presence of short range ordering in YSZ. The enthalpy of formation of calcia stabilized zirconia as a function of calcia content x, is approximated as DeltaHf,c = (-91.4 +/- 3.8) x + (13.5 +/- 1.7) kJ/mol. The enthalpy of oxygen-nitrogen substitution, DeltaHO-N, in zirconium oxynitrides is a linear function of nitrogen content. DeltaH O-N ˜ -500 kJ/mol N is for Ca (Y)-Zr-N-O and Zr-N-O oxynitrides and DeltaHO-N ˜ -950 kJ/mol N is for Mg-Zr-N-O oxynitrides. X-ray amorphous zirconia is 58.6 +/- 3.3 kJ/mol less

Study and development of sulfated zirconia based proton exchange fuel cell membranes

NASA Astrophysics Data System (ADS)

Kemp, Brittany Wilson

With the increasing consumption of energy, fuel cells are among the most promising alternatives to fossil fuels, provided some technical challenges are overcome. Proton exchange membrane fuel cells (PEMFCs) have been investigated and improvements have been made, but the problem with NafionRTM, the main membrane for PEMFCs, has not been solved. NafionRTM restricts the membranes from operating at higher temperatures, thus preventing them from working in small electronics. The problem is to develop a novel fuel cell membrane that performs comparably to NafionRTM in PEMFCs. The membranes were fabricated by applying sulfated zirconia, via template wetting, to porous alumina membranes. The fabricated membranes showed a proton conductivity of 0.016 S/cm in comparison to the proton conductivity of Nafion RTM (0.05 S/cm). Both formic acid and methanol had a lower crossover flux through the sulfated zirconia membranes (formic acid- 2.89x10 -7 mols/cm2s and methanol-1.78x10-9 mols/cm2s) than through NafionRTM (formic acid-2.03x10 -8 mols/cm2s methanol-2.42x10-6 mols/cm 2s), indicating that a sulfated zirconia PEMFC may serve as a replacement for NafionRTM.

[Effects of colorants on yttria stabilized tetragonal zirconia polycrystals powder].

PubMed

Wang, Bo; Chen, Jianfeng; Zhang, Yanchun; Wang, Ru

2015-10-01

To evaluate the effect of Fe2O3 and CeO2 as colorants on yttria stabilized tetragonal zirconia poly-crystals (Y-TZP) powder. The spray granulation slurry of colored zirconia was prepared with different concentrations of Fe2O3 (0.15%) and CeO2 (4%), which were added in Y-TZP. Zirconia powder was made by spray granulation. The powder specimens were divided into three groups: uncolored zirconia, Fe2O3 (0.15%) zirconia, and CeO2 (4%) zirconia. The particle morphologies of the powder specimens were measured with a laser particle size analyzer and an optical microscope. The differences in D50 among the three groups were statistically significant (P<0.05). Group Fe2O3 showed a significant difference from groups CeO2 and uncolored zirconia (P<0.05). Group uncolored zirconia showed no significant difference from group CeO2 (P>0.05). Mostly spherical powder was observed in the three groups. Fe2O3 as a colorant can affect particles, whereas CeO2 has no effect.

Synthesis and characterization of nanocrystalline mesoporous zirconia using supercritical drying.

PubMed

Tyagi, Beena; Sidhpuria, Kalpesh; Shaik, Basha; Jasra, Raksh Vir

2006-06-01

Synthesis of nano-crystalline zirconia aerogel was done by sol-gel technique and supercritical drying using n-propanol solvent at and above supercritical temperature (235-280 degrees C) and pressure (48-52 bar) of n-propanol. Zirconia xerogel samples have also been prepared by conventional thermal drying method to compare with the super critically dried samples. Crystalline phase, crystallite size, surface area, pore volume, and pore size distribution were determined for all the samples in detail to understand the effect of gel drying methods on these properties. Supercritical drying of zirconia gel was observed to give thermally stable, nano-crystalline, tetragonal zirconia aerogels having high specific surface area and porosity with narrow and uniform pore size distribution as compared to thermally dried zirconia. With supercritical drying, zirconia samples show the formation of only mesopores whereas in thermally dried samples, substantial amount of micropores are observed along with mesopores. The samples prepared using supercritical drying yield nano-crystalline zirconia with smaller crystallite size (4-6 nm) as compared to higher crystallite size (13-20 nm) observed with thermally dried zirconia.

Resin adhesion strengths to zirconia ceramics after primer treatment with silane coupling monomer or oligomer.

PubMed

Okada, Masahiro; Inoue, Kazusa; Irie, Masao; Taketa, Hiroaki; Torii, Yasuhiro; Matsumoto, Takuya

2017-09-26

Resin bonding to zirconia ceramics is difficult to achieve using the standard methods for conventional silica-based dental ceramics, which employ silane coupling monomers as primers. The hypothesis in this study was that a silane coupling oligomer -a condensed product of silane coupling monomers- would be a more suitable primer for zirconia. To prove this hypothesis, the shear bond strengths between a composite resin and zirconia were compared after applying either a silane coupling monomer or oligomer. The shear bond strength increased after applying a non-activated ethanol solution of the silane coupling oligomer compared with that achieved when applying the monomer. Thermal treatment of the zirconia at 110°C after application of the silane coupling agents was essential to improve the shear bond strength between the composite resin cement and zirconia.

Molybdenum disilicide composites reinforced with zirconia and silicon carbide

DOEpatents

Petrovic, J.J.

1995-01-17

Compositions are disclosed consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

Use of chiral derivatization for the determination of dichlorprop in tea samples by ultra performance LC with fluorescence detection.

PubMed

Inoue, Koichi; Prayoonhan, Nuntawat; Tsutsui, Haruhito; Sakamoto, Tasuku; Nishimura, Maiko; Toyo'oka, Toshimasa

2013-04-01

Dichlorprop is available for agricultural use as a chiral pesticide. In this study, the stereoselective determination of dichlorprop enantiomers in tea samples such as green, black, jasmine, and oolong was developed by ultra performance LC with fluorescence spectrometry after covalent chiral derivatization. The separation was achieved on an Acquity BEH C18 column with the mobile phase consisting of 0.1% formic acid in acetonitrile/water at a flow rate of 0.4 mL/min. In the covalent chiral derivatization using (S)-(+)-4-(N,N-dimethylaminosulfonyl)-7-(3-aminopyrrolidin-1-yl)-2,1,3-benzoxadiazole, the peak resolution between the S and R-dichlorprop enantiomers was 2.6. LODs and LOQs values were 10 and 50 ng/mL standard solution. The linearity of the calibration curves yielded the coefficients (r(2) > 0.99, ranging from 0.05 to 5 μg/mL) of determination of each of the dichlorprop enantiomers. SPE extraction was used for the sample preparation of dichlorprop in various tea samples. Recoveries were in the range of 82.4-97.6% with associated precision values (within-day: 82.4-95.8%, n = 6, and between-day: 83.7-97.6% for 3 days) for repeatability and reproducibility. Based on this result, our method has been proven to be highly efficient and suitable for the routine assay of dichlorprop enantiomers in various tea samples. We propose that the ultra performance LC assay after covalent chiral derivatization would be the renewed tools in the era of chiral stationary platform for chiral pesticide residues in foods. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Internal Nano Voids in Yttria-Stabilised Zirconia (YSZ) Powder

PubMed Central

Barad, Chen; Shekel, Gal; Shandalov, Michael; Hayun, Hagay; Kimmel, Giora; Shamir, Dror; Gelbstein, Yaniv

2017-01-01

Porous yttria-stabilised zirconia ceramics have been gaining popularity throughout the years in various fields, such as energy, environment, medicine, etc. Although yttria-stabilised zirconia is a well-studied material, voided yttria-stabilised zirconia powder particles have not been demonstrated yet, and might play an important role in future technology developments. A sol-gel synthesis accompanied by a freeze-drying process is currently being proposed as a method of obtaining sponge-like nano morphology of embedded faceted voids inside yttria-stabilised zirconia particles. The results rely on a freeze-drying stage as an effective and simple method for generating nano-voided yttria-stabilised zirconia particles without the use of template-assisted additives. PMID:29258227

Internal Nano Voids in Yttria-Stabilised Zirconia (YSZ) Powder.

PubMed

Barad, Chen; Shekel, Gal; Shandalov, Michael; Hayun, Hagay; Kimmel, Giora; Shamir, Dror; Gelbstein, Yaniv

2017-12-18

Porous yttria-stabilised zirconia ceramics have been gaining popularity throughout the years in various fields, such as energy, environment, medicine, etc. Although yttria-stabilised zirconia is a well-studied material, voided yttria-stabilised zirconia powder particles have not been demonstrated yet, and might play an important role in future technology developments. A sol-gel synthesis accompanied by a freeze-drying process is currently being proposed as a method of obtaining sponge-like nano morphology of embedded faceted voids inside yttria-stabilised zirconia particles. The results rely on a freeze-drying stage as an effective and simple method for generating nano-voided yttria-stabilised zirconia particles without the use of template-assisted additives.

[Microwave sintering of nanometer powder of alumina and zirconia-based dental ceramics].

PubMed

Chen, Yi-Fan; Lu, Dong-Mei; Wan, Qian-Bing; Jin, Yong; Zhu, Ju-Mu

2006-02-01

The objective of the present study was to investigate the feasibility and reliability of sintering alumina and zirconia-based all-ceramic materials through a recently introduced microwave heating technique. The variation of crystal phases, the growth of grain sizes and microstructural features of these materials were evaluated after sintering. Four different groups of powder (l00%Al2O3, 60%Al2O3+40%ZrO2, 40% Al2O3+60%ZrO2, 100% ZrO2) were respectively press-compacted to fabricate green disk samples, 5 specimen of each group were prepared. All the samples were surrounded by refractory materials for heat containment and processed at 1 600 degrees C in a domestic microwave oven (850 W, 2 450 MHz), 1 600 degrees C/5 min for heating rate, 10 min for holding time. After sintering, the phase composition and average grain size of these ceramics were examined using X-ray diffraction (XRD). Their microstructure characteristics were studied by scanning electron microscopy (SEM). All the specimens were successfully sintered with the application of microwave heating system in combination with a suitable thermal insulator. No phase change was found in alumina while monoclinic-zirconia was found to be transformed to tetragonal-zirconia. A little grain size growth of Al2O3 and ZrO2 has been observed with Al2O3 24.1 nm/before and 51.8 nm/after; ZrO2 25.3 nm/before and 29.7 nm/after. The SEM photos indicated that the microwave-sintered Al2O3-ZrO2 ceramics had a uniform crystal distribution and their crystal sizes could be maintained within the range of nanometers. It is expected that in the near future microwave heating system could be a promising substitute for conventional processing methods due to its unparalled advantages, including more rapid heating rate, shortened sintering time, superfine grain size, improved microstructure and much less expensive equipment.

Thermally driven spin-Seebeck transport in chiral dsDNA-based molecular devices

NASA Astrophysics Data System (ADS)

Nian, L. L.; Zhang, Rong; Tang, F. R.; Tang, Jun; Bai, Long

2018-03-01

By employing the nonequilibrium Green's function technique, we study the thermal-induced spin-Seebeck transport through a chiral double-stranded DNA (dsDNA) connected to a normal-metal and a ferromagnetic lead. How the main parameters of the dsDNA-based system influence the spin-Seebeck transport is analyzed at length, and the thermally created charge (spin-related) current displays the rectification effect and the negative differential thermal conductance feature. More importantly, the spin current exhibits the rectification behavior of the spin-Seebeck effect; even the perfect spin-Seebeck effect can be obtained with the null charge current. Thus, the chiral dsDNA-based system can act as a spin(charge)-Seebeck diode, spin(charge)-Seebeck switch, and spin(charge)-Seebeck transistor. Our results provide new ways to design spin caloritronic devices based on dsDNA or other organic molecules.

Sulfation of ceria-zirconia model automotive emissions control catalysts

NASA Astrophysics Data System (ADS)

Nelson, Alan Edwin

Cerium-zirconium mixed metal oxides are used in automotive emissions control catalysts to regulate the partial pressure of oxygen near the catalyst surface. The near surface oxygen partial pressure is regulated through transfer of atomic oxygen from the ceria-zirconia solid matrix to the platinum group metals to form metal oxides capable of oxidizing carbon monoxide and unburned hydrocarbons. Although the addition of zirconium in the cubic lattice of ceria increases the oxygen storage capacity and thermal stability of the ceria matrix, the cerium-zirconium oxide system remains particularly susceptible to deactivation from sulfur compounds. While the overall effect of sulfur on these systems is understood (partially irreversible deactivation), the fundamental and molecular interaction of sulfur with ceria-zirconia remains a challenging problem. Ceria-zirconia metal oxide solid solutions have been prepared through co-precipitation with nitrate precursors. The prepared powders were calcined and subsequently formed into planer wafers and characterized for chemical and physical attributes. The prepared samples were subsequently exposed to a sulfur dioxide based environment and characterized with spectroscopic techniques to characterize the extent of sulfation and the nature of surface sulfur species. The extent of sulfation of the model ceria-zirconia systems was characterized with Auger electron spectroscopy (AES) prior to and after treatment in a microreactor. Strong dependencies were observed between the atomic ratio of ceria to zirconia and the extent of sulfation. In addition, the partial pressure of sulfur dioxide during treatments also correlated to the extent of sulfation, while temperature only slightly effected the extent of sulfation. The AES data suggests the gas phase sulfur dioxide preferentially chemisorbs on surface ceria atoms and the extent of sulfation is heavily dependent on sulfur dioxide concentrations and only slightly dependent on catalyst

Synthesis and thermal stability of zirconia and yttria-stabilized zirconia microspheres.

PubMed

Leib, Elisabeth W; Vainio, Ulla; Pasquarelli, Robert M; Kus, Jonas; Czaschke, Christian; Walter, Nils; Janssen, Rolf; Müller, Martin; Schreyer, Andreas; Weller, Horst; Vossmeyer, Tobias

2015-06-15

Zirconia microparticles produced by sol-gel synthesis have great potential for photonic applications. To this end, identifying synthetic methods that yield reproducible control over size uniformity is important. Phase transformations during thermal cycling can disintegrate the particles. Therefore, understanding the parameters driving these transformations is essential for enabling high-temperature applications. Particle morphology is expected to influence particle processability and stability. Yttria-doping should improve the thermal stability of the particles, as it does in bulk zirconia. Zirconia and YSZ particles were synthesized by improved sol-gel approaches using fatty acid stabilizers. The particles were heated to 1500 °C, and structural and morphological changes were monitored by SEM, ex situ XRD and high-energy in situ XRD. Zirconia particles (0.4-4.3 μm in diameter, 5-10% standard deviation) synthesized according to the modified sol-gel approaches yielded significantly improved monodispersities. As-synthesized amorphous particles transformed to the tetragonal phase at ∼450 °C with a volume decrease of up to ∼75% and then to monoclinic after heating from ∼650 to 850 °C. Submicron particles disintegrated at ∼850 °C and microparticles at ∼1200 °C due to grain growth. In situ XRD revealed that the transition from the amorphous to tetragonal phase was accompanied by relief in microstrain and the transition from tetragonal to monoclinic was correlated with the tetragonal grain size. Early crystallization and smaller initial grain sizes, which depend on the precursors used for particle synthesis, coincided with higher stability. Yttria-doping reduced grain growth, stabilized the tetragonal phase, and significantly improved the thermal stability of the particles. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Overview of zirconia with respect to gas turbine applications

NASA Technical Reports Server (NTRS)

Cawley, J. D.

1984-01-01

Phase relationships and the mechanical properties of zirconia are examined as well as the thermal conductivity, deformation, diffusion, and chemical reactivity of this refractory material. Observations from the literature particular to plasma-sprayed material and implications for gas turbine engine applications are discussed. The literature review indicates that Mg-PSZ (partially stabilized zirconia) and Ca-PSZ are unsuitable for advanced gas turbine applications; a thorough characterization of the microstructure of plasma-sprayed zirconia is needed. Transformation-toughened zirconia may be suitable for use in monolithic components.

A non-stationary cost-benefit based bivariate extreme flood estimation approach

NASA Astrophysics Data System (ADS)

Qi, Wei; Liu, Junguo

2018-02-01

Cost-benefit analysis and flood frequency analysis have been integrated into a comprehensive framework to estimate cost effective design values. However, previous cost-benefit based extreme flood estimation is based on stationary assumptions and analyze dependent flood variables separately. A Non-Stationary Cost-Benefit based bivariate design flood estimation (NSCOBE) approach is developed in this study to investigate influence of non-stationarities in both the dependence of flood variables and the marginal distributions on extreme flood estimation. The dependence is modeled utilizing copula functions. Previous design flood selection criteria are not suitable for NSCOBE since they ignore time changing dependence of flood variables. Therefore, a risk calculation approach is proposed based on non-stationarities in both marginal probability distributions and copula functions. A case study with 54-year observed data is utilized to illustrate the application of NSCOBE. Results show NSCOBE can effectively integrate non-stationarities in both copula functions and marginal distributions into cost-benefit based design flood estimation. It is also found that there is a trade-off between maximum probability of exceedance calculated from copula functions and marginal distributions. This study for the first time provides a new approach towards a better understanding of influence of non-stationarities in both copula functions and marginal distributions on extreme flood estimation, and could be beneficial to cost-benefit based non-stationary bivariate design flood estimation across the world.

Optimization of chiral lattice based metastructures for broadband vibration suppression using genetic algorithms

NASA Astrophysics Data System (ADS)

Abdeljaber, Osama; Avci, Onur; Inman, Daniel J.

2016-05-01

One of the major challenges in civil, mechanical, and aerospace engineering is to develop vibration suppression systems with high efficiency and low cost. Recent studies have shown that high damping performance at broadband frequencies can be achieved by incorporating periodic inserts with tunable dynamic properties as internal resonators in structural systems. Structures featuring these kinds of inserts are referred to as metamaterials inspired structures or metastructures. Chiral lattice inserts exhibit unique characteristics such as frequency bandgaps which can be tuned by varying the parameters that define the lattice topology. Recent analytical and experimental investigations have shown that broadband vibration attenuation can be achieved by including chiral lattices as internal resonators in beam-like structures. However, these studies have suggested that the performance of chiral lattice inserts can be maximized by utilizing an efficient optimization technique to obtain the optimal topology of the inserted lattice. In this study, an automated optimization procedure based on a genetic algorithm is applied to obtain the optimal set of parameters that will result in chiral lattice inserts tuned properly to reduce the global vibration levels of a finite-sized beam. Genetic algorithms are considered in this study due to their capability of dealing with complex and insufficiently understood optimization problems. In the optimization process, the basic parameters that govern the geometry of periodic chiral lattices including the number of circular nodes, the thickness of the ligaments, and the characteristic angle are considered. Additionally, a new set of parameters is introduced to enable the optimization process to explore non-periodic chiral designs. Numerical simulations are carried out to demonstrate the efficiency of the optimization process.

Antagonist wear of monolithic zirconia crowns after 2 years.

PubMed

Lohbauer, Ulrich; Reich, Sven

2017-05-01

The aim of this study was to evaluate the amount of wear on the antagonist occlusal surfaces of clinically placed monolithic zirconia premolar and molar crowns (LAVA Plus, 3M ESPE). Fourteen in situ monolithic zirconia crowns and their opposing antagonists (n = 26) are the subject of an ongoing clinical trial and have been clinically examined at baseline and after 24 months. Silicone impressions were taken and epoxy replicas produced for qualitative SEM analysis and quantitative analysis using optical profilometry. Based on the baseline replicas, the follow-up situation has been scanned and digitally matched with the initial topography in order to calculate the mean volume loss (in mm 3 ) as well as the mean maximum vertical loss (in mm) after 2 years in service. The mean volume loss for enamel antagonist contacts (n = 7) was measured to 0.361 mm 3 and the mean of the maximum vertical loss to 0.204 mm. The mean volume loss for pure ceramic contacts (n = 10) was measured to 0.333 mm 3 and the mean of the maximum vertical loss to 0.145 mm. The wear rates on enamel contacts were not significantly different from those measured on ceramic antagonists. Based on the limitations of this study, it can be concluded for the monolithic zirconia material LAVA Plus that the measured wear rates are in consensus with other in vivo studies on ceramic restorations. Further, that no significant difference was found between natural enamel antagonists and ceramic restorations as antagonists. The monolithic zirconia restorations do not seem to be affected by wear within the first 2 years. The monolithic zirconia crowns (LAVA Plus) show acceptable antagonist wear rates after 2 years in situ, regardless of natural enamel or ceramics as antagonist materials.

A fractographic study of clinically retrieved zirconia-ceramic and metal-ceramic fixed dental prostheses.

PubMed

Pang, Zhen; Chughtai, Asima; Sailer, Irena; Zhang, Yu

2015-10-01

A recent 3-year randomized controlled trial (RCT) of tooth supported three- to five-unit zirconia-ceramic and metal-ceramic posterior fixed dental prostheses (FDPs) revealed that veneer chipping and fracture in zirconia-ceramic systems occurred more frequently than those in metal-ceramic systems [1]. This study seeks to elucidate the underlying mechanisms responsible for the fracture phenomena observed in this RCT using a descriptive fractographic analysis. Vinyl-polysiloxane impressions of 12 zirconia-ceramic and 6 metal-ceramic FDPs with veneer fractures were taken from the patients at the end of a mean observation of 40.3±2.8 months. Epoxy replicas were produced from these impressions [1]. All replicas were gold coated, and inspected under the optical microscope and scanning electron microscope (SEM) for descriptive fractography. Among the 12 zirconia-ceramic FDPs, 2 had small chippings, 9 had large chippings, and 1 exhibited delamination. Out of 6 metal-ceramic FDPs, 5 had small chippings and 1 had large chipping. Descriptive fractographic analysis based on SEM observations revealed that fracture initiated from the wear facet at the occlusal surface in all cases, irrespective of the type of restoration. Zirconia-ceramic and metal-ceramic FDPs all fractured from microcracks that emanated from occlusal wear facets. The relatively low fracture toughness and high residual tensile stress in porcelain veneer of zirconia restorations may contribute to the higher chipping rate and larger chip size in zirconia-ceramic FDPs relative to their metal-ceramic counterparts. The low veneer/core interfacial fracture energy of porcelain-veneered zirconia may result in the occurrence of delamination in zirconia-ceramic FDPs. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Chiral pesticides: identification, description, and environmental implications.

PubMed

Ulrich, Elin M; Morrison, Candice N; Goldsmith, Michael R; Foreman, William T

2012-01-01

, synthetic musks, and their degradates (Kallenborn and Hiihnerfuss 2001;Heeb et al. 2007; Hihnerfuss and Shah 2009). The stereoisomers of pesticides can have widely different efficacy, toxicity to nontarget organisms, and metabolic rates in biota. For these reasons, it is important to first be aware of likely fate and effect differences, to incorporate molecular asymmetry insights into research projects, and to study the individual stereoisomers of the applied pesticide material.With the advent of enantioselective chromatography techniques, the chirality of pesticides has been increasingly studied. While the ChirBase (Advanced ChemistryDevelopment 1997-2010) database does not include all published chiral analytical separations, it does contain more than 3,500 records for 146 of the 482 chiral pesticides (30%). The majority of the records are found in the liquid chromatography database (2,677 or 76%), followed by the gas chromatography database (652 or 18%),and the capillary electrophoresis database (203 or 6%). The finding that only 30% of the chiral pesticides covered in this review have entries in ChirBase highlights the need for expanded efforts to develop additional enantioselective chromatographic methods. Other techniques (e.g., nuclear magnetic resonance and other spectroscopy)are available for investigation of chiral compounds, but often are not utilized because of cost, complexity, or simply not recognizing that a pesticide is chiral.In this review, we have listed and have briefly described the general nature of chiral fungicides, herbicides, insecticides, and other miscellaneous classes. A data-set generated for this review contains 1,693 pesticides, the number of enantioselective separation records in ChirBase, pesticide usage class, SMILES structure string and counts of stereogenic centers. This dataset is publically available for download at the following website: http://www.epa.gov/heasd/products/products.html. With the information herein coupled to the

Multiaxial Polarity Determines Individual Cellular and Nuclear Chirality

PubMed Central

Raymond, Michael J.; Ray, Poulomi; Kaur, Gurleen; Fredericks, Michael; Singh, Ajay V.; Wan, Leo Q.

2016-01-01

Intrinsic cell chirality has been implicated in the left-right (LR) asymmetry of embryonic development. Impaired cell chirality could lead to severe birth defects in laterality. Previously, we detected cell chirality with an in vitro micropatterning system. Here, we demonstrate for the first time that chirality can be quantified as the coordination of multiaxial polarization of individual cells and nuclei. Using an object labeling, connected component based method, we characterized cell chirality based on cell and nuclear shape polarization and nuclear positioning of each cell in multicellular patterns of epithelial cells. We found that the cells adopted a LR bias the boundaries by positioning the sharp end towards the leading edge and leaving the nucleus at the rear. This behavior is consistent with the directional migration observed previously on the boundary of micropatterns. Although the nucleus is chirally aligned, it is not strongly biased towards or away from the boundary. As the result of the rear positioning of nuclei, the nuclear positioning has an opposite chirality to that of cell alignment. Overall, our results have revealed deep insights of chiral morphogenesis as the coordination of multiaxial polarization at the cellular and subcellular levels. PMID:28360944

Multiaxial Polarity Determines Individual Cellular and Nuclear Chirality.

PubMed

Raymond, Michael J; Ray, Poulomi; Kaur, Gurleen; Fredericks, Michael; Singh, Ajay V; Wan, Leo Q

2017-02-01

Intrinsic cell chirality has been implicated in the left-right (LR) asymmetry of embryonic development. Impaired cell chirality could lead to severe birth defects in laterality. Previously, we detected cell chirality with an in vitro micropatterning system. Here, we demonstrate for the first time that chirality can be quantified as the coordination of multiaxial polarization of individual cells and nuclei. Using an object labeling, connected component based method, we characterized cell chirality based on cell and nuclear shape polarization and nuclear positioning of each cell in multicellular patterns of epithelial cells. We found that the cells adopted a LR bias the boundaries by positioning the sharp end towards the leading edge and leaving the nucleus at the rear. This behavior is consistent with the directional migration observed previously on the boundary of micropatterns. Although the nucleus is chirally aligned, it is not strongly biased towards or away from the boundary. As the result of the rear positioning of nuclei, the nuclear positioning has an opposite chirality to that of cell alignment. Overall, our results have revealed deep insights of chiral morphogenesis as the coordination of multiaxial polarization at the cellular and subcellular levels.

Chiral geometry in multiple chiral doublet bands

NASA Astrophysics Data System (ADS)

Zhang, Hao; Chen, Qibo

2016-02-01

The chiral geometry of multiple chiral doublet bands with identical configuration is discussed for different triaxial deformation parameters γ in the particle rotor model with . The energy spectra, electromagnetic transition probabilities B(M1) and B(E2), angular momenta, and K-distributions are studied. It is demonstrated that the chirality still remains not only in the yrast and yrare bands, but also in the two higher excited bands when γ deviates from 30°. The chiral geometry relies significantly on γ, and the chiral geometry of the two higher excited partner bands is not as good as that of the yrast and yrare doublet bands. Supported by Plan Project of Beijing College Students’ Scientific Research and Entrepreneurial Action, Major State 973 Program of China (2013CB834400), National Natural Science Foundation of China (11175002, 11335002, 11375015, 11461141002), National Fund for Fostering Talents of Basic Science (NFFTBS) (J1103206), Research Fund for Doctoral Program of Higher Education (20110001110087) and China Postdoctoral Science Foundation (2015M580007)

Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate

PubMed Central

Jiang, Wenge; Pacella, Michael S.; Athanasiadou, Dimitra; Nelea, Valentin; Vali, Hojatollah; Hazen, Robert M.; Gray, Jeffrey J.; McKee, Marc D.

2017-01-01

Chirality is ubiquitous in biology, including in biomineralization, where it is found in many hardened structures of invertebrate marine and terrestrial organisms (for example, spiralling gastropod shells). Here we show that chiral, hierarchically organized architectures for calcium carbonate (vaterite) can be controlled simply by adding chiral acidic amino acids (Asp and Glu). Chiral, vaterite toroidal suprastructure having a ‘right-handed' (counterclockwise) spiralling morphology is induced by L-enantiomers of Asp and Glu, whereas ‘left-handed' (clockwise) morphology is induced by D-enantiomers, and sequentially switching between amino-acid enantiomers causes a switch in chirality. Nanoparticle tilting after binding of chiral amino acids is proposed as a chiral growth mechanism, where a ‘mother' subunit nanoparticle spawns a slightly tilted, consequential ‘daughter' nanoparticle, which by amplification over various length scales creates oriented mineral platelets and chiral vaterite suprastructures. These findings suggest a molecular mechanism for how biomineralization-related enantiomers might exert hierarchical control to form extended chiral suprastructures. PMID:28406143

Chirality effect in disordered graphene ribbon junctions

NASA Astrophysics Data System (ADS)

Long, Wen

2012-05-01

We investigate the influence of edge chirality on the electronic transport in clean or disordered graphene ribbon junctions. By using the tight-binding model and the Landauer-Büttiker formalism, the junction conductance is obtained. In the clean sample, the zero-magnetic-field junction conductance is strongly chirality-dependent in both unipolar and bipolar ribbons, whereas the high-magnetic-field conductance is either chirality-independent in the unipolar or chirality-dependent in the bipolar ribbon. Furthermore, we study the disordered sample in the presence of magnetic field and find that the junction conductance is always chirality-insensitive for both unipolar and bipolar ribbons with adequate disorders. In addition, the disorder-induced conductance plateaus can exist in all chiral bipolar ribbons provided the disorder strength is moderate. These results suggest that we can neglect the effect of edge chirality in fabricating electronic devices based on the magnetotransport in a disordered graphene ribbon.

Zirconia coating stabilized super-iron alkaline cathodes

NASA Astrophysics Data System (ADS)

Yu, Xingwen; Licht, Stuart

A low-level zirconia coating significantly stabilizes high energy alkaline super-iron cathodes, and improves the energy storage capacity of super-iron batteries. Zirconia coating is derived from ZrCl 4 in an organic medium through the conversion of ZrCl 4 to ZrO 2. In alkaline battery system, ZrO 2 provides an intact shield for the cathode materials and the hydroxide shuttle through the coating sustains alkaline cathode redox chemistry. Most super-iron cathodes are solid-state stable, such as K 2FeO 4 and Cs 2FeO 4, but tend to be passivated in alkaline electrolyte due to the formation of Fe(III) over layer. Zirconia coating effectively enhances the stability of these super-iron cathodes. However, for solid-state unstable super-iron cathode (e.g. BaFeO 4), only a little stabilization effect of zirconia coating is observed.

Nanomaterials as stationary phases and supports in liquid chromatography.

PubMed

Beeram, Sandya R; Rodriguez, Elliott; Doddavenkatanna, Suresh; Li, Zhao; Pekarek, Allegra; Peev, Darin; Goerl, Kathryn; Trovato, Gianfranco; Hofmann, Tino; Hage, David S

2017-10-01

The development of various nanomaterials over the last few decades has led to many applications for these materials in liquid chromatography (LC). This review will look at the types of nanomaterials that have been incorporated into LC systems and the applications that have been explored for such systems. A number of carbon-based nanomaterials and inorganic nanomaterials have been considered for use in LC, ranging from carbon nanotubes, fullerenes and nanodiamonds to metal nanoparticles and nanostructures based on silica, alumina, zirconia and titanium dioxide. Many ways have been described for incorporating these nanomaterials into LC systems. These methods have included covalent immobilization, adsorption, entrapment, and the synthesis or direct development of nanomaterials as part of a chromatographic support. Nanomaterials have been used in many types of LC. These applications have included the reversed-phase, normal-phase, ion-exchange, and affinity modes of LC, as well as related methods such as chiral separations, ion-pair chromatography and hydrophilic interaction liquid chromatography. Both small and large analytes (e.g., dyes, drugs, amino acids, peptides and proteins) have been used to evaluate possible applications for these nanomaterial-based methods. The use of nanomaterials in columns, capillaries and planar chromatography has been considered as part of these efforts. Potential advantages of nanomaterials in these applications have included their good chemical and physical stabilities, the variety of interactions many nanomaterials can have with analytes, and their unique retention properties in some separation formats. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of zirconia (ZrO2) nanowires via chemical vapor deposition

NASA Astrophysics Data System (ADS)

Baek, M. K.; Park, S. J.; Choi, D. J.

2017-02-01

Monoclinic zirconia nanowires were synthesized by chemical vapor deposition using ZrCl4 powder as a starting material at 1200 °C and 760 Torr. Graphite was employed as a substrate, and an Au thin film was pre-deposited on the graphite as a catalyst. The zirconia nanostructure morphology was observed through scanning electron microscopy and transmission electron microscopy. Based on X-ray diffraction, selected area electron diffraction, and Raman spectroscopy data, the resulting crystal structure was found to be single crystalline monoclinic zirconia. The homogeneous distributions of Zr, O and Au were studied by scanning transmission electron microscopy with energy dispersive X-ray spectroscopy mapping, and there was no metal droplet at the nanowire tips despite the use of an Au metal catalyst. This result is apart from that of conventional metal catalyzed nanowires.

Catalytic Enantioselective Olefin Metathesis in Natural Product Synthesis. Chiral Metal-Based Complexes that Deliver High Enantioselectivity and More

PubMed Central

Malcolmson, Steven J.; Meek, Simon J.; Zhugralin, Adil R.

2012-01-01

Chiral olefin metathesis catalysts enable chemists to access enantiomerically enriched small molecules with high efficiency; synthesis schemes involving such complexes can be substantially more concise than those that would involve enantiomerically pure substrates and achiral Mo alkylidenes or Ru-based carbenes. The scope of research towards design and development of chiral catalysts is not limited to discovery of complexes that are merely the chiral versions of the related achiral variants. A chiral olefin metathesis catalyst, in addition to furnishing products of high enantiomeric purity, can offer levels of efficiency, product selectivity and/or olefin stereoselectivity that are unavailable through the achiral variants. Such positive attributes of chiral catalysts (whether utilized in racemic or enantiomerically enriched form) should be considered as general, applicable to other classes of transformations. PMID:19967680

Comparison of bond strengths of ceramic brackets bonded to zirconia surfaces using different zirconia primers and a universal adhesive.

PubMed

Lee, Ji-Yeon; Ahn, Jaechan; An, Sang In; Park, Jeong-Won

2018-02-01

The aim of this study is to compare the shear bond strengths of ceramic brackets bonded to zirconia surfaces using different zirconia primers and universal adhesive. Fifty zirconia blocks (15 × 15 × 10 mm, Zpex, Tosoh Corporation) were polished with 1,000 grit sand paper and air-abraded with 50 µm Al 2 O 3 for 10 seconds (40 psi). They were divided into 5 groups: control (CO), Metal/Zirconia primer (MZ, Ivoclar Vivadent), Z-PRIME Plus (ZP, Bisco), Zirconia Liner (ZL, Sun Medical), and Scotchbond Universal adhesive (SU, 3M ESPE). Transbond XT Primer (used for CO, MZ, ZP, and ZL) and Transbond XT Paste was used for bracket bonding (Gemini clear ceramic brackets, 3M Unitek). After 24 hours at 37°C storage, specimens underwent 2,000 thermocycles, and then, shear bond strengths were measured (1 mm/min). An adhesive remnant index (ARI) score was calculated. The data were analyzed using one-way analysis of variance and the Bonferroni test ( p = 0.05). Surface treatment with primers resulted in increased shear bond strength. The SU group showed the highest shear bond strength followed by the ZP, ZL, MZ, and CO groups, in that order. The median ARI scores were as follows: CO = 0, MZ = 0, ZP = 0, ZL = 0, and SU = 3 ( p < 0.05). Within this experiment, zirconia primer can increase the shear bond strength of bracket bonding. The highest shear bond strength is observed in SU group, even when no primer is used.

Comparison of bond strengths of ceramic brackets bonded to zirconia surfaces using different zirconia primers and a universal adhesive

PubMed Central

2018-01-01

Objectives The aim of this study is to compare the shear bond strengths of ceramic brackets bonded to zirconia surfaces using different zirconia primers and universal adhesive. Materials and Methods Fifty zirconia blocks (15 × 15 × 10 mm, Zpex, Tosoh Corporation) were polished with 1,000 grit sand paper and air-abraded with 50 µm Al2O3 for 10 seconds (40 psi). They were divided into 5 groups: control (CO), Metal/Zirconia primer (MZ, Ivoclar Vivadent), Z-PRIME Plus (ZP, Bisco), Zirconia Liner (ZL, Sun Medical), and Scotchbond Universal adhesive (SU, 3M ESPE). Transbond XT Primer (used for CO, MZ, ZP, and ZL) and Transbond XT Paste was used for bracket bonding (Gemini clear ceramic brackets, 3M Unitek). After 24 hours at 37°C storage, specimens underwent 2,000 thermocycles, and then, shear bond strengths were measured (1 mm/min). An adhesive remnant index (ARI) score was calculated. The data were analyzed using one-way analysis of variance and the Bonferroni test (p = 0.05). Results Surface treatment with primers resulted in increased shear bond strength. The SU group showed the highest shear bond strength followed by the ZP, ZL, MZ, and CO groups, in that order. The median ARI scores were as follows: CO = 0, MZ = 0, ZP = 0, ZL = 0, and SU = 3 (p < 0.05). Conclusions Within this experiment, zirconia primer can increase the shear bond strength of bracket bonding. The highest shear bond strength is observed in SU group, even when no primer is used. PMID:29487838

Shear bond strength of a denture base acrylic resin and gingiva-colored indirect composite material to zirconia ceramics.

PubMed

Kubochi, Kei; Komine, Futoshi; Fushiki, Ryosuke; Yagawa, Shogo; Mori, Serina; Matsumura, Hideo

2017-04-01

To evaluate the shear bond strengths of two gingiva-colored materials (an indirect composite material and a denture base acrylic resin) to zirconia ceramics and determine the effects of surface treatment with various priming agents. A gingiva-colored indirect composite material (CER) or denture base acrylic resin (PAL) was bonded to zirconia disks with unpriming (UP) or one of seven priming agents (n=11 each), namely, Alloy Primer (ALP), Clearfil Photo Bond (CPB), Clearfil Photo Bond with Clearfil Porcelain Bond Activator (CPB+Act), Metal Link (MEL), Meta Fast Bonding Liner (MFB), MR. bond (MRB), and V-Primer (VPR). Shear bond strength was determined before and after 5000 thermocycles. The data were analyzed with the Kruskal-Wallis test and Steel-Dwass test. The mean pre-/post-thermalcycling bond strengths were 1.0-14.1MPa/0.1-12.1MPa for the CER specimen and 0.9-30.2MPa/0.1-11.1MPa for the PAL specimen. For the CER specimen, the ALP, CPB, and CPB+Act groups had significantly higher bond strengths among the eight groups, at both 0 and 5000 thermocycles. For the PAL specimen, shear bond strength was significantly lower after thermalcycling in all groups tested. After 5000 thermocycles, bond strengths were significantly higher in the CPB and CPB+Act groups than in the other groups. For the PAL specimens, bond strengths were significantly lower after thermalcycling in all groups tested. The MDP functional monomer improved bonding of a gingiva-colored indirect composite material and denture base acrylic resin to zirconia ceramics. Copyright © 2016 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Crystallization stabilization mechanism of yttria-doped zirconia by hydrothermal treatment of mechanical mixtures of zirconia xerogel and crystalline yttria

NASA Astrophysics Data System (ADS)

Dell'Agli, G.; Mascolo, G.; Mascolo, M. C.; Pagliuca, C.

2005-06-01

Mechanical mixtures of zirconia xerogel and crystalline Y 2O 3 were hydrothermally treated by microwave and traditional route, respectively. Some mixtures were used either as powders form or as cylindrical compacts isostatically pressed at 150 MPa. The microwave-hydrothermal treatments were performed at 110, 150 and 200 °C for reaction times up to 2 h, whereas the traditional hydrothermal treatments were performed at 110 °C at increasing reaction times up to 7 days. All the treatments were performed in the presence of diluted (0.2 M) or concentrated (2.0 M) solution of (K 2CO 3+KOH) mineralizer. The crystallization-stabilization mechanism of synthesized Y-based zirconia powders and the reaction times for the full crystallization at the low temperature of hydrothermal treatments are discussed.

Synthesis of Mesoporous Nanocrystalline Zirconia by Surfactant-Assisted Hydrothermal Approach.

PubMed

Nath, Soumav; Biswas, Ashik; Kour, Prachi P; Sarma, Loka S; Sur, Ujjal Kumar; Ankamwar, Balaprasad G

2018-08-01

In this paper, we have reported the chemical synthesis of thermally stable mesoporous nanocrystalline zirconia with high surface area using a surfactant-assisted hydrothermal approach. We have employed different type of surfactants such as CTAB, SDS and Triton X-100 in our synthesis. The synthesized nanocrystalline zirconia multistructures exhibit various morphologies such as rod, mortar-pestle with different particle sizes. We have characterized the zirconia multistructures by X-ray diffraction study, Field emission scanning electron microscopy, Attenuated total refection infrared spectroscopy, UV-Vis spectroscopy and photoluminescence spectroscopy. The thermal stability of as synthesized zirconia multistructures was studied by thermo gravimetric analysis, which shows the high thermal stability of nanocrystalline zirconia around 900 °C temperature.

Oxygen separation from air using zirconia solid electrolyte membranes

NASA Technical Reports Server (NTRS)

Suitor, J. W.; Marner, W. J.; Schroeder, J. E.; Losey, R. W.; Ferrall, J. F.

1988-01-01

Air separation using a zirconia solid electrolyte membrane is a possible alternative source of oxygen. The process of zirconia oxygen separation is reviewed, and an oxygen plant concept using such separation is described. Potential cell designs, stack designs, and testing procedures are examined. Fabrication of the materials used in a zirconia module as well as distribution plate design and fabrication are examined.

On the interfacial fracture of porcelain/zirconia and graded zirconia dental structures.

PubMed

Chai, Herzl; Lee, James J-W; Mieleszko, Adam J; Chu, Stephen J; Zhang, Yu

2014-08-01

Porcelain fused to zirconia (PFZ) restorations are widely used in prosthetic dentistry. However, their susceptibility to fracture remains a practical problem. The failure of PFZ prostheses often involves crack initiation and growth in the porcelain, which may be followed by fracture along the porcelain/zirconia (P/Z) interface. In this work, we characterized the process of fracture in two PFZ systems, as well as a newly developed graded glass-zirconia structure with emphases placed on resistance to interfacial cracking. Thin porcelain layers were fused onto Y-TZP plates with or without the presence of a glass binder. The specimens were loaded in a four-point-bending fixture with the thin porcelain veneer in tension, simulating the lower portion of the connectors and marginal areas of a fixed dental prosthesis (FDP) during occlusal loading. The evolution of damage was observed by a video camera. The fracture was characterized by unstable growth of cracks perpendicular to the P/Z interface (channel cracks) in the porcelain layer, which was followed by stable cracking along the P/Z interface. The interfacial fracture energy GC was determined by a finite-element analysis taking into account stress-shielding effects due to the presence of adjacent channel cracks. The resulting GC was considerably less than commonly reported values for similar systems. Fracture in the graded Y-TZP samples occurred via a single channel crack at a much greater stress than for PFZ. No delamination between the residual glass layer and graded zirconia occurred in any of the tests. Combined with its enhanced resistance to edge chipping and good esthetic quality, graded Y-TZP emerges as a viable material concept for dental restorations. Copyright © 2014 Acta Materialia Inc. All rights reserved.

Initial Bacterial Adhesion on Different Yttria-Stabilized Tetragonal Zirconia Implant Surfaces in Vitro

PubMed Central

Karygianni, Lamprini; Jähnig, Andrea; Schienle, Stefanie; Bernsmann, Falk; Adolfsson, Erik; Kohal, Ralf J.; Chevalier, Jérôme; Hellwig, Elmar; Al-Ahmad, Ali

2013-01-01

Bacterial adhesion to implant biomaterials constitutes a virulence factor leading to biofilm formation, infection and treatment failure. The aim of this study was to examine the initial bacterial adhesion on different implant materials in vitro. Four implant biomaterials were incubated with Enterococcus faecalis, Staphylococcus aureus and Candida albicans for 2 h: 3 mol % yttria-stabilized tetragonal zirconia polycrystal surface (B1a), B1a with zirconium oxide (ZrO2) coating (B2a), B1a with zirconia-based composite coating (B1b) and B1a with zirconia-based composite and ZrO2 coatings (B2b). Bovine enamel slabs (BES) served as control. The adherent microorganisms were quantified and visualized using scanning electron microscopy (SEM); DAPI and live/dead staining. The lowest bacterial count of E. faecalis was detected on BES and the highest on B1a. The fewest vital C. albicans strains (42.22%) were detected on B2a surfaces, while most E. faecalis and S. aureus strains (approximately 80%) were vital overall. Compared to BES; coated and uncoated zirconia substrata exhibited no anti-adhesive properties. Further improvement of the material surface characteristics is essential. PMID:28788415

Initial Bacterial Adhesion on Different Yttria-Stabilized Tetragonal Zirconia Implant Surfaces in Vitro.

PubMed

Karygianni, Lamprini; Jähnig, Andrea; Schienle, Stefanie; Bernsmann, Falk; Adolfsson, Erik; Kohal, Ralf J; Chevalier, Jérôme; Hellwig, Elmar; Al-Ahmad, Ali

2013-12-04

Bacterial adhesion to implant biomaterials constitutes a virulence factor leading to biofilm formation, infection and treatment failure. The aim of this study was to examine the initial bacterial adhesion on different implant materials in vitro . Four implant biomaterials were incubated with Enterococcus faecalis , Staphylococcus aureus and Candida albicans for 2 h: 3 mol % yttria-stabilized tetragonal zirconia polycrystal surface (B1a), B1a with zirconium oxide (ZrO₂) coating (B2a), B1a with zirconia-based composite coating (B1b) and B1a with zirconia-based composite and ZrO₂ coatings (B2b). Bovine enamel slabs (BES) served as control. The adherent microorganisms were quantified and visualized using scanning electron microscopy (SEM); DAPI and live/dead staining. The lowest bacterial count of E. faecalis was detected on BES and the highest on B1a. The fewest vital C. albicans strains (42.22%) were detected on B2a surfaces, while most E. faecalis and S. aureus strains (approximately 80%) were vital overall. Compared to BES; coated and uncoated zirconia substrata exhibited no anti-adhesive properties. Further improvement of the material surface characteristics is essential.

Chiral Cliffs: Investigating the Influence of Chirality on Binding Affinity.

PubMed

Schneider, Nadine; Lewis, Richard A; Fechner, Nikolas; Ertl, Peter

2018-05-11

Chirality is understood by many as a binary concept: a molecule is either chiral or it is not. In terms of the action of a structure on polarized light, this is indeed true. When examined through the prism of molecular recognition, the answer becomes more nuanced. In this work, we investigated chiral behavior on protein-ligand binding: when does chirality make a difference in binding activity? Chirality is a property of the 3D structure, so recognition also requires an appreciation of the conformation. In many situations, the bioactive conformation is undefined. We set out to address this by defining and using several novel 2D descriptors to capture general characteristic features of the chiral center. Using machine-learning methods, we built different predictive models to estimate if a chiral pair (a set of two enantiomers) might exhibit a chiral cliff in a binding assay. A set of about 3800 chiral pairs extracted from the ChEMBL23 database was used to train and test our models. By achieving an accuracy of up to 75 %, our models provide good performance in discriminating chiral cliffs from non-cliffs. More importantly, we were able to derive some simple guidelines for when one can reasonably use a racemate and when an enantiopure compound is needed in an assay. We critically discuss our results and show detailed examples of using our guidelines. Along with this publication we provide our dataset, our novel descriptors, and the Python code to rebuild the predictive models. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Long-term Bond Strength between Layering Indirect Composite Material and Zirconia Coated with Silicabased Ceramics.

PubMed

Fushiki, Ryosuke; Komine, Futoshi; Honda, Junichi; Kamio, Shingo; Blatz, Markus B; Matsumura, Hideo

2015-06-01

This study evaluated the long-term shear bond strength between an indirect composite material and a zirconia framework coated with silica-based ceramics, taking the effect of different primers into account. A total of 165 airborne-particle abraded zirconia disks were subjected to one of three pretreatments: no pretreatment (ZR-AB), airborne-particle abrasion of zirconia coated with feldspathic porcelain (ZR-PO-AB), and 9.5% hydrofluoric acid etching of zirconia coated with feldspathic porcelain (ZR-PO-HF). An indirect composite material (Estenia C&B) was then bonded to the zirconia disks after they were treated with one of the following primers: Clearfil Photo Bond (CPB), Clearfil Photo Bond with Clearfil Porcelain Bond Activator (CPB + Activator), Estenia Opaque Primer (EOP), Porcelain Liner M Liquid B (PLB), or no priming (CON, control group). Shear bond strength was tested after 100,000 thermocycles, and the data were analyzed using the Steel-Dwass U-test (α = 0.05). For ZR-PO-AB and ZR-PO-HF specimens, bond strength was highest in the CPB+Activator group (25.8 MPa and 22.4 MPa, respectively). Bond strengths were significantly lower for ZR-AB specimens in the CON and PLB groups and for ZR-PO-AB specimens in the CON, CPB, and EOP groups. Combined application of a hydrophobic phosphate monomer (MDP) and silane coupling agent enhanced the long-term bond strength of indirect composite material to a zirconia coated with silica-based ceramics.

Optical properties of pre-colored dental monolithic zirconia ceramics.

PubMed

Kim, Hee-Kyung; Kim, Sung-Hun

2016-12-01

The purposes of this study were to evaluate the optical properties of recently marketed pre-colored monolithic zirconia ceramics and to compare with those of veneered zirconia and lithium disilicate glass ceramics. Various shades of pre-colored monolithic zirconia, veneered zirconia, and lithium disilicate glass ceramic specimens were tested (17.0×17.0×1.5mm, n=5). CIELab color coordinates were obtained against white, black, and grey backgrounds with a spectrophotometer. Color differences of the specimen pairs were calculated by using the CIEDE2000 (ΔE 00 ) formula. The translucency parameter (TP) was derived from ΔE 00 of the specimen against a white and a black background. X-ray diffraction was used to determine the crystalline phases of monolithic zirconia specimens. Data were analyzed with 1-way ANOVA, Scheffé post hoc, and Pearson correlation testing (α=0.05). For different shades of the same ceramic brand, there were significant differences in L * , a * , b * , and TP values in most ceramic brands. With the same nominal shade (A2), statistically significant differences were observed in L * , a * , b * , and TP values among different ceramic brands and systems (P<0.001). The color differences between pre-colored monolithic zirconia and veneered zirconia or lithium disilicate glass ceramics of the corresponding nominal shades ranged beyond the acceptability threshold. Due to the high L * values and low a * and b * values, pre-colored monolithic zirconia ceramics can be used with additional staining to match neighboring restorations or natural teeth. Due to their high value and low chroma, unacceptable color mismatch with adjacent ceramic restorations might be expected. Copyright © 2016 Elsevier Ltd. All rights reserved.

SEM evaluation of human gingival fibroblasts growth onto CAD/CAM zirconia and veneering ceramic for zirconia

PubMed Central

Zizzari, Vincenzo; Borelli, Bruna; De Colli, Marianna; Tumedei, Margherita; Di Iorio, Donato; Zara, Susi; Sorrentino, Roberto; Cataldi, Amelia; Gherlone, Enrico Felice; Zarone, Fernando; Tetè, Stefano

2013-01-01

Summary Aim To evaluate the growth of Human Gingival Fibroblasts (HGFs) cultured onto sample discs of CAD/CAM zirconia and veneering ceramic for zirconia by means of Scanning Electron Microscope (SEM) analysis at different experimental times. Methods A total of 26 experimental discs, divided into 2 groups, were used: Group A) CAD/CAM zirconia (3Y-TZP) discs (n=13); Group B) veneering ceramic for zirconia discs (n=13). HGFs were obtained from human gingival biopsies, isolated and placed in culture plates. Subsequently, cells were seeded on experimental discs at 7,5×103/cm2 concentration and cultured for a total of 7 days. Discs were processed for SEM observation at 3h, 24h, 72h and 7 days. Results In Group A, after 3h, HGFs were adherent to the surface and showed a flattened profile. The disc surface covered by HGFs resulted to be wider in Group A than in Group B samples. At SEM observation, after 24h and 72h, differences in cell attachment were slightly noticeable between the groups, with an evident flattening of HGFs on both surfaces. All differences between Group A and group B became less significant after 7 days of culture in vitro. Conclusions SEM analysis of HGFs showed differences in terms of cell adhesion and proliferation, especially in the early hours of culture. Results showed a better adhesion and cell growth in Group A than in Group B, especially up to 72h in vitro. Differences decreased after 7 days, probably because of the rougher surface of CAD/CAM zirconia, promoting better cell adhesion, compared to the smoother surface of veneering ceramic. PMID:24611089

Chiral spiral waveguides based on MMI crossings: theory and experiments

NASA Astrophysics Data System (ADS)

Cherchi, Matteo; Ylinen, Sami; Harjanne, Mikko; Kapulainen, Markku; Vehmas, Tapani; Aalto, Timo

2016-03-01

We introduce a novel type of chiral spiral waveguide where the usual waveguide crossings are replaced by 100:0 Multimode Interferometers (MMIs), i.e. 2x2 splitters that couple all the input light in the cross output port. Despite the topological equivalence with the standard configuration, we show how resorting to long MMIs has non-trivial advantages in terms of footprint and propagation length. An accurate analytic model is also introduced to show the impact of nonidealities on the spiral performances, including propagation loss and cross-talk. We have designed and fabricated three chiral spirals on our platform, based on 3 μm thick silicon strip waveguides with 0.13 dB/cm propagation loss, and 1.58 mm long MMIs. The fabricated spirals have 7, 13 and 49 loops respectively, corresponding to the effective lengths 6.6 cm, 12.5 cm and 47.9 cm. The proposed model is successfully applied to the experimental results, highlighting MMI extinction ratio of about 16.5 dB and MMI loss of about 0.08 dB, that are much worse compared to the simulated 50 dB extinction and 0.01 dB loss. This imposes an upper limit to the number of rounds, because light takes shortcuts through the bar MMI ports. Nevertheless, the novel chiral spiral waveguides outperform what is achievable in mainstream silicon photonics platforms based on submicron waveguides in terms of length and propagation losses, and they are promising candidates for the realization of integrated gyroscopes. They can be significantly further improved by replacing the MMIs with adiabatic 100:0 splitters, ensuring lower cross-talk and broader bandwidth.

Enantiospecific Detection of Chiral Nanosamples Using Photoinduced Force

NASA Astrophysics Data System (ADS)

Kamandi, Mohammad; Albooyeh, Mohammad; Guclu, Caner; Veysi, Mehdi; Zeng, Jinwei; Wickramasinghe, Kumar; Capolino, Filippo

2017-12-01

We propose a high-resolution microscopy technique for enantiospecific detection of chiral samples down to sub-100-nm size based on force measurement. We delve into the differential photoinduced optical force Δ F exerted on an achiral probe in the vicinity of a chiral sample when left and right circularly polarized beams separately excite the sample-probe interactive system. We analytically prove that Δ F is entangled with the enantiomer type of the sample enabling enantiospecific detection of chiral inclusions. Moreover, we demonstrate that Δ F is linearly dependent on both the chiral response of the sample and the electric response of the tip and is inversely related to the quartic power of probe-sample distance. We provide physical insight into the transfer of optical activity from the chiral sample to the achiral tip based on a rigorous analytical approach. We support our theoretical achievements by several numerical examples highlighting the potential application of the derived analytic properties. Lastly, we demonstrate the sensitivity of our method to enantiospecify nanoscale chiral samples with chirality parameter on the order of 0.01 and discuss how the sensitivity of our proposed technique can be further improved.

Electric line source illumination of a chiral cylinder placed in another chiral background medium

NASA Astrophysics Data System (ADS)

Aslam, M.; Saleem, A.; Awan, Z. A.

2018-05-01

An electric line source illumination of a chiral cylinder embedded in a chiral background medium is considered. The field expressions inside and outside of a chiral cylinder have been derived using the wave field decomposition approach. The effects of various chiral cylinders, chiral background media and source locations upon the scattering gain pattern have been investigated. It is observed that the chiral background reduces the backward scattering gain as compared to the free space background for a dielectric cylinder. It is also studied that by moving a line source away from a cylinder reduces the backward scattering gain for a chiral cylinder placed in a chiral background under some specific conditions. A unique phenomenon of reduced scattering gain has been observed at a specific observation angle for a chiral cylinder placed in a chiral background having an electric line source location of unity free space wavelength. An isotropic scattering gain pattern is observed for a chiral nihility background provided that if cylinder is chiral or chiral nihility type. It is also observed that this isotropic behaviour is independent of background and cylinder chirality.

Chiral dynamics with (non)strange quarks

NASA Astrophysics Data System (ADS)

Kubis, Bastian; Meißner, Ulf-G.

2017-01-01

We review the results and achievements of the project B.3. Topics addressed include pion photoproduction off the proton and off deuterium, three-flavor chiral perturbation theory studies, chiral symmetry tests in Goldstone boson decays, the development of unitarized chiral perturbation theory to next-to-leading order, the two-pole structure of the Λ(1405), the dynamical generation of the lowest S11 resonances, the theory of hadronic atoms and its application to various systems, precision studies in light-meson decays based on dispersion theory, the Roy-Steiner analysis of pion-nucleon scattering, a high-precision extraction of the elusive pion-nucleon σ-term, and aspects of chiral dynamics in few-nucleon systems.

A chiral sensor based on weak measurement for the determination of Proline enantiomers in diverse measuring circumstances.

PubMed

Li, Dongmei; Guan, Tian; He, Yonghong; Liu, Fang; Yang, Anping; He, Qinghua; Shen, Zhiyuan; Xin, Meiguo

2018-07-01

A new chiral sensor based on weak measurement to accurately measure the optical rotation (OR) has been developed for the estimation of a trace amount of chiral molecule. With the principle of optical weak measurement in frequency domain, the central wavelength shift of output spectra is quantitatively relative to the angle of preselected polarization. Hence, a chiral molecule (e.g., L-amino acid, or D-amino acid) can be enantioselectively determined by modifying the preselection angle with the OR, which will cause the rotation of a polarization plane. The concentration of the chiral sample, corresponding to its optical activity, is quantitatively analyzed with the central wavelength shift of output spectra, which can be collected in real time. Immune to the refractive index change, the proposed chiral sensor is valid in complicated measuring circumstance. The detections of Proline enantiomer concentration in different solvents were implemented. The results demonstrated that weak measurement acted as a reliable method to chiral recognition of Proline enantiomers in diverse circumstance with the merits of high precision and good robustness. In addition, this real-time monitoring approach plays a crucial part in asymmetric synthesis and biological systems. Copyright © 2018. Published by Elsevier B.V.

An overview of zirconia ceramics: basic properties and clinical applications.

PubMed

Manicone, Paolo Francesco; Rossi Iommetti, Pierfrancesco; Raffaelli, Luca

2007-11-01

Zirconia (ZrO2) is a ceramic material with adequate mechanical properties for manufacturing of medical devices. Zirconia stabilized with Y2O3 has the best properties for these applications. When a stress occurs on a ZrO2 surface, a crystalline modification opposes the propagation of cracks. Compression resistance of ZrO2 is about 2000 MPa. Orthopedic research led to this material being proposed for the manufacture of hip head prostheses. Prior to this, zirconia biocompatibility had been studied in vivo; no adverse responses were reported following the insertion of ZrO2 samples into bone or muscle. In vitro experimentation showed absence of mutations and good viability of cells cultured on this material. Zirconia cores for fixed partial dentures (FPD) on anterior and posterior teeth and on implants are now available. Clinical evaluation of abutments and periodontal tissue must be performed prior to their use. Zirconia opacity is very useful in adverse clinical situations, for example, for masking of dischromic abutment teeth. Radiopacity can aid evaluation during radiographic controls. Zirconia frameworks are realized by using computer-aided design/manufacturing (CAD/CAM) technology. Cementation of Zr-ceramic restorations can be performed with adhesive luting. Mechanical properties of zirconium oxide FPDs have proved superior to those of other metal-free restorations. Clinical evaluations, which have been ongoing for 3 years, indicate a good success rate for zirconia FPDs. Zirconia implant abutments can also be used to improve the aesthetic outcome of implant-supported rehabilitations. Newly proposed zirconia implants seem to have good biological and mechanical properties; further studies are needed to validate their application.

Phase field modeling of tetragonal to monoclinic phase transformation in zirconia

NASA Astrophysics Data System (ADS)

Mamivand, Mahmood

Zirconia based ceramics are strong, hard, inert, and smooth, with low thermal conductivity and good biocompatibility. Such properties made zirconia ceramics an ideal material for different applications form thermal barrier coatings (TBCs) to biomedicine applications like femoral implants and dental bridges. However, this unusual versatility of excellent properties would be mediated by the metastable tetragonal (or cubic) transformation to the stable monoclinic phase after a certain exposure at service temperatures. This transformation from tetragonal to monoclinic, known as LTD (low temperature degradation) in biomedical application, proceeds by propagation of martensite, which corresponds to transformation twinning. As such, tetragonal to monoclinic transformation is highly sensitive to mechanical and chemomechanical stresses. It is known in fact that this transformation is the source of the fracture toughening in stabilized zirconia as it occurs at the stress concentration regions ahead of the crack tip. This dissertation is an attempt to provide a kinetic-based model for tetragonal to monoclinic transformation in zirconia. We used the phase field technique to capture the temporal and spatial evolution of monoclinic phase. In addition to morphological patterns, we were able to calculate the developed internal stresses during tetragonal to monoclinic transformation. The model was started form the two dimensional single crystal then was expanded to the two dimensional polycrystalline and finally to the three dimensional single crystal. The model is able to predict the most physical properties associated with tetragonal to monoclinic transformation in zirconia including: morphological patterns, transformation toughening, shape memory effect, pseudoelasticity, surface uplift, and variants impingement. The model was benched marked with several experimental works. The good agreements between simulation results and experimental data, make the model a reliable tool for

Cooperative expression of atomic chirality in inorganic nanostructures.

PubMed

Wang, Peng-Peng; Yu, Shang-Jie; Govorov, Alexander O; Ouyang, Min

2017-02-02

Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks.

Cooperative expression of atomic chirality in inorganic nanostructures

PubMed Central

Wang, Peng-peng; Yu, Shang-Jie; Govorov, Alexander O; Ouyang, Min

2017-01-01

Cooperative chirality phenomena extensively exist in biomolecular and organic systems via intra- and inter-molecular interactions, but study of inorganic materials has been lacking. Here we report, experimentally and theoretically, cooperative chirality in colloidal cinnabar mercury sulfide nanocrystals that originates from chirality interplay between the crystallographic lattice and geometric morphology at different length scales. A two-step synthetic scheme is developed to allow control of critical parameters of these two types of handedness, resulting in different chiral interplays expressed as observables through materials engineering. Furthermore, we adopt an electromagnetic model with the finite element method to elucidate cooperative chirality in inorganic systems, showing excellent agreement with experimental results. Our study enables an emerging class of nanostructures with tailored cooperative chirality that is vital for fundamental understanding of nanoscale chirality as well as technology applications based on new chiroptical building blocks. PMID:28148957

Chiral ligand exchange high-speed countercurrent chromatography: mechanism, application and comparison with conventional liquid chromatography in enantioseparation of aromatic α-hydroxyl acids

PubMed Central

Tong, Shengqiang; Shen, Mangmang; Cheng, Dongping; Ito, Yoichiro; Yan, Jizhong

2014-01-01

This work concentrates on the separation mechanism and application of chiral ligand exchange high-speed countercurrent chromatography (HSCCC) in enantioseparations, and comparison with traditional chiral ligand exchange high performance liquid chromatography (HPLC). The enantioseparation of ten aromatic α-hydroxyl acids were performed by these two chromatographic methods. Results showed that five of the racemates were successfully enantioseparated by HSCCC while only three of the racemates could be enantioseparated by HPLC using a suitable chiral ligand mobile phase additive. For HSCCC, the two-phase solvent system was composed of butanol-water (1:1, v/v), to which N-n-dodecyl-L-proline was added in the organic phase as chiral ligand and cupric acetate was added in the aqueous phase as a transition metal ion. Various operation parameters in HSCCC were optimized by enantioselective liquid-liquid extraction. Based on the results of the present studies the separation mechanism for HSCCC was proposed. For HPLC, the optimized mobile phase composed of aqueous solution containing 6 mmol L−1 L-phenylalanine and 3 mmol L−1 cupric sulfate and methanol was used for enantioseparation. Among three ligands tested on a conventional reverse stationary phase column, only one was found to be effective. In the present studies HSCCC presented unique advantages due to its high versatility of two-phase solvent systems and it could be used as an alternative method for enantioseparations. PMID:25087742

Shear bond strength between resin cement and colored zirconia made with metal chlorides.

PubMed

Kim, Ga-Hyun; Park, Sang-Won; Lee, Kwangmin; Oh, Gye-Jeong; Lim, Hyun-Pil

2015-06-01

Although the application of zirconia in esthetic prostheses has increased, the shear bond strength (SBS) between colored zirconia and resin cement has not been investigated. The purpose of this study was to compare the SBS between resin cement and colored zirconia made with metal chlorides. Sixty-four zirconia specimens were divided into 2 groups: one in which the specimens were bonded with resin cement, including 4-META (4-methacryloxyethyl trimellitic anhydride), and one in which the specimens were bonded with resin cement (SEcure, Sun Medical) after being processed with zirconia primer (Zirconia Liner), including 4-META. Each group was then divided into 4 subgroups depending on the coloring liquid. The subgroups were noncolored (control), commercial coloring liquid VITA In-Ceram 2000 YZ LL1, aqueous chromium chloride solution 0.1 wt%, and aqueous molybdenum chloride solution 0.1 wt%. Composite resin cylinders (Filtek Z250, 3M ESPE) were fabricated and bonded to the surface of the zirconia specimen with resin cement (SEcure). All specimens were stored in 37°C distilled water for 24 hours, and the SBS was measured with a universal testing machine. All data were analyzed statistically with 2-way ANOVA and tested post hoc with the Tukey test (α=.05). Significant differences were observed among the SBS values of the colored zirconia depending on the coloring liquid (P<.001) and whether they were processed with zirconia primer (P<.001). The SBS between colored zirconia and resin cement was significantly higher than that of noncolored zirconia and resin cement in groups processed with zirconia primer (P<.05). Colored zirconia immersed in aqueous molybdenum chloride solution showed a significantly higher SBS. Coloring liquid enhanced the SBS between resin cement and zirconia processed with zirconia primer. In particular, colored zirconia immersed in aqueous molybdenum chloride solution showed the highest SBS. Copyright © 2015 Editorial Council for the Journal of

Active chiral fluids.

PubMed

Fürthauer, S; Strempel, M; Grill, S W; Jülicher, F

2012-09-01

Active processes in biological systems often exhibit chiral asymmetries. Examples are the chirality of cytoskeletal filaments which interact with motor proteins, the chirality of the beat of cilia and flagella as well as the helical trajectories of many biological microswimmers. Here, we derive constitutive material equations for active fluids which account for the effects of active chiral processes. We identify active contributions to the antisymmetric part of the stress as well as active angular momentum fluxes. We discuss four types of elementary chiral motors and their effects on a surrounding fluid. We show that large-scale chiral flows can result from the collective behavior of such motors even in cases where isolated motors do not create a hydrodynamic far field.

Chemical interaction mechanism of 10-MDP with zirconia

PubMed Central

Nagaoka, Noriyuki; Yoshihara, Kumiko; Feitosa, Victor Pinheiro; Tamada, Yoshiyuki; Irie, Masao; Yoshida, Yasuhiro; Van Meerbeek, Bart; Hayakawa, Satoshi

2017-01-01

Currently, the functional monomer 10-methacryloyloxy-decyl-dihydrogen-phosphate (10-MDP) was documented to chemically bond to zirconia ceramics. However, little research has been conducted to unravel the underlying mechanisms. This study aimed to assess the chemical interaction and to demonstrate the mechanisms of coordination between 10-MDP and zirconium oxide using 1H and 31P magic angle spinning (MAS) nuclear magnetic resonance (NMR) and two dimensional (2D) 1H → 31P heteronuclear correlation (HETCOR) NMR. In addition, shear bond-strength (SBS) tests were conducted to determine the effect of 10-MDP concentration on the bonding effectiveness to zirconia. These SBS tests revealed a 10-MDP concentration-dependent SBS with a minimum of 1-ppb 10-MDP needed. 31P-NMR revealed that one P-OH non-deprotonated of the PO3H2 group from 10-MDP chemically bonded strongly to zirconia. 1H-31P HETCOR NMR indicated that the 10-MDP monomer can be adsorbed onto the zirconia particles by hydrogen bonding between the P=O and Zr-OH groups or via ionic interactions between partially positive Zr and deprotonated 10-MDP (P-O−). The combination of 1H NMR and 2D 1H-31P HETCOR NMR enabled to describe the different chemical states of the 10-MDP bonds with zirconia; they not only revealed ionic but also hydrogen bonding between 10-MDP and zirconia. PMID:28358121

Chiral discrimination of α-hydroxy acids and N-Ts-α-amino acids induced by tetraaza macrocyclic chiral solvating agents by using 1H NMR spectroscopy.

PubMed

Lv, Caixia; Feng, Lei; Zhao, Hongmei; Wang, Guo; Stavropoulos, Pericles; Ai, Lin

2017-02-21

In the field of chiral recognition, reported chiral discrimination by 1 H NMR spectroscopy has mainly focused on various chiral analytes with a single chiral center, regarded as standard chiral substrates to evaluate the chiral discriminating abilities of a chiral auxiliary. Among them, chiral α-hydroxy acids, α-amino acids and their derivatives are chiral organic molecules involved in a wide variety of biological processes, and also play an important role in the area of preparation of pharmaceuticals, as they are part of the synthetic process in the production of chiral drug intermediates and protein-based drugs. In this paper, several α-hydroxy acids and N-Ts-α-amino acids were used to evaluate the chiral discriminating abilities of tetraaza macrocyclic chiral solvating agents (TAMCSAs) 1a-1d by 1 H NMR spectroscopy. The results indicate that α-hydroxy acids and N-Ts-α-amino acids were successfully discriminated in the presence of TAMCSAs 1a-1d by 1 H NMR spectroscopy in most cases. The enantiomers of the α-hydroxy acids and N-Ts-α-amino acids were assigned based on the change of integration of the 1 H NMR signals of the corresponding protons. The enantiomeric excesses (ee) of N-Ts-α-amino acids 11 with different optical compositions were calculated based on the integration of the 1 H NMR signals of the CH 3 protons (Ts group) of the enantiomers of (R)- and (S)-11 in the presence of TAMCSA 1b. At the same time, the possible chiral discriminating behaviors have been discussed by means of the Job plots of (±)-2 with TAMCSAs 1b and proposed theoretical models of the enantiomers of 2 and 6 with TAMCSA 1a, respectively.

Bonding effectiveness to different chemically pre-treated dental zirconia.

PubMed

Inokoshi, Masanao; Poitevin, André; De Munck, Jan; Minakuchi, Shunsuke; Van Meerbeek, Bart

2014-09-01

The objective of this study was to evaluate the effect of different chemical pre-treatments on the bond durability to dental zirconia. Fully sintered IPS e.max ZirCAD (Ivoclar Vivadent) blocks were subjected to tribochemical silica sandblasting (CoJet, 3M ESPE). The zirconia samples were additionally pre-treated using one of four zirconia primers/adhesives (Clearfil Ceramic Primer, Kuraray Noritake; Monobond Plus, Ivoclar Vivadent; Scotchbond Universal, 3M ESPE; Z-PRIME Plus, Bisco). Finally, two identically pre-treated zirconia blocks were bonded together using composite cement (RelyX Ultimate, 3M ESPE). The specimens were trimmed at the interface to a cylindrical hourglass and stored in distilled water (7 days, 37 °C), after which they were randomly tested as is or subjected to mechanical ageing involving cyclic tensile stress (10 N, 10 Hz, 10,000 cycles). Subsequently, the micro-tensile bond strength was determined, and SEM fractographic analysis performed. Weibull analysis revealed the highest Weibull scale and shape parameters for the 'Clearfil Ceramic Primer/mechanical ageing' combination. Chemical pre-treatment of CoJet (3M ESPE) sandblasted zirconia using Clearfil Ceramic Primer (Kuraray Noritake) and Monobond Plus (Ivoclar Vivadent) revealed a significantly higher bond strength than when Scotchbond Universal (3M ESPE) and Z-PRIME Plus (Bisco) were used. After ageing, Clearfil Ceramic Primer (Kuraray Noritake) revealed the most stable bond durability. Combined mechanical/chemical pre-treatment, the latter with either Clearfil Ceramic Primer (Kuraray Noritake) or Monobond Plus (Ivoclar Vivadent), resulted in the most durable bond to zirconia. As a standard procedure to durably bond zirconia to tooth tissue, the application of a combined 10-methacryloyloxydecyl dihydrogen phosphate/silane ceramic primer to zirconia is clinically highly recommended.

Osteogenic Responses to Zirconia with Hydroxyapatite Coating by Aerosol Deposition

PubMed Central

Cho, Y.; Hong, J.; Ryoo, H.; Kim, D.; Park, J.

2015-01-01

Previously, we found that osteogenic responses to zirconia co-doped with niobium oxide (Nb2O5) or tantalum oxide (Ta2O5) are comparable with responses to titanium, which is widely used as a dental implant material. The present study aimed to evaluate the in vitro osteogenic potential of hydroxyapatite (HA)-coated zirconia by an aerosol deposition method for improved osseointegration. Surface analysis by scanning electron microscopy and x-ray diffraction proved that a thin as-deposited HA film on zirconia showed a shallow, regular, crater-like surface. Deposition of dense and uniform HA films was measured by SEM, and the contact angle test demonstrated improved wettability of the HA-coated surface. Confocal laser scanning microscopy indicated that MC3T3-E1 pre-osteoblast attachment did not differ notably between the titanium and zirconia surfaces; however, cells on the HA-coated zirconia exhibited a lower proliferation than those on the uncoated zirconia late in the culture. Nevertheless, ALP, alizarin red S staining, and bone marker gene expression analysis indicated good osteogenic responses on HA-coated zirconia. Our results suggest that HA-coating by aerosol deposition improves the quality of surface modification and is favorable to osteogenesis. PMID:25586588

Chiral Graphene Quantum Dots

DOE PAGES

Suzuki, Nozomu; Wang, Yichun; Elvati, Paolo; ...

2016-01-15

Chiral nanostructures from metals and semiconductors attract wide interest as components for polarization-enabled optoelectronic devices. Similarly to other fields of nanotechnology, graphene-based materials can greatly enrich physical and chemical phenomena associated with optical and electronic properties of chiral nanostructures and facilitate their applications in biology as well as other areas. Here, we report that covalent attachment of l/d-cysteine moieties to the edges of graphene quantum dots (GQDs) leads to their helical buckling due to chiral interactions at the “crowded” edges. Circular dichroism (CD) spectra of the GQDs revealed bands at ca. 210–220 and 250–265 nm that changed their signs formore » different chirality of the cysteine edge ligands. The high-energy chiroptical peaks at 210–220 nm correspond to the hybridized molecular orbitals involving the chiral center of amino acids and atoms of graphene edges. Diverse experimental and modeling data, including density functional theory calculations of CD spectra with probabilistic distribution of GQD isomers, indicate that the band at 250–265 nm originates from the three-dimensional twisting of the graphene sheet and can be attributed to the chiral excitonic transitions. The positive and negative low-energy CD bands correspond to the left and right helicity of GQDs, respectively. Exposure of liver HepG2 cells to l/d-GQDs reveals their general biocompatibility and a noticeable difference in the toxicity of the stereoisomers. Molecular dynamics simulations demonstrated that d-GQDs have a stronger tendency to accumulate within the cellular membrane than l-GQDs. Finally, emergence of nanoscale chirality in GQDs decorated with biomolecules is expected to be a general stereochemical phenomenon for flexible sheets of nanomaterials.« less

Chiral magnetic effect in lattice QCD with a chiral chemical potential.

PubMed

Yamamoto, Arata

2011-07-15

We perform a first lattice QCD simulation including a two-flavor dynamical fermion with a chiral chemical potential. Because the chiral chemical potential gives rise to no sign problem, we can exactly analyze a chirally imbalanced QCD matter by Monte Carlo simulation. By applying an external magnetic field to this system, we obtain a finite induced current along the magnetic field, which corresponds to the chiral magnetic effect. The obtained induced current is proportional to the magnetic field and to the chiral chemical potential, which is consistent with an analytical prediction.

Temperature-Triggered Switchable Helix-Helix Inversion of Poly(phenylacetylene) Bearing l-Valine Ethyl Ester Pendants and Its Chiral Recognition Ability.

PubMed

Zhou, Yanli; Zhang, Chunhong; Qiu, Yuan; Liu, Lijia; Yang, Taotao; Dong, Hongxing; Satoh, Toshifumi; Okamoto, Yoshio

2016-11-21

A phenylacetylene containing the l-valine ethyl ester pendant (PAA-Val) was synthesized and polymerized by an organorhodium catalyst (Rh(nbd)BPh₄) to produce the corresponding one-handed helical cis -poly(phenylacetylene) (PPAA-Val). PPAA-Val showed a unique temperature-triggered switchable helix-sense in chloroform, while it was not observed in highly polar solvents, such as N , N '-dimethylformamide (DMF). By heating the solution of PPAA-Val in chloroform, the sign of the CD absorption became reversed, but recovered after cooling the solution to room temperature. Even after six cycles of the heating-cooling treatment, the helix sense of the PPAA-Val's backbone was still switchable without loss of the CD intensity. The PPAA-Val was then coated on silica gel particles to produce novel chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). These novel PPAA-Val based CSPs showed a high chiral recognition ability for racemic mandelonitrile ( α = 2.18) and racemic trans - N , N '-diphenylcyclohexane-1,2-dicarboxamide ( α = 2.60). Additionally, the one-handed helical cis -polyene backbone of PPAA-Val was irreversibly destroyed to afford PPAA-Val-H by heating in dimethyl sulfoxide (DMSO) accompanied by the complete disappearance of the Cotton effect. Although PPAA-Val-H had the same l-valine ethyl ester pendants as its cis -isomer PPAA-Val, it showed no chiral recognition. It was concluded that the one-handed helical cis -polyene backbone of PPAA-Val plays an important role in the chiral recognition ability.

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids.

PubMed

Suzuki, Yumiko

2018-06-01

Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines.

[Measurement of chromaticity of five hued zirconia].

PubMed

Wen, Ning; Shao, Long-quan; Yi, Yuan-fu; Deng, Bin; Liu, Hong-chen

2009-05-01

To determine the chroma value of sintered IL1-IL5 zirconia materials in comparison with the Vita In-Ceram YZ color shade. Five types of shading dental zirconia ceramics with color gradient were prepared by adding Fe2O3, CeO2, and Bi2O3 to the zirconia powder, and their chroma values were determined using a spectrophotometer and the color difference was calculated. The chroma value ranges were L: 67.76-77.78, a: -2.19-3.80, and b: 12.13-25.01. Slight deltaE was found between IL1 and LL1, IL2 and LL2, and IL3 and LL3. The deltaE between IL4 and LL4 could be compensated by veneering porcelain, whereas deltaL between IL5 and LL5 could not be compensated in this manner. Shading dental zirconia ceramics can be prepared by addition of metal oxides with color similar to the Vita In-Ceram YZ color shades to match that of the veneering porcelain in clinical practice.

Large scale synthesis of nanostructured zirconia-based compounds from freeze-dried precursors

NASA Astrophysics Data System (ADS)

Gómez, A.; Villanueva, R.; Vie, D.; Murcia-Mascaros, S.; Martínez, E.; Beltrán, A.; Sapiña, F.; Vicent, M.; Sánchez, E.

2013-01-01

Nanocrystalline zirconia powders have been obtained at the multigram scale by thermal decomposition of precursors resulting from the freeze-drying of aqueous acetic solutions. This technique has equally made possible to synthesize a variety of nanostructured yttria or scandia doped zirconia compositions. SEM images, as well as the analysis of the XRD patterns, show the nanoparticulated character of those solids obtained at low temperature, with typical particle size in the 10-15 nm range when prepared at 673 K. The presence of the monoclinic, the tetragonal or both phases depends on the temperature of the thermal treatment, the doping concentration and the nature of the dopant. In addition, Rietveld refinement of the XRD profiles of selected samples allows detecting the coexistence of the tetragonal and the cubic phases for high doping concentration and high thermal treatment temperatures. Raman experiments suggest the presence of both phases also at relatively low treatment temperatures.

Positron annihilation studies of zirconia doped with metal cations of different valence

NASA Astrophysics Data System (ADS)

Prochazka, I.; Cizek, J.; Melikhova, O.; Konstantinova, T. E.; Danilenko, I. A.; Yashchishyn, I. A.; Anwand, W.; Brauer, G.

2013-06-01

New results obtained by applying positron annihilation spectroscopy to the investigation of zirconia-based nanomaterials doped with metal cations of different valence are reported. The slow-positron implantation spectroscopy combined with Doppler broadening measurements was employed to study the sintering of pressure-compacted nanopowders of tetragonal yttria-stabilised zirconia (t-YSZ) and t-YSZ with chromia additive. Positronium (Ps) formation in t-YSZ was proven by detecting 3γ-annihilations of ortho-Ps and was found to gradually decrease with increasing sintering temperature. A subsurface layer with enhanced 3γ-annihilations, compared to the deeper regions, could be identified. Addition of chromia was found to inhibit Ps formation. In addition, first results of positron lifetime measurements on nanopowders of zirconia phase-stabilised with MgO and CeO2 are presented.

Processing of Alumina-Toughened Zirconia Composites

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Choi, Sung R.

2003-01-01

Dense and crack-free 10-mol%-yttria-stabilized zirconia (10YSZ)-alumina composites, containing 0 to 30 mol% of alumina, have been fabricated by hot pressing. Release of pressure before onset of cooling was crucial in obtaining crack-free material. Hot pressing at 1600 C resulted in the formation of ZrC by reaction of zirconia with grafoil. However, no such reaction was observed at 1500 C. Cubic zirconia and -alumina were the only phases detected from x-ray diffraction indicating no chemical reaction between the composite constituents during hot pressing. Microstructure of the composites was analyzed by scanning electron microscopy and transmission electron microscopy. Density and elastic modulus of the composites followed the rule-of-mixtures. Addition of alumina to 10YSZ resulted in lighter, stronger, and stiffer composites by decreasing density and increasing strength and elastic modulus.

Acylation of Chiral Alcohols: A Simple Procedure for Chiral GC Analysis.

PubMed

Oromí-Farrús, Mireia; Torres, Mercè; Canela, Ramon

2012-01-01

The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC.

A web site for calculating the degree of chirality.

PubMed

Zayit, Amir; Pinsky, Mark; Elgavi, Hadassah; Dryzun, Chaim; Avnir, David

2011-01-01

The web site, http://www.csm.huji.ac.il/, uses the Continuous Chirality Measure to evaluate quantitatively the degree of chirality of a molecule, a structure, a fragment. The value of this measure ranges from zero, the molecule is achiral, to higher values (the upper limit is 100); the higher the chirality value, the more chiral the molecule is. The measure is based on the distance between the chiral molecule and the nearest structure that is achiral. Questions such as the following can be addressed: by how much is one molecule more chiral than the other? how does chirality change along conformational motions? is there a correlation between chirality and enantioselectivity in a series of molecules? Both elementary and advanced features are offered. Related calculation options are the symmetry measures and shape measures. Copyright © 2009 Wiley-Liss, Inc.

The effect of plasma on shear bond strength between resin cement and colored zirconia

PubMed Central

2017-01-01

PURPOSE To investigate the effect of non-thermal atmospheric pressure plasma (NTAPP) treatment on shear bond strength (SBS) between resin cement and colored zirconia made with metal chlorides. MATERIALS AND METHODS 60 zirconia specimens were divided into 3 groups using coloring liquid. Each group was divided again into 2 sub-groups using plasma treatment; the experimental group was treated with plasma, and the control group was untreated. The sub-groups were: N (non-colored), C (0.1 wt% aqueous chromium chloride solution), M (0.1 wt% aqueous molybdenum chloride solution), NP (non-colored with plasma), CP (0.1 wt% aqueous chromium chloride solution with plasma), and MP (0.1 wt% aqueous molybdenum chloride solution with plasma). Composite resin cylinders were bonded to zirconia specimens with MDP-based resin cement, and SBS was measured using a universal testing machine. All data was analyzed statistically using a 2-way ANOVA test and a Tukey test. RESULTS SBS significantly increased when specimens were treated with NTAPP regardless of coloring (P<.001). Colored zirconia containing molybdenum showed the highest value of SBS, regardless of NTAPP. The molybdenum group showed the highest SBS, whereas the chromium group showed the lowest. CONCLUSION NTAPP may increase the SBS of colored zirconia and resin cement. The NTAPP effect on SBS is not influenced by the presence of zirconia coloring. PMID:28435621

Translucency of Zirconia Ceramics before and after Artificial Aging.

PubMed

Walczak, Katarzyna; Meißner, Heike; Range, Ursula; Sakkas, Andreas; Boening, Klaus; Wieckiewicz, Mieszko; Konstantinidis, Ioannis

2018-03-11

The aging of zirconia ceramics (Y-TZP) is associated with tetragonal to monoclinic phase transformation. This change in microstructure may affect the optical properties of the ceramic. This study examines the effect of aging on the translucency of different zirconia materials. 120 disc-shaped specimens were fabricated from four zirconia materials: Cercon ht white, BruxZir Solid Zirconia, Zenostar T0, Lava Plus (n = 30 per group). Accelerated aging was performed in a steam autoclave (134°C, 0.2 MPa, 5 hours). CIELab coordinates (L*, a*, b*) and luminous reflectance (Y) were measured with a spectrophotometer before and after aging. Contrast ratio (CR) and translucency parameter (TP) were calculated from the L*, a*, b*, and Y tristimulus values. The general linear model (Bonferroni adjusted) was used to compare both parameters before and after aging, as well as between the different zirconia materials (p ≤ 0.05). CR and TP differed significantly before and after aging in all groups tested. Before aging, Zenostar T showed the highest and Lava Plus showed the lowest translucency. After aging, Cercon ht and Zenostar T showed the highest and BruxZir and Lava Plus the lowest translucency. Aging reduced the translucency in all specimens tested. Furthermore, translucency differed between the zirconia brands tested. Nevertheless, the differences were below the detectability threshold of the human eye. The aging process can influence the translucency and thus the esthetic outcome of zirconia restorations; however, the changes in translucency were minimal and probably undetectable by the human eye. © 2018 by the American College of Prosthodontists.

Hot Corrosion of Yttrium Stabilized Zirconia Coatings Deposited by Air Plasma Spray on a Nickel-Based Superalloy

NASA Astrophysics Data System (ADS)

Vallejo, N. Diaz; Sanchez, O.; Caicedo, J. C.; Aperador, W.; Zambrano, G.

In this research, the electrochemical impedance spectroscopy (EIS) and Tafel analysis were utilized to study the hot corrosion performance at 700∘C of air plasma-sprayed (APS) yttria-stabilized zirconia (YSZ) coatings with a NiCrAlY bond coat grown by high velocity oxygen fuel spraying (HVOF), deposited on an INCONEL 625 substrate, in contact with corrosive solids salts as vanadium pentoxide V2O5 and sodium sulfate Na2SO4. The EIS data were interpreted based on proposed equivalent electrical circuits using a suitable fitting procedure performed with Echem AnalystTM Software. Phase transformations and microstructural development were examined using X-ray diffraction (XRD), with Rietveld refinement for quantitative phase analysis, scanning electron microscopy (SEM) was used to determinate the coating morphology and corrosion products. The XRD analysis indicated that the reaction between sodium vanadate (NaVO3) and yttrium oxide (Y2O3) produces yttrium vanadate (YVO4) and leads to the transformation from tetragonal to monoclinic zirconia phase.

Chiral Polymers.

DTIC Science & Technology

1984-10-01

regardless of the method of polymerization. The styrene-bead copolymers were packed in HPLC columns, but none were especiall, effective in separating...enantiomers in a racemic mixture. The chiral butyrolactone polymer was coated on silica, but this material did not effect resolution of racemic mixtures in an...been effected utilizing chiral oxazolines3 prompted the initial efforts to synthesize various chiral 2-vinyl- oxazoline monomers for incorporation

Chiral Separation of G-type Chemical Warfare Nerve Agents via Analytical Supercritical Fluid Chromatography

PubMed Central

Kasten, Shane A; Zulli, Steven; Jones, Jonathan L; Dephillipo, Thomas; Cerasoli, Douglas M

2014-01-01

Chemical warfare nerve agents (CWNAs) are extremely toxic organophosphorus compounds that contain a chiral phosphorus center. Undirected synthesis of G-type CWNAs produces stereoisomers of tabun, sarin, soman, and cyclosarin (GA, GB, GD, and GF, respectively). Analytical-scale methods were developed using a supercritical fluid chromatography (SFC) system in tandem with a mass spectrometer for the separation, quantitation, and isolation of individual stereoisomers of GA, GB, GD, and GF. Screening various chiral stationary phases (CSPs) for the capacity to provide full baseline separation of the CWNAs revealed that a Regis WhelkO1 (SS) column was capable of separating the enantiomers of GA, GB, and GF, with elution of the P(+) enantiomer preceding elution of the corresponding P(–) enantiomer; two WhelkO1 (SS) columns had to be connected in series to achieve complete baseline resolution. The four diastereomers of GD were also resolved using two tandem WhelkO1 (SS) columns, with complete baseline separation of the two P(+) epimers. A single WhelkO1 (RR) column with inverse stereochemistry resulted in baseline separation of the GD P(–) epimers. The analytical methods described can be scaled to allow isolation of individual stereoisomers to assist in screening and development of countermeasures to organophosphorus nerve agents. Chirality 26:817–824, 2014. © 2014 The Authors. Chirality published by John Wiley Periodicals, Inc. PMID:25298066

Can a Non-Chiral Object Be Made of Two Identical Chiral Moieties?

ERIC Educational Resources Information Center

LeMarechal, Jean Francois

2008-01-01

Several pedagogical objects can be used to discuss chirality. Here, we use the cut of an apple to show that the association of identical chiral moieties can form a non-chiral object. Octahedral chirality is used to find situations equivalent to the cut of the apple. (Contains 5 figures.)

Enhanced Chiral Discriminatory van der Waals Interactions Mediated by Chiral Surfaces

NASA Astrophysics Data System (ADS)

Barcellona, Pablo; Safari, Hassan; Salam, A.; Buhmann, Stefan Yoshi

2017-05-01

We predict a discriminatory interaction between a chiral molecule and an achiral molecule which is mediated by a chiral body. To achieve this, we generalize the van der Waals interaction potential between two ground-state molecules with electric, magnetic, and chiral response to nontrivial environments. The force is evaluated using second-order perturbation theory with an effective Hamiltonian. Chiral media enhance or reduce the free interaction via many-body interactions, making it possible to measure the chiral contributions to the van der Waals force with current technology. The van der Waals interaction is discriminatory with respect to enantiomers of different handedness and could be used to separate enantiomers. We also suggest a specific geometric configuration where the electric contribution to the van der Waals interaction is zero, making the chiral component the dominant effect.

Selective catalytic reduction system and process using a pre-sulfated zirconia binder

DOEpatents

Sobolevskiy, Anatoly; Rossin, Joseph A.

2010-06-29

A selective catalytic reduction (SCR) process with a palladium catalyst for reducing NOx in a gas, using hydrogen as a reducing agent is provided. The process comprises contacting the gas stream with a catalyst system, the catalyst system comprising (ZrO.sub.2)SO.sub.4, palladium, and a pre-sulfated zirconia binder. The inclusion of a pre-sulfated zirconia binder substantially increases the durability of a Pd-based SCR catalyst system. A system for implementing the disclosed process is further provided.

Illuminating the chirality of Weyl fermions

NASA Astrophysics Data System (ADS)

Ma, Qiong; Xu, Su-Yang; Chan, Ching-Kit; Zhang, Cheng-Long; Chang, Guoqing; Lin, Hsin; Jia, Shuang; Lee, Patrick; Gedik, Nuh; Jarillo-Herrero, Pablo

In particle physics, Weyl fermions (WF) are elementary particles that travel at the speed of light and have a definite chirality. In condensed matter, it has been recently realized that WFs can arise as magnetic monopoles in the momentum space of a novel topological metal, the Weyl semimetal (WSM). Their chirality, given by the sign of the monopole charge, is the defining property of a WSM, since it directly serves as the topological number and gives rise to exotic properties such as Fermi arcs and the chiral anomaly. Moreover, the two chiralities, analogous to the two valleys in 2D materials, lead to a new degree of freedom in a 3D crystal, suggesting novel pathways to store and carry information. By shining circularly polarized light on the WSM TaAs, we illuminate the chirality of the WFs and achieve an electrical current that is highly controllable based on the WFs' chirality. Our results open up a wide range of new possibilities for experimentally studying and controlling the WFs and their associated quantum anomalies by optical and electrical means, which suggest the exciting prospect of ``Weyltronics''.

Selectively transporting small chiral particles with circularly polarized Airy beams.

PubMed

Lu, Wanli; Chen, Huajin; Guo, Sandong; Liu, Shiyang; Lin, Zhifang

2018-05-01

Based on the full wave simulation, we demonstrate that a circularly polarized vector Airy beam can selectively transport small chiral particles along a curved trajectory via the chirality-tailored optical forces. The transverse optical forces can draw the chiral particles with different particle chirality towards or away from the intensity maxima of the beam, leading to the selective trapping in the transverse plane. The transversely trapped chiral particles are then accelerated along a curved trajectory of the Airy beam by the chirality-tailored longitudinal scattering force, rendering an alternative way to sort and/or transport chiral particles with specified helicity. Finally, the underlying physics of the chirality induced transverse trap and de-trap phenomena are examined by the analytical theory within the dipole approximation.

Chiral plasmonics

PubMed Central

Hentschel, Mario; Schäferling, Martin; Duan, Xiaoyang; Giessen, Harald; Liu, Na

2017-01-01

We present a comprehensive overview of chirality and its optical manifestation in plasmonic nanosystems and nanostructures. We discuss top-down fabricated structures that range from solid metallic nanostructures to groupings of metallic nanoparticles arranged in three dimensions. We also present the large variety of bottom-up synthesized structures. Using DNA, peptides, or other scaffolds, complex nanoparticle arrangements of up to hundreds of individual nanoparticles have been realized. Beyond this static picture, we also give an overview of recent demonstrations of active chiral plasmonic systems, where the chiral optical response can be controlled by an external stimulus. We discuss the prospect of using the unique properties of complex chiral plasmonic systems for enantiomeric sensing schemes. PMID:28560336

Furo-fused BINOL based crown as a fluorescent chiral sensor for enantioselective recognition of phenylethylamine and ethyl ester of valine.

PubMed

Upadhyay, Sunil P; Pissurlenkar, Raghuvir R S; Coutinho, Evans C; Karnik, Anil V

2007-07-20

A furo-fused BINOL based chiral crown was developed as an enantioselective chiral sensor for phenylethylamine and ethyl ester of valine. Fusion of furan to BINOL has resulted in a highly stereo-discriminating backbone for the chiral crown developed. This chiral crown exhibited a fluorescence enhancement difference of 2.97 times between two enantiomers of phenylethylamine and 2.55 times between two enantiomers of ethyl ester of valine. The ratio of association constants for two diastereomeric complexes of two enantiomers of phenylethylamine was found to be 11.30, and the ratio for two enantiomers of ethyl ester of valine was 7.02.

Asymmetric Michael Addition Mediated by Chiral Ionic Liquids

PubMed Central

Suzuki, Yumiko

2018-01-01

Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines. PMID:29861702

Chiral Symmetry Breaking and Complete Chiral Purity by Thermodynamic-Kinetic Feedback Near Equilibrium: Implications for the Origin of Biochirality

NASA Astrophysics Data System (ADS)

Viedma, Cristobal

2007-05-01

Chiral symmetry breaking occurs when a physical or chemical process spontaneously generates a large excess of one of the two enantiomers-left-handed (L) or right-handed (D)--with no preference as to which of the two enantiomers is produced. From the viewpoint of energy, these two enantiomers can exist with an equal probability, and inorganic processes that involve chiral products commonly yield a racemic mixture of both. The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking in chirality and has long intrigued the science community. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, some 140 years ago. Here, it is shown that two populations of chiral crystals of left and right hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking can be explained by the feedback between the thermodynamic control of dissolution and the kinetics of the growth process near equilibrium. This ``thermodynamic-kinetic feedback near equilibrium'' is established as a mechanism to achieve complete chiral purity in solid state from a previously solid racemic medium. The way in which this mechanism could operate in solutions of chiral biomolecules is described. Finally, based on this mechanism, experiments designed to search for chiral purity in a new way are proposed: chiral purity of amino acids or biopolymers is predicted in solid phase from a previously solid racemic medium. This process may have played a key role in the origin of biochirality.

Enantioselectively controlled release of chiral drug (metoprolol) using chiral mesoporous silica materials

NASA Astrophysics Data System (ADS)

Guo, Zhen; Du, Yu; Liu, Xianbin; Ng, Siu-Choon; Chen, Yuan; Yang, Yanhui

2010-04-01

Chiral porous materials have attracted burgeoning attention on account of their potential applications in many areas, such as enantioseparation, chiral catalysis, chemical sensors and drug delivery. In this report, chiral mesoporous silica (CMS) materials with various pore sizes and structures were prepared using conventional achiral templates (other than chiral surfactant) and a chiral cobalt complex as co-template. The synthesized CMS materials were characterized by x-ray diffraction, nitrogen physisorption, scanning electron microscope and transmission electron microscope. These CMS materials, as carriers, were demonstrated to be able to control the enantioselective release of a representative chiral drug (metoprolol). The release kinetics, as modeled by the power law equation, suggested that the release profiles of metoprolol were remarkably dependent on the pore diameter and pore structure of CMS materials. More importantly, R- and S-enantiomers of metoprolol exhibited different release kinetics on CMS compared to the corresponding achiral mesoporous silica (ACMS), attributable to the existence of local chirality on the pore wall surface of CMS materials. The chirality of CMS materials on a molecular level was further substantiated by vibrational circular dichroism measurements.

Thermal chiral vortical and magnetic waves: New excitation modes in chiral fluids

DOE PAGES

Kalaydzhyan, Tigran; Murchikova, Elena

2017-03-24

In certain circumstances, chiral (parity-violating) medium can be described hydrodynamically as a chiral fluid with microscopic quantum anomalies. Possible examples of such systems include strongly coupled quark–gluon plasma, liquid helium 3He-A, neutron stars and the Early Universe. Here, we study first-order hy-drodynamics of a chiral fluid on a vortex background and in an external magnetic field. We show that there are two previously undiscovered modes describing heat waves propagating along the vortex and magnetic field. We call them the Thermal Chiral Vortical Wave and Thermal Chiral Magnetic Wave. We also identify known gapless excitations of density (chiral vortical and chiralmore » magnetic waves) and transverse velocity (chiral Alfvén wave). We also demonstrate that the velocity of the chiral vortical wave is zero, when the full hydrodynamic framework is applied, and hence the wave is absent and the excitation reduces to the charge diffusion mode. We also comment on the frame-dependent contributions to the obtained propagation velocities.« less

Effect of cements on fracture resistance of monolithic zirconia crowns

PubMed Central

Nakamura, Keisuke; Mouhat, Mathieu; Nergård, John Magnus; Lægreid, Solveig Jenssen; Kanno, Taro; Milleding, Percy; Örtengren, Ulf

2016-01-01

Abstract Objectives The present study investigated the effect of cements on fracture resistance of monolithic zirconia crowns in relation to their compressive strength. Materials and methods Four different cements were tested: zinc phosphate cement (ZPC), glass-ionomer cement (GIC), self-adhesive resin-based cement (SRC) and resin-based cement (RC). RC was used in both dual cure mode (RC-D) and chemical cure mode (RC-C). First, the compressive strength of each cement was tested according to a standard (ISO 9917-1:2004). Second, load-to-failure test was performed to analyze the crown fracture resistance. CAD/CAM-produced monolithic zirconia crowns with a minimal thickness of 0.5 mm were prepared and cemented to dies with each cement. The crown–die samples were loaded until fracture. Results The compressive strength of SRC, RC-D and RC-C was significantly higher than those of ZPC and GIC (p < 0.05). However, there was no significant difference in the fracture load of the crown between the groups. Conclusion The values achieved in the load-to-failure test suggest that monolithic zirconia crowns with a minimal thickness of 0.5 mm may have good resistance against fracture regardless of types of cements. PMID:27335900

Comparison of light transmittance in different thicknesses of zirconia under various light curing units

PubMed Central

Egilmez, Ferhan; Ergun, Gulfem

2012-01-01

PURPOSE The objective of this study was to compare the light transmittance of zirconia in different thicknesses using various light curing units. MATERIALS AND METHODS A total of 21 disc-shaped zirconia specimens (5 mm in diameter) in different thicknesses (0.3, 0.5 and 0.8 mm) were prepared. The light transmittance of the specimens under three different light-curing units (quartz tungsten halogen, light-emitting diodes and plasma arc) was compared by using a hand-held radiometer. Statistical significance was determined using two-way ANOVA (α=.05). RESULTS ANOVA revealed that thickness of zirconia and light curing unit had significant effects on light transmittance (P<.001). CONCLUSION Greater thickness of zirconia results in lower light transmittance. Light-emitting diodes light-curing units might be considered as effective as Plasma arc light-curing units or more effective than Quartz-tungsten-halogen light-curing units for polymerization of the resin-based materials. PMID:22737314

Fabrication and Performance of Zirconia Electrolysis Cells for Cabon Dioxide Reduction for Mars In Situ Resource Utilization Applications

NASA Technical Reports Server (NTRS)

Minh, N. Q.; Chung, B. W.; Doshi, R.; Lear, G. R.; Montgomery, K.; Ong, E. T.

1999-01-01

Use of the Martian atmosphere (95% CO2) to produce oxygen (for propellant and life support) can significantly lower the required launch mass and dramatically reduce the total cost for Mars missions. Zirconia electrolysis cells are one of the technologies being considered for oxygen generation from carbon dioxide in Mars In Situ Resource Utilization (ISRU) production plants. The attractive features of the zirconia cell for this application include simple operation and lightweight, low volume system. A zirconia electrolysis cell is an all-solid state device, based on oxygen-ion conducting zirconia electrolytes, that electrochemically reduces carbon dioxide to oxygen and carbon monoxide. The cell consists of two porous electrodes (the anode and cathode) separated by a dense zirconia electrolyte. Typical zirconia cells contain an electrolyte layer which is 200 to 400 micrometer thick. The electrical conductivity requirement for the electrolyte necessitates an operating temperature of 9000 to 10000C. Recently, the fabrication of zirconia cells by the tape calendering has been evaluated. This fabrication process provides a simple means of making cells having very thin electrolytes (5 to 30 micrometers). Thin zirconia electrolytes reduce cell ohmic losses, permitting efficient operation at lower temperatures (8000C or below). Thus, tape-calendered cells provides not only the potential of low temperature operation but also the flexibility in operating temperatures. This paper describes the fabrication of zirconia cells by the tape calendering method and discusses the performance results obtained to date.

Dehydration and crystallization kinetics of zirconia-yttria gels

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

Ramanathan, S.; Muraleedharan, R.V.; Roy, S.K.

1995-02-01

Zirconia and zirconia-yttria gels containing 4 and 8 mol% yttria were obtained by coprecipitation and drying at 373 K. The dehydration and crystallization behavior of the dried gels was studied by DSC, TG, and XRD. The gels undergo elimination of water over a wide temperature range of 373--673 K. The peak temperature of the endotherm corresponding to dehydration and the kinetic constants for the process were not influenced by the yttria content of the gel. The enthalpy of dehydration observed was in good agreement with the heat of vaporization data. The dehydration was followed by a sharp exothermic crystallization process.more » The peak temperature of the exotherm and the activation energy of the process increased with an increase in yttria content, while the enthalpy of crystallization showed a decrease. The ``glow effect`` reduced with increasing yttria content. Pure zirconia crystallizes in the tetragonal form while the zirconia containing 4 and 8 mol% yttria appears to crystallize in the cubic form.« less

Scandia-and-Yttria-Stabilized Zirconia for Thermal Barriers

NASA Technical Reports Server (NTRS)

Mess, Derek

2003-01-01

yttria in suitable proportions has shown promise of being a superior thermal- barrier coating (TBC) material, relative to zirconia stabilized with yttria only. More specifically, a range of compositions in the zirconia/scandia/yttria material system has been found to afford increased resistance to deleterious phase transformations at temperatures high enough to cause deterioration of yttria-stabilized zirconia. Yttria-stabilized zirconia TBCs have been applied to metallic substrates in gas turbine and jet engines to protect the substrates against high operating temperatures. These coatings have porous and microcracked structures, which can accommodate strains induced by thermal-expansion mismatch and thermal shock. The longevity of such a coating depends upon yttria as a stabilizing additive that helps to maintain the zirconia in an yttria-rich, socalled non-transformable tetragonal crystallographic phase, thus preventing transformation to the monoclinic phase with an associated deleterious volume change. However, at a temperature greater than about 1,200 C, there is sufficient atomic mobility that the equilibrium, transformable zirconia phase is formed. Upon subsequent cooling, this phase transforms to the monoclinic phase, with an associated volume change that adversely affects the integrity of the coating. Recently, scandia was identified as a stabilizer that could be used instead of, or in addition to, yttria. Of particular interest are scandia-and-yttria-stabilized zirconia (SYSZ) compositions of about 6 mole percent scandia and 1 mole percent yttria, which have been found to exhibit remarkable phase stability at a temperature of 1,400 C in simple aging tests. Unfortunately, scandia is expensive, so that the problem becomes one of determining whether there are compositions with smaller proportions of scandia that afford the required high-temperature stability. In an attempt to solve this problem, experiments were performed on specimens made with reduced

Impedance spectroscopy of reduced monoclinic zirconia.

PubMed

Eder, Dominik; Kramer, Reinhard

2006-10-14

Zirconia doped with low-valent cations (e.g. Y3+ or Ca2+) exhibits an exceptionally high ionic conductivity, making them ideal candidates for various electrochemical applications including solid oxide fuel cells (SOFC) and oxygen sensors. It is nevertheless important to study the undoped, monoclinic ZrO2 as a model system to construct a comprehensive picture of the electrical behaviour. In pure zirconia a residual number of anion vacancies remains because of contaminants in the material as well as the thermodynamic disorder equilibrium, but electronic conduction may also contribute to the observed conductivity. Reduction of zirconia in hydrogen leads to the adsorption of hydrogen and to the formation of oxygen vacancies, with their concentration affected by various parameters (e.g. reduction temperature and time, surface area, and water vapour pressure). However, there is still little known about the reactivities of defect species and their effect on the ionic and electronic conduction. Thus, we applied electrochemical impedance spectroscopy to investigate the electric performance of pure monoclinic zirconia with different surface areas in both oxidizing and reducing atmospheres. A novel equivalent circuit model including parallel ionic and electronic conduction has previously been developed for titania and is used herein to decouple the conduction processes. The concentration of defects and their formation energies were measured using volumetric oxygen titration and temperature programmed oxidation/desorption.

Laminar and Turbulent Dynamos in Chiral Magnetohydrodynamics. II. Simulations

NASA Astrophysics Data System (ADS)

Schober, Jennifer; Rogachevskii, Igor; Brandenburg, Axel; Boyarsky, Alexey; Fröhlich, Jürg; Ruchayskiy, Oleg; Kleeorin, Nathan

2018-05-01

Using direct numerical simulations (DNS), we study laminar and turbulent dynamos in chiral magnetohydrodynamics with an extended set of equations that accounts for an additional contribution to the electric current due to the chiral magnetic effect (CME). This quantum phenomenon originates from an asymmetry between left- and right-handed relativistic fermions in the presence of a magnetic field and gives rise to a chiral dynamo. We show that the magnetic field evolution proceeds in three stages: (1) a small-scale chiral dynamo instability, (2) production of chiral magnetically driven turbulence and excitation of a large-scale dynamo instability due to a new chiral effect (α μ effect), and (3) saturation of magnetic helicity and magnetic field growth controlled by a conservation law for the total chirality. The α μ effect becomes dominant at large fluid and magnetic Reynolds numbers and is not related to kinetic helicity. The growth rate of the large-scale magnetic field and its characteristic scale measured in the numerical simulations agree well with theoretical predictions based on mean-field theory. The previously discussed two-stage chiral magnetic scenario did not include stage (2), during which the characteristic scale of magnetic field variations can increase by many orders of magnitude. Based on the findings from numerical simulations, the relevance of the CME and the chiral effects revealed in the relativistic plasma of the early universe and of proto-neutron stars are discussed.

Three- to nine-year survival estimates and fracture mechanisms of zirconia- and alumina-based restorations using standardized criteria to distinguish the severity of ceramic fractures.

PubMed

Moráguez, Osvaldo D; Wiskott, H W Anselm; Scherrer, Susanne S

2015-12-01

The aims of this study were set as follows: 1. To provide verifiable criteria to categorize the ceramic fractures into non-critical (i.e., amenable to polishing) or critical (i.e., in need of replacement) 2. To establish the corresponding survival rates for alumina and zirconia restorations 3. To establish the mechanism of fracture using fractography Fifty-eight patients restored with 115 alumina-/zirconia-based crowns and 26 zirconia-based fixed dental prostheses (FDPs) were included. Ceramic fractures were classified into four types and further subclassified into "critical" or "non-critical." Kaplan-Meier survival estimates were calculated for "critical fractures only" and "all fractures." Intra-oral replicas were taken for fractographic analyses. Kaplan-Meier survival estimates for "critical fractures only" and "all fractures" were respectively: Alumina single crowns: 90.9 and 68.3 % after 9.5 years (mean 5.71 ± 2.6 years). Zirconia single crowns: 89.4 and 80.9 % after 6.3 years (mean 3.88 ± 1.2 years). Zirconia FDPs: 68.6 % (critical fractures) and 24.6 % (all fractures) after 7.2 and 4.6 years respectively (FDP mean observation time 3.02 ± 1.4 years). No core/framework fractures were detected. Survival estimates varied significantly depending on whether "all" fractures were considered as failures or only those deemed as "critical". For all restorations, fractographic analyses of failed veneering ceramics systematically demonstrated heavy occlusal wear at the failure origin. Therefore, the relief of local contact pressures on unsupported ceramic is recommended. Occlusal contacts on mesial or distal ridges should systematically be eliminated. A classification standard for ceramic fractures into four categories with subtypes "critical" and "non-critical" provides a differentiated view of the survival of ceramic restorations.

Fracture load of metal-ceramic, monolithic, and bi-layered zirconia-based posterior fixed dental prostheses after thermo-mechanical cycling.

PubMed

López-Suárez, Carlos; Castillo-Oyagüe, Raquel; Rodríguez-Alonso, Verónica; Lynch, Christopher D; Suárez-García, María-Jesús

2018-06-01

This study aims to evaluate the fracture load of differently fabricated 3-unit posterior fixed dental prostheses (FDPs) with an intermediate pontic. Fifty sets of two stainless-steel abutments were randomly assigned to five groups (n = 10 each) depending on the material and technique used for manufacturing the FDPs: (1) Metal-ceramic (MC, control); (2) Lava Zirconia (LZ, bi-layered); (3) Lava Plus (LM, monolithic); (4) VITA In-Ceram YZ (YZ, bi-layered); and (5) IPS e-max ZirCAD (ZZ, bi-layered). After being luted to the dies, all FDPs were submitted to thermo-mechanical cycling (120,000 masticatory cycles, 50 N; plus 774 thermal cycles of 5 °C/55 °C, dwell time: 30 s). Samples were then subjected to a three-point bending test until fracture in a universal testing machine (cross-head speed: 1 mm/min). Fracture load of the veneering ceramic (VF) and total fracture load (TF) were recorded. Microstructure and failure patterns were assessed. Data was analysed using one-way ANOVA and Tukey HSD post-hoc tests (α = 0.05). MC restorations recorded higher VF and TF values than did zirconia FDPs (p = 0.0001), which showed no between-group differences. Within the bi-layered groups, TF was significantly higher than VF. LM pieces registered lower average grain size than did LZ specimens (p = 0.001). Overall, the connector was the weakest part. All of the groups tested could withstand clinical chewing forces in terms of average fracture load. Zirconia-based samples performed similarly to each other, but showed lower mean fracture load values than did metal-ceramic ones. Monolithic zirconia may be recommendable for solving the chipping problem. Copyright © 2018 Elsevier Ltd. All rights reserved.

Understanding Cooperative Chirality at the Nanoscale

NASA Astrophysics Data System (ADS)

Yu, Shangjie; Wang, Pengpeng; Govorov, Alexander; Ouyang, Min

Controlling chirality of organic and inorganic structures plays a key role in many physical, chemical and biochemical processes, and may offer new opportunity to create technology applications based on chiroptical effect. In this talk, we will present a theoretical model and simulation to demonstrate how to engineer nanoscale chirality in inorganic nanostructures via synergistic control of electromagnetic response of both lattice and geometry, leading to rich tunability of chirality at the nanoscale. Our model has also been applied to understand recent materials advancement of related control with excellent agreement, and can elucidate physical origins of circular dichroism features in the experiment.

Wear properties of alumina/zirconia composite ceramics for joint prostheses measured with an end-face apparatus.

PubMed

Morita, Yusuke; Nakata, Kenichi; Kim, Yoon-Ho; Sekino, Tohru; Niihara, Koichi; Ikeuchi, Ken

2004-01-01

While only alumina is applied to all-ceramic joint prostheses at present, a stronger ceramic is required to prevent fracture and chipping due to impingement and stress concentration. Zirconia could be a potential substitute for alumina because it has high strength and fracture toughness. However, the wear of zirconia/zirconia combination is too high for clinical use. Although some investigations on composite ceramics revealed that mixing of different ceramics was able to improve the mechanical properties of ceramics, there are few reports about wear properties of composite ceramics for joint prosthesis. Since acetabular cup and femoral head of artificial hip joint are finished precisely, they indicate high geometric conformity. Therefore, wear test under flat contact was carried out with an end-face wear testing apparatus for four kinds of ceramics: alumina monolith, zirconia monolith, alumina-based composite ceramic, and zirconia based composite ceramic. Mean contact pressure was 10 MPa and sliding velocity was 40 mm/s. The wear test continued for 72 hours and total sliding distance was 10 km. After the test, the wear factor was calculated. Worn surfaces were observed with a scanning electron micrograph (SEM). The results of this wear test show that the wear factors of the both composite ceramics are similarly low and their mechanical properties are much better than those of the alumina monolith and the zirconia monolith. According to these results, it is predicted that joint prostheses of the composite ceramics are safer against break down and have longer lifetime compared with alumina/alumina joint prostheses.

Tensor algebra-based geometric methodology to codify central chirality on organic molecules.

PubMed

García-Jacas, C R; Marrero-Ponce, Y; Hernández-Ortega, T; Martinez-Mayorga, K; Cabrera-Leyva, L; Ledesma-Romero, J C; Aguilera-Fernández, I; Rodríguez-León, A R

2017-06-01

A novel mathematical procedure to codify chiral features of organic molecules in the QuBiLS-MIDAS framework is introduced. This procedure constitutes a generalization to that commonly used to date, where the values 1 and -1 (correction factor) are employed to weight the molecular vectors when each atom is labelled as R (rectus) or S (sinister) according to the Cahn-Ingold-Prelog rules. Therefore, values in the range [Formula: see text] with steps equal to 0.25 may be accounted for. The atoms labelled R or S can have negative and positive values assigned (e.g. -3 for an R atom and 1 for an S atom, or vice versa), opposed values (e.g. -3 for an R atom and 3 for an S atom, or vice versa), positive values (e.g. 3 for an R atom and 1 for an S atom) or negative values (e.g. -3 for an R atom and -1 for an S atom). These proposed Chiral QuBiLS-MIDAS 3D-MDs are real numbers, non-symmetric and reduced to 'classical' (non-chiral) QuBiLS-MIDAS 3D-MDs when symmetry is not codified (correction factor equal to zero). In this report, only the factors with opposed values were considered with the purpose of demonstrating the feasibility of this proposal. From QSAR modelling carried out on four chemical datasets (Cramer's steroids, fenoterol stereoisomer derivatives, N-alkylated 3-(3-hydroxyphenyl)-piperidines, and perindoprilat stereoisomers), it was demonstrated that the use of several correction factors contributes to the building of models with greater robustness and predictive ability than those reported in the literature, as well as with respect to the models exclusively developed with QuBiLS-MIDAS 3D-MDs based on the factor 1 | -1. In conclusion, it can be stated that this novel strategy constitutes a suitable alternative to computed chirality-based descriptors, contributing to the development of good models to predict properties depending on symmetry.

Characterizing optical chirality

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

Bliokh, Konstantin Y.; Advanced Science Institute, RIKEN, Wako-shi, Saitama 351-0198; Nori, Franco

We examine the recently introduced measure of chirality of a monochromatic optical field [Y. Tang and A. E. Cohen, Phys. Rev. Lett. 104, 163901 (2010)] using the momentum (plane-wave) representation and helicity basis. Our analysis clarifies the physical meaning of the measure of chirality and unveils its close relation to the polarization helicity, spin angular momentum, energy density, and Poynting energy flow. We derive the operators of the optical chirality and of the corresponding chiral momentum, which acquire remarkably simple forms in the helicity representation.

Mechanical behavior of single-layer ceramized zirconia abutments for dental implant prosthetic rehabilitation

PubMed Central

Jiménez-Melendo, Manuel; Llena-Blasco, Oriol; Bruguera, August; Llena-Blasco, Jaime; Yáñez-Vico, Rosa-María; García-Calderón, Manuel; Vaquero-Aguilar, Cristina; Velázquez-Cayón, Rocío; Gutiérrez-Pérez, José-Luis

2014-01-01

Objectives: This study was undertaken to characterize the mechanical response of bare (as-received) and single-layer ceramized zirconia abutments with both internal and external connections that have been developed to enhanced aesthetic restorations. Material and Methods: Sixteen zirconia implant abutments (ZiReal Post®, Biomet 3i, USA) with internal and external connections have been analyzed. Half of the specimens were coated with a 0.5mm-thick layer of a low-fusing fluroapatite ceramic. Mechanical tests were carried out under static (constant cross-head speed of 1mm/min until fracture) and dynamic (between 100 and 400N at a frequency of 1Hz) loading conditions. The failure location was identified by electron microscopy. The removal torque of the retaining screws after testing was also evaluated. Results: The average fracture strength was above 300N for all the abutments, regardless of connection geometry and coating. In most of the cases (94%), failure occurred by abutment fracture. No significant differences were observed either in fatigue behavior and removal torque between the different abutment groups. Conclusions: Mechanical behavior of Zireal zirconia abutments is independent of the type of internal/external connection and the presence/absence of ceramic coating. This may be clinically valuable in dental rehabilitation to improve the aesthetic outcome of zirconia-based dental implant systems. Key words:Dental implant, zirconia, ceramic structure, mechanical properties. PMID:25674313

Improvements to Zirconia Thick-Film Oxygen Sensors

NASA Astrophysics Data System (ADS)

Maskell, William C.; Brett, Daniel J. L.; Brandon, Nigel P.

2013-06-01

Thick-film zirconia gas sensors are normally screen-printed onto a planar substrate. A sandwich of electrode-electrolyte-electrode is fired at a temperature sufficient to instigate sintering of the zirconia electrolyte. The resulting porous zirconia film acts as both the electrolyte and as the diffusion barrier through which oxygen diffuses. The high sintering temperature results in de-activation of the electrodes so that sensors must be operated at around 800 °C for measurements in the percentage range of oxygen concentration. This work shows that the use of cobalt oxide as a sintering aid allows reduction of the sensor operating temperature by 100-200 °C with clear benefits. Furthermore, an interesting and new technique is presented for the investigation of the influence of dopants and of the through-porosity of ionically-conducting materials.

Inducing Axial Chirality in a Supramolecular Catalyst.

PubMed

Wenz, Katharina Marie; Leonhardt-Lutterbeck, Günter; Breit, Bernhard

2018-03-06

A new type of ligand, which is able to form axially chiral, supramolecular complexes was designed using DFT calculations. Two chiral monomers, each featuring a covalently bound chiral auxiliary, form a bidentate phosphine ligand with a twisted, hydrogen-bonded backbone upon coordination to a transition metal center which results in two diastereomeric, tropos complexes. The ratio of the diastereomers in solution is very temperature- and solvent-dependent. Rhodium and platinum complexes were analyzed through a combination of NMR studies, ESI-MS measurements, as well as UV-VIS and circular dichroism spectroscopy. The chiral self-organized ligands were evaluated in the rhodium-catalyzed asymmetric hydrogenation of α-dehydrogenated amino acids and resulted in good conversion and high enantioselectivity. This research opens the way for new ligand designs based on stereocontrol of supramolecular assemblies through stereodirecting chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multinuclear NMR study of silica fiberglass modified with zirconia.

PubMed

Lapina, O B; Khabibulin, D F; Terskikh, V V

2011-01-01

Silica fiberglass textiles are emerging as uniquely suited supports in catalysis, which offer unprecedented flexibility in designing advanced catalytic systems for chemical and auto industries. During manufacturing fiberglass materials are often modified with additives of various nature to improve glass properties. Glass network formers, such as zirconia and alumina, are known to provide the glass fibers with higher strength and to slow down undesirable devitrification processes. In this work multinuclear (1)H, (23)Na, (29)Si, and (91)Zr NMR spectroscopy was used to characterize the effect of zirconia on the molecular-level fiberglass structure. (29)Si NMR results help in understanding why zirconia-modified fiberglass is more stable towards devitrification comparing with pure silica glass. Internal void spaces formed in zirconia-silica glass fibers after acidic leaching correlate with sodium and water distributions in the starting bulk glass as probed by (23)Na and (1)H NMR. These voids spaces are important for stabilization of catalytically active species in the supported catalysts. Potentials of high-field (91)Zr NMR spectroscopy to study zirconia-containing glasses and similarly disordered systems are illustrated. Copyright © 2011 Elsevier Inc. All rights reserved.

High-temperature zirconia insulation and method for making same

DOEpatents

Wrenn, G.E. Jr.; Holcombe, C.E. Jr.; Lewis, J. Jr.

The present invention is directed to a highly pure, partially stabilized, fibrous zirconia composite for use as thermal insulation in environments where temperatures up to about 2,000/sup 0/C are utilized. The composite of the present invention is fabricated into any suitable configuration such as a cone, cylinder dome or the like by vacuum molding an aqueous slurry of partially stabilized zirconia fibers into a desired configuration on a suitably shaped mandrel. The molded fibers are infiltrated with zirconyl nitrate and the resulting structure is then dried to form a rigid structure which may be removed and placed in a furnace. The structure is then heated in air to a temperature of about 600/sup 0/C for driving off the nitrate from the structure and for oxidizing the zirconyl ion to zirconia. Thereafter, the structure is heated to about 950/sup 0/ to 1,250/sup 0/C to fuse the zirconia fibers at their nexi in a matrix of zirconia. The composite produced by the present invention is self-supporting and can be readily machined to desired final dimensions. Additional heating to about 1800/sup 0/ to 2000/sup 0/C further improves structural rigidity.

High-temperature zirconia insulation and method for making same

DOEpatents

Wrenn, G.E. Jr.; Holcombe, C.E. Jr.; Lewis, J. Jr.

1988-05-10

The present invention is directed to a highly pure, partially stabilized, fibrous zirconia composite for use as thermal insulation in environments where temperatures up to about 2,000 C are utilized. The composite of the present invention is fabricated into any suitable configuration such as a cone, cylinder, dome or the like by vacuum molding an aqueous slurry of partially stabilized zirconia fibers into a desired configuration on a suitably shaped mandrel. The molded fibers are infiltrated with zirconyl nitrate and the resulting structure is then dried to form a rigid structure which may be removed and placed in a furnace. The structure is then heated in air to a temperature of about 600 C for driving off the nitrate from the structure and for oxidizing the zirconyl ion to zirconia. Thereafter, the structure is heated to about 950 to 1,250 C to fuse the zirconia fibers at their nexi in a matrix of zirconia. The composite produced by the present invention is self-supporting and can be readily machined to desired final dimensions. Additional heating to about 1,800 to 2,000 C further improves structural rigidity.

High-temperature zirconia insulation and method for making same

DOEpatents

Wrenn, Jr., George E.; Holcombe, Jr., Cressie E.; Lewis, Jr., John

1988-01-01

The present invention is directed to a highly pure, partially stabilized, fibrous zirconia composite for use as thermal insulation in environments where temperatures up to about 2000.degree. C. are utilized. The composite of the present invention is fabricated into any suitable configuration such as a cone, cylinder, dome or the like by vacuum molding an aqueous slurry of partially stabilized zirconia fibers into a desired configuration on a suitably shaped mandrel. The molded fibers are infiltrated with zirconyl nitrate and the resulting structure is then dried to form a rigid structure which may be removed and placed in a furnace. The structure is then heated in air to a temperature of about 600.degree. C. for driving off the nitrate from the structure and for oxidizing the zirconyl ion to zirconia. Thereafter, the structure is heated to about 950.degree. to 1,250.degree. C. to fuse the zirconia fibers at their nexi in a matrix of zirconia. The composite produced by the present invention is self-supporting and can be readily machined to desired final dimensions. Additional heating to about 1800.degree. to 2000.degree. C. further improves structural rigidity.

Inversion of Supramolecular Chirality by Sonication-Induced Organogelation

PubMed Central

Maity, Sibaprasad; Das, Priyadip; Reches, Meital

2015-01-01

Natural helical structures have inspired the formation of well-ordered peptide-based chiral nanostructures in vitro. These structures have drawn much attention owing to their diverse applications in the area of asymmetric catalysts, chiral photonic materials, and nanoplasmonics. The self-assembly of two enantiomeric fluorinated aromatic dipeptides into ordered chiral fibrillar nanostructures upon sonication is described. These fibrils form organogels. Our results clearly indicate that fluorine-fluorine interactions play an important role in self-assembly. Circular dichroism analysis revealed that both peptides (peptides 1 and 2), containing two fluorines, depicted opposite cotton effects in their monomeric form compared with their aggregated form. This shows that supramolecular chirality inversion took place during the stimuli-responsive self-aggregation process. Conversely, peptide 3, containing one fluorine, did not exhibit chirality inversion in sonication-induced organogelation. Therefore, our results clearly indicate that fluorination plays an important role in the organogelation process of these aromatic dipeptides. Our findings may have broad implications regarding the design of chiral nanostructures for possible applications such as chiroptical switches, asymmetric catalysis, and chiral recognitions. PMID:26553508

Can the chirality of the ISM be measured

NASA Technical Reports Server (NTRS)

Pendleton, Y.; Sandford, S. A.; Werner, Michael W.; Lauer, J.; Chang, Sherwood

1990-01-01

Many moderately complex carbon-based molecules of the type associated with biological systems can exist in one of two mirror-image forms (left-handed and right-handed), which can be distinguished on the basis of their influence on the state of polarization of a light beam. Both forms are possible in nature; yet in living organisms it is invariably the rule that one of these two species predominates. This gives rise to a net chirality. One possible explanation for the net chirality is that the early earth was somehow seeded from the ISM with an excess of chiral organic compounds which led to the development of life forms which are based on left-handed amino acids and right-handed sugars. Molecular spectroscopy of the interstellar medium (ISM) has revealed a complex variety of molecular species similar to those thought to have been available in the oceans and atmospheres of the earth at the time life formed. The detection of such molecules demonstrates the generality of the chemical processes occurring in both environments. If this generality extends to the processes which produce chirality, it may be possible to detect a net chirality in the ISM. This is of particular interest because determining whether or not net chirality exists elsewhere in the universe is an essential aspect of understanding how life developed on earth and how widely distributed it might be. Researchers report preliminary results of a feasibility study to determine whether or not a net chirality in the ISM can be measured. If laboratory results identify candidate chiral molecules that might exist in the ISM, the next step in this feasibility study will be to estimate the detectability of the chiral signature in astrophysical environments.

Twenty-nine-month follow-up of a paediatric zirconia dental crown.

PubMed

Lopez Cazaux, Serena; Hyon, Isabelle; Prud'homme, Tony; Dajean Trutaud, Sylvie

2017-06-14

The aim of this paper is to present the long-term follow-up of one paediatric zirconia crown on a deciduous molar. Preformed crowns are part of the armamentarium in paediatric dentistry. In recent years, aesthetic alternatives to preformed metal crowns have been developed, first preveneered crowns and then zirconia crowns. This paper describes the restoration of a primary molar with a zirconia crown (EZ-Pedo, Loomis, California, USA) in an 8-year-old boy. In this clinical case, the protocol for the implementation and maintenance of zirconia crowns is detailed. The patient was followed up for 29 months until the natural exfoliation of his primary molar. The adaptation of the zirconia crown, the gingival health and the wear on the opposing tooth were considered. In this case, the paediatric zirconia crown allowed sustainable functional restoration while restoring a natural appearance of the tooth. © BMJ Publishing Group Ltd (unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Influence of cement thickness on resin-zirconia microtensile bond strength

PubMed Central

Lee, Tae-Hoon; Ahn, Jin-Soo; Shim, June-Sung; Han, Chong-Hyun

2011-01-01

PURPOSE The aim of this study was to evaluate the influence of resin cement thickness on the microtensile bond strength between zirconium-oxide ceramic and resin cement. MATERIALS AND METHODS Thirty-two freshly extracted molars were transversely sectioned at the deep dentin level and bonded to air-abraded zirconium oxide ceramic disks. The specimens were divided into 8 groups based on the experimental conditions (cement type: Rely X UniCem or Panavia F 2.0, cement thickness: 40 or 160 µm, storage: thermocycled or not). They were cut into microbeams and stored in 37℃ distilled water for 24 h. Microbeams of non-thermocycled specimens were submitted to a microtensile test, whereas those of thermocycled groups were thermally cycled for 18,000 times immediately before the microtensile test. Three-way ANOVA and Sheffe's post hoc tests were used for statistical analysis (α=95%). RESULTS All failures occurred at the resin-zirconia interface. Thermocycled groups showed lower microtensile bond strength than non-thermocycled groups (P<.001). Differences in cement thickness did not influence the resin-zirconia microtensile bond strength given the same resin cement or storage conditions (P>.05). The number of adhesive failures increased after thermocycling in all experimental conditions. No cohesive failure was observed in any experimental group. CONCLUSION When resin cements of adhesive monomers are applied over air-abraded zirconia restorations, the degree of fit does not influence the resin-zirconia microtensile bond strength. PMID:22053241

Boundary stress tensor and asymptotically AdS3 non-Einstein spaces at the chiral point

NASA Astrophysics Data System (ADS)

Giribet, Gaston; Goya, Andrés; Leston, Mauricio

2011-09-01

Chiral gravity admits asymptotically AdS3 solutions that are not locally equivalent to AdS3; meaning that solutions do exist which, while obeying the strong boundary conditions usually imposed in general relativity, happen not to be Einstein spaces. In topologically massive gravity (TMG), the existence of non-Einstein solutions is particularly connected to the question about the role played by complex saddle points in the Euclidean path integral. Consequently, studying (the existence of) nonlocally AdS3 solutions to chiral gravity is relevant to understanding the quantum theory. Here, we discuss a special family of nonlocally AdS3 solutions to chiral gravity. In particular, we show that such solutions persist when one deforms the theory by adding the higher-curvature terms of the so-called new massive gravity. Moreover, the addition of higher-curvature terms to the gravity action introduces new nonlocally AdS3 solutions that have no analogues in TMG. Both stationary and time-dependent, axially symmetric solutions that asymptote AdS3 space without being locally equivalent to it appear. Defining the boundary stress tensor for the full theory, we show that these non-Einstein geometries have associated vanishing conserved charges.

Single Crystal Growth of Zirconia Utilizing a Skull Melting Technique,

DTIC Science & Technology

1979-08-01

23 REFERENCES 24 Illustrations 1. Cutaway View of Skull Crucible 11 2. Section View of Skull Crucible 11 3. Stabilized Zirconia Powder Being Added to...E. R., (1968) J. Cryst. Growth, 2:243. 11 ... . . l l&I. .. . .:. . . N ’ - . . . . . . i . . . . . . . . .: P Figure 3. Stabilized Zirconia Powder Figure...colorless. The zirconia powder used in these experiments was obtained from N. L. Industries, Inc. Samples of the powder with 25 weight percent Y 2 0 3

Effect of molecular structure of tartrates on chiral recognition of tartrate-boric acid complex chiral selectors in chiral microemulsion electrokinetic chromatography.

PubMed

Hu, Shao-Qiang; Chen, Yong-Lei; Zhu, Hua-Dong; Shi, Hai-Jun; Yan, Na; Chen, Xing-Guo

2010-08-20

Eight l-tartrates and a d-tartrate with different alcohol moieties were used as chiral oils to prepare chiral microemulsions, which were utilized in conjunction with borate buffer to separate the enantiomers of beta-blockers or structurally related compounds by the chiral microemulsion electrokinetic chromatography (MEEKC) method. Among them, six were found to have a relatively good chiral separation performance and their chiral recognition effect in terms of both enantioselectivity and resolution increases linearly with the number of carbon atoms in the alkyl group of alcohol moiety. The tartrates containing alkyl groups of different structures but the same number of carbon atoms, i.e. one of straight chain and one of branched chain, provide similar enantioseparations. The trend was elucidated according to the changes in the difference of the steric matching between the molecules of two enantiomers and chiral selector. Furthermore, it was demonstrated for the first time that a water insoluble solid compound, di-i-butyl l-tartrate (mp. 73.5 degrees C), can be used as an oil to prepare a stable microemulsion to be used in the chiral MEEKC successfully. And a critical effect of the microemulsion for chiral separation, which has never been reported before, was found in this experiment, namely providing a hydrophobic environment to strengthen the interactions between the chiral selector and enantiomers. Copyright 2010 Elsevier B.V. All rights reserved.

Extracting stationary segments from non-stationary synthetic and cardiac signals

NASA Astrophysics Data System (ADS)

Rodríguez, María. G.; Ledezma, Carlos A.; Perpiñán, Gilberto; Wong, Sara; Altuve, Miguel

2015-01-01

Physiological signals are commonly the result of complex interactions between systems and organs, these interactions lead to signals that exhibit a non-stationary behaviour. For cardiac signals, non-stationary heart rate variability (HRV) may produce misinterpretations. A previous work proposed to divide a non-stationary signal into stationary segments by looking for changes in the signal's properties related to changes in the mean of the signal. In this paper, we extract stationary segments from non-stationary synthetic and cardiac signals. For synthetic signals with different signal-to-noise ratio levels, we detect the beginning and end of the stationary segments and the result is compared to the known values of the occurrence of these events. For cardiac signals, RR interval (cardiac cycle length) time series, obtained from electrocardiographic records during stress tests for two populations (diabetic patients with cardiovascular autonomic neuropathy and control subjects), were divided into stationary segments. Results on synthetic signals reveal that the non-stationary sequence is divided into more stationary segments than needed. Additionally, due to HRV reduction and exercise intolerance reported on diabetic cardiovascular autonomic neuropathy patients, non-stationary RR interval sequences from these subjects can be divided into longer stationary segments compared to the control group.

Simultaneous enantioselective determination of phenylpyrazole insecticide flufiprole and its chiral metabolite in paddy field ecosystem by ultra-high performance liquid chromatography/tandem mass spectrometry.

PubMed

Li, Jing; Zhang, Yuting; Cheng, Youpu; Yuan, Shankui; Liu, Lei; Shao, Hui; Li, Hui; Li, Na; Zhao, Pengyue; Guo, Yongze

2016-03-20

A novel and sensitive ultra-high performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method was developed and validated for simultaneous enantioselective determination of flufiprole and its hydrolysis metabolite in paddy field ecosystem. The separation and determination were performed using reversed-phase chromatography on a novel cellulose chiral stationary phase, a Lux Cellulose-4 (150 mm × 2.0 mm) column, under isocratic conditions at 0.25 mL/min flow rate. The effects of other four different polysaccharide-based chiral stationary phases (CSPs) on the separation and simultaneous enantioseparation of the two target compounds were also evaluated. The elution orders of the eluting enantiomers were identified by an optical rotation detector. Modified QuEChERS (acronym for Quick, Easy, Cheap, Effective, Rugged and Safe) method and solid-phase extraction (SPE) were used for the enrichment and cleanup of paddy water, rice straw, brown rice and paddy soil samples, respectively. Parameters including the matrix effect, linearity, precision, accuracy and stability were evaluated. Under the optimal conditions, the mean recoveries for all enantiomers from the above four sample matrix were ranged from 83.6% to 107%, with relative standard deviations (RSD) in the range of 1.0-5.8%. Coefficients of determination R(2)≥0.998 were achieved for each enantiomer in paddy water, rice straw, brown rice and paddy soil matrix calibration curves within the range of 5-500 μg/kg. The limits of quantification (LOQ) for all stereoisomers in the above four matrices were all below 2.0 μg/kg. The methodology was successfully applied for simultaneously enantioselective analysis of flufiprole enantiomers and their chiral metabolite in the real samples, indicating its efficacy in investigating the environmental stereochemistry of flufiprole in paddy field ecosystem. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of nanoparticles dispersion on viscoelastic properties of epoxy–zirconia polymer nanocomposites

NASA Astrophysics Data System (ADS)

Singh, Sushil Kumar; Kumar, Abhishek; Jain, Anuj

2018-03-01

In the present work zirconia-nanoparticles were dispersed in epoxy matrix to form epoxy-zirconia polymer nanocomposites using ultrasonication and viscoelastic properties of nanocomposites were investigated. For the same spherical zirconia-nanoparticles (45 nm) were dispersed in weight fraction of 2, 4, 6 and 8 % to reinforce the epoxy. DMA results show the significant enhancement in viscoelastic properties with the dispersion of zirconia nanoparticles in the epoxy matrix. The value of storage modulus and glass transition temperature increases from 179 MPa (pristine) to 225 MPa (6 wt.% ZrO2) and 61 °C (pristine) to 70 °C (6 wt.% ZrO2) respectively with the dispersion of zirconia nanoparticles in the epoxy.

Effect of nanoparticles dispersion on viscoelastic properties of epoxy-zirconia polymer nanocomposites

NASA Astrophysics Data System (ADS)

Singh, Sushil Kumar; Kumar, Abhishek; Jain, Anuj

2018-03-01

In the present work zirconia-nanoparticles were dispersed in epoxy matrix to form epoxy-zirconia polymer nanocomposites using ultrasonication and viscoelastic properties of nanocomposites were investigated. For the same spherical zirconia-nanoparticles (45 nm) were dispersed in weight fraction of 2, 4, 6 and 8 % to reinforce the epoxy. DMA results show the significant enhancement in viscoelastic properties with the dispersion of zirconia nanoparticles in the epoxy matrix. The value of storage modulus and glass transition temperature increases from 179 MPa (pristine) to 225 MPa (6 wt.% ZrO2) and 61 °C (pristine) to 70 °C (6 wt.% ZrO2) respectively with the dispersion of zirconia nanoparticles in the epoxy.

Surface roughness of zirconia for full-contour crowns after clinically simulated grinding and polishing.

PubMed

Hmaidouch, Rim; Müller, Wolf-Dieter; Lauer, Hans-Christoph; Weigl, Paul

2014-12-01

The aim of this study was to evaluate the effect of controlled intraoral grinding and polishing on the roughness of full-contour zirconia compared to classical veneered zirconia. Thirty bar-shaped zirconia specimens were fabricated and divided into two groups (n=15). Fifteen specimens (group 1) were glazed and 15 specimens (group 2) were veneered with feldspathic ceramic and then glazed. Prior to grinding, maximum roughness depth (Rmax) values were measured using a profilometer, 5 times per specimen. Simulated clinical grinding and polishing were performed on the specimens under water coolant for 15 s and 2 N pressure. For grinding, NTI diamonds burs with grain sizes of 20 µm, 10 µm, and 7.5 µm were used sequentially. The ground surfaces were polished using NTI kits with coarse, medium and fine polishers. After each step, Rmax values were determined. Differences between groups were examined using one-way analysis of variance (ANOVA). The roughness of group 1 was significantly lower than that of group 2. The roughness increased significantly after coarse grinding in both groups. The results after glazing were similar to those obtained after fine grinding for non-veneered zirconia. However, fine-ground veneered zirconia had significantly higher roughness than venerred, glazed zirconia. No significant difference was found between fine-polished and glazed zirconia, but after the fine polishing of veneered zirconia, the roughness was significantly higher than after glazing. It can be concluded that for full-contour zirconia, fewer defects and lower roughness values resulted after grinding and polishing compared to veneered zirconia. After polishing zirconia, lower roughness values were achieved compared to glazing; more interesting was that the grinding of glazed zirconia using the NTI three-step system could deliver smooth surfaces comparable to untreated glazed zirconia surfaces.

Surface roughness of zirconia for full-contour crowns after clinically simulated grinding and polishing

PubMed Central

Hmaidouch, Rim; Müller, Wolf-Dieter; Lauer, Hans-Christoph; Weigl, Paul

2014-01-01

The aim of this study was to evaluate the effect of controlled intraoral grinding and polishing on the roughness of full-contour zirconia compared to classical veneered zirconia. Thirty bar-shaped zirconia specimens were fabricated and divided into two groups (n=15). Fifteen specimens (group 1) were glazed and 15 specimens (group 2) were veneered with feldspathic ceramic and then glazed. Prior to grinding, maximum roughness depth (Rmax) values were measured using a profilometer, 5 times per specimen. Simulated clinical grinding and polishing were performed on the specimens under water coolant for 15 s and 2 N pressure. For grinding, NTI diamonds burs with grain sizes of 20 µm, 10 µm, and 7.5 µm were used sequentially. The ground surfaces were polished using NTI kits with coarse, medium and fine polishers. After each step, Rmax values were determined. Differences between groups were examined using one-way analysis of variance (ANOVA). The roughness of group 1 was significantly lower than that of group 2. The roughness increased significantly after coarse grinding in both groups. The results after glazing were similar to those obtained after fine grinding for non-veneered zirconia. However, fine-ground veneered zirconia had significantly higher roughness than venerred, glazed zirconia. No significant difference was found between fine-polished and glazed zirconia, but after the fine polishing of veneered zirconia, the roughness was significantly higher than after glazing. It can be concluded that for full-contour zirconia, fewer defects and lower roughness values resulted after grinding and polishing compared to veneered zirconia. After polishing zirconia, lower roughness values were achieved compared to glazing; more interesting was that the grinding of glazed zirconia using the NTI three-step system could deliver smooth surfaces comparable to untreated glazed zirconia surfaces. PMID:25059249

Stationary and non-stationary extreme value modeling of extreme temperature in Malaysia

NASA Astrophysics Data System (ADS)

Hasan, Husna; Salleh, Nur Hanim Mohd; Kassim, Suraiya

2014-09-01

Extreme annual temperature of eighteen stations in Malaysia is fitted to the Generalized Extreme Value distribution. Stationary and non-stationary models with trend are considered for each station and the Likelihood Ratio test is used to determine the best-fitting model. Results show that three out of eighteen stations i.e. Bayan Lepas, Labuan and Subang favor a model which is linear in the location parameter. A hierarchical cluster analysis is employed to investigate the existence of similar behavior among the stations. Three distinct clusters are found in which one of them consists of the stations that favor the non-stationary model. T-year estimated return levels of the extreme temperature are provided based on the chosen models.

Bond Strength of Resin Cements to Zirconia Ceramic Using Adhesive Primers.

PubMed

Stefani, Ariovaldo; Brito, Rui Barbosa; Kina, Sidney; Andrade, Oswaldo Scopin; Ambrosano, Gláucia Maria Bovi; Carvalho, Andreia Assis; Giannini, Marcelo

2016-07-01

To evaluate the influence of adhesive primers on the microshear bond strength of resin cements to zirconia ceramic. Fifty zirconia plates (12 mm × 5 mm × 1.5 mm thick) of a commercially available zirconium oxide ceramic (ZirCad) were sintered, sandblasted with aluminum oxide particles, and cleaned ultrasonically before bonding. The plates were randomly divided into five groups of 10. Three resin cements were selected (RelyX ARC, Multilink Automix, Clearfil SA Cement self-adhesive resin cement), along with two primers (Metal-Zirconia Primer, Alloy Primer) and one control group. The primers and resin cements were used according to manufacturers' recommendations. The control group comprised the conventional resin cement (RelyX ARC) without adhesive primer. Test cylinders (0.75 mm diameter × 1 mm high) were formed on zirconia surfaces by filling cylindrical Tygon tube molds with resin cement. The specimens were stored in distilled water for 24 hours at 37°C, then tested for shear strength on a Shimadzu EZ Test testing machine at 0.5 mm/min. Bond strength data were analyzed statistically by two-way ANOVA and Dunnett's test (5%). The bond strength means in MPa (± s.d.) were: RelyX ARC: 28.1 (6.6); Multilink Automix: 37.6 (4.5); Multilink Automix + Metal-Zirconia Primer: 55.7 (4.0); Clearfil SA Cement: 46.2 (3.3); and Clearfil SA Cement + Alloy Primer: 47.0 (4.1). Metal-Zirconia Primer increased the bond strength of Multilink Automix resin cement to zirconia, but no effect was observed for Alloy Primer using Clearfil SA Cement. RelyX ARC showed the lowest bond strength to zirconia. © 2015 by the American College of Prosthodontists.

Retention Forces between Titanium and Zirconia Components of Two-Part Implant Abutments with Different Techniques of Surface Modification.

PubMed

von Maltzahn, Nadine Freifrau; Holstermann, Jan; Kohorst, Philipp

2016-08-01

The adhesive connection between titanium base and zirconia coping of two-part abutments may be responsible for the failure rate. A high mechanical stability between both components is essential for the long-term success. The aim of the present in-vitro study was to evaluate the influence of different surface modification techniques and resin-based luting agents on the retention forces between titanium and zirconia components in two-part implant abutments. A total of 120 abutments with a titanium base bonded to a zirconia coping were investigated. Two different resin-based luting agents (Panavia F 2.0 and RelyX Unicem) and six different surface modifications were used to fix these components, resulting in 12 test groups (n = 10). The surface of the test specimens was mechanically pretreated with aluminium oxide blasting in combination with application of two surface activating primers (Alloy Primer, Clearfil Ceramic Primer) or a tribological conditioning (Rocatec), respectively. All specimens underwent 10,000 thermal cycles between 5°C and 55°C in a moist environment. A pull-off test was then conducted to determine retention forces between the titanium and zirconia components, and statistical analysis was performed (two-way anova). Finally, fracture surfaces were analyzed by light and scanning electron microscopy. No significant differences were found between Panavia F 2.0 and RelyX Unicem. However, the retention forces were significantly influenced by the surface modification technique used (p < 0.001). For both luting agents, the highest retention forces were found when adhesion surfaces of both the titanium bases and the zirconia copings were pretreated with aluminium oxide blasting, and with the application of Clearfil Ceramic Primer. Surface modification techniques crucially influence the retention forces between titanium and zirconia components in two-part implant abutments. All adhesion surfaces should be pretreated by sandblasting. Moreover, a

Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

NASA Astrophysics Data System (ADS)

Sherly, K. B.; Rakesh, K.

2014-01-01

Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl2ṡ8H2O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with the theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.

Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

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

Sherly, K. B.; Rakesh, K.

Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl{sub 2}⋅8H{sub 2}O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with themore » theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.« less

3D-characterization of the veneer-zirconia interface using FIB nano-tomography.

PubMed

Mainjot, Amélie K; Douillard, Thierry; Gremillard, Laurent; Sadoun, Michaël J; Chevalier, Jérôme

2013-02-01

The phenomena occurring during zirconia frameworks veneering process are not yet fully understood. In particular the study of zirconia behavior at the interface with the veneer remains a challenge. However this interface has been reported to act on residual stress in the veneering ceramic, which plays a significant role in clinical failures such as chipping. The objective of this study was thus to investigate the veneer-zirconia interface using a recent 3D-analysis tool and to confront these observations to residual stress measurements in the veneering ceramic. Two cross-sectioned bilayered disc samples (veneer on zirconia), exhibiting different residual stress profiles in the veneering ceramic, were investigated using 2D and 3D imaging (respectively Scanning Electron Microscopy (SEM) and Focused Ion Beam nanotomography (FIB-nt), associated with chemical analysis by Energy Dispersive X-ray Spectroscopy (EDS). The observations did not reveal any structural change in the bulk of zirconia layer of both samples. However the presence of structural alterations and sub-surface microcracks were highlighted in the first micrometer of zirconia surface, exclusively for the sample exhibiting interior tensile stress in the veneering ceramic. No interdiffusion phenomena were observed. FIB nanotomography was proven to be a powerful technique to study the veneer-zirconia interface. The determination of the origin and the nature of zirconia alterations need to be further studied. The results of the present study support the hypothesis that zirconia surface property changes could be involved in the development of tensile stress in the veneering ceramic, increasing the risk of chipping. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Surface crystalline phases and nanoindentation hardness of explanted zirconia femoral heads.

PubMed

Catledge, Shane A; Cook, Monique; Vohra, Yogesh K; Santos, Erick M; McClenny, Michelle D; David Moore, K

2003-10-01

One new and nine explanted zirconia femoral heads were studied using glancing angle X-ray diffraction, scanning electron microscopy, and nanoindentation hardness techniques. All starting zirconia implants consisted only of tetragonal zirconia polycrystals (TZP). For comparison, one explanted alumina femoral head was also studied. Evidence for a surface tetragonal-to-monoclinic zirconia phase transformation was observed in some implants, the extent of which was varied for different in-service conditions. A strong correlation was found between increasing transformation to the monoclinic phase and decreasing surface hardness. Microscopic investigations of some of the explanted femoral heads revealed ultra high molecular weight polyethylene and metallic transfer wear debris.

Alumina-Reinforced Zirconia Composites

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Bansal, Narottam P.

2003-01-01

Alumina-reinforced zirconia composites, used as electrolyte materials for solid oxide fuel cells, were fabricated by hot pressing 10 mol percent yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina particulates and platelets each containing 0 to 30 mol percent alumina. Major mechanical and physical properties of both particulate and platelet composites including flexure strength, fracture toughness, slow crack growth, elastic modulus, density, Vickers microhardness, thermal conductivity, and microstructures were determined as a function of alumina content either at 25 C or at both 25 and 1000 C. Flexure strength and fracture toughness at 1000 C were maximized with 30 particulate and 30 mol percent platelet composites, respectively, while resistance to slow crack growth at 1000 C in air was greater for 30 mol percent platelet composite than for 30 mol percent particulate composites.

Spin-Selective Transmission and Devisable Chirality in Two-Layer Metasurfaces.

PubMed

Li, Zhancheng; Liu, Wenwei; Cheng, Hua; Chen, Shuqi; Tian, Jianguo

2017-08-15

Chirality is a nearly ubiquitous natural phenomenon. Its minute presence in most naturally occurring materials makes it incredibly difficult to detect. Recent advances in metasurfaces indicate that they exhibit devisable chirality in novel forms; this finding offers an effective opening for studying chirality and its features in such nanostructures. These metasurfaces display vast possibilities for highly sensitive chirality discrimination in biological and chemical systems. Here, we show that two-layer metasurfaces based on twisted nanorods can generate giant spin-selective transmission and support engineered chirality in the near-infrared region. Two designed metasurfaces with opposite spin-selective transmission are proposed for treatment as enantiomers and can be used widely for spin selection and enhanced chiral sensing. Specifically, we demonstrate that the chirality in these proposed metasurfaces can be adjusted effectively by simply changing the orientation angle between the twisted nanorods. Our results offer simple and straightforward rules for chirality engineering in metasurfaces and suggest intriguing possibilities for the applications of such metasurfaces in spin optics and chiral sensing.

Fracture resistance and failure mode of posterior fixed dental prostheses fabricated with two zirconia CAD/CAM systems

PubMed Central

López-Suárez, Carlos; Gonzalo, Esther; Peláez, Jesús; Rodríguez, Verónica

2015-01-01

Background In recent years there has been an improvement of zirconia ceramic materials to replace posterior missing teeth. To date little in vitro studies has been carried out on the fracture resistance of zirconia veneered posterior fixed dental prostheses. This study investigated the fracture resistance and the failure mode of 3-unit zirconia-based posterior fixed dental prostheses fabricated with two CAD/CAM systems. Material and Methods Twenty posterior fixed dental prostheses were studied. Samples were randomly divided into two groups (n=10 each) according to the zirconia ceramic analyzed: Lava and Procera. Specimens were loaded until fracture under static load. Data were analyzed using Wilcoxon´s rank sum test and Wilcoxon´s signed-rank test (P<0.05). Results Partial fracture of the veneering porcelain occurred in 100% of the samples. Within each group, significant differences were shown between the veneering and the framework fracture resistance (P=0.002). The failure occurred in the connector cervical area in 80% of the cases. Conclusions All fracture load values of the zirconia frameworks could be considered clinically acceptable. The connector area is the weak point of the restorations. Key words:Fixed dental prostheses, zirconium-dioxide, zirconia, fracture resistance, failure mode. PMID:26155341

Retention characteristics of a new butylimidazolium-based stationary phase. Part II: anion exchange and partitioning.

PubMed

Van Meter, David S; Sun, Yaqin; Parker, Kevin M; Stalcup, Apryll M

2008-02-01

A surface-confined ionic liquid (SCIL) and a commercial quaternary amine silica-based stationary phase were characterized employing the linear solvation energy relationship (LSER) method in binary methanol/water mobile phases. The retention properties of the stationary phases were evaluated in terms of intermolecular interactions between 28 test solutes and the stationary phases. The comparison reveals a difference in the hydrophobic and hydrogen bond acceptance interaction properties between the two phases. The anion exchange retention mechanism of the SCIL phase was demonstrated using nucleotides. The utility of the SCIL phase in predicting logk (IL/water) values by chromatographic methods is also discussed.

Optical properties and light irradiance of monolithic zirconia at variable thicknesses.

PubMed

Sulaiman, Taiseer A; Abdulmajeed, Aous A; Donovan, Terrence E; Ritter, André V; Vallittu, Pekka K; Närhi, Timo O; Lassila, Lippo V

2015-10-01

The aims of this study were to: (1) estimate the effect of polishing on the surface gloss of monolithic zirconia, (2) measure and compare the translucency of monolithic zirconia at variable thicknesses, and (3) determine the effect of zirconia thickness on irradiance and total irradiant energy. Four monolithic partially stabilized zirconia (PSZ) brands; Prettau® (PRT, Zirkonzahn), Bruxzir® (BRX, Glidewell), Zenostar® (ZEN, Wieland), Katana® (KAT, Noritake), and one fully stabilized zirconia (FSZ); Prettau Anterior® (PRTA, Zirkonzahn) were used to fabricate specimens (n=5/subgroup) with different thicknesses (0.5, 0.7, 1.0, 1.2, 1.5, and 2.0mm). Zirconia core material ICE® Zircon (ICE, Zirkonzahn) was used as a control. Surface gloss and translucency were evaluated using a reflection spectrophotometer. Irradiance and total irradiant energy transmitted through each specimen was quantified using MARC® Resin Calibrator. All specimens were then subjected to a standardized polishing method and the surface gloss, translucency, irradiance, and total irradiant energy measurements were repeated. Statistical analysis was performed using two-way ANOVA and post-hoc Tukey's tests (p<0.05). Surface gloss was significantly affected by polishing (p<0.05), regardless of brand and thickness. Translucency values ranged from 5.65 to 20.40 before polishing and 5.10 to 19.95 after polishing. The ranking from least to highest translucent (after polish) was: BRX=ICE=PRTzirconia and the amount was brand dependent (p<0.05). Brand selection, thickness, and polishing of monolithic zirconia can affect the ultimate clinical outcome of the optical properties of zirconia restorations. FSZ is relatively more polishable and translucent than PSZ. Copyright © 2015 Academy of Dental

Influence of cleaning methods on resin bonding to saliva-contaminated zirconia.

PubMed

Yoshida, Keiichi

2018-02-08

The aim of this study was to investigate the influence of different cleaning methods on the shear bond strengths of 2 resin cements to saliva-contaminated zirconia. After saliva contamination, alumina-blasted zirconia specimens were cleaned with 1 of 5 methods of water-rinsing (SA), K-etchant GEL phosphoric acid (PA), Ivoclean (IC), AD Gel (ADG), or additional alumina-blasting (AB). Alumina-blasted zirconia without saliva contamination was used as control group (Cont). Composite cylinders were bonded to the zirconia with 1 of 2 dual-cured resin cements. The bond strengths were measured by shear testing after 24 hours (TC0) and after thermal cycling at 4°C-60°C (TC10 000) and specimen surfaces were evaluated using X-ray photoelectron spectroscopy (XPS). Data were statistically analyzed using 3-way analysis of variance and Tukey test (α = 0.05). There were no significant differences in the bond strengths of 2 resin cements between the Cont ADG, and AB groups before and after TCs (P > .05). SA, PA, and IC groups did not exhibit durable resin bonding to zirconia. XPS showed that carbon and nitrogen increased in the SA group in comparison to the Cont group. The concentration of carbon in other 4 groups returned to the concentration range of the Cont group; however, nitrogen was not detected in the only AB group. Saliva contamination significantly reduced the bond strength of 2 resin cements to zirconia. Additional AB or cleaning with ADG resulted in effective cleaning of saliva contamination and preserved resin cement bond strength to zirconia. Saliva contamination occurs during clinical procedures for adjustment of zirconia ceramic restorations in the oral environment. AD Gel application is effective for removing saliva contaminants on the alumina-blasted zirconia surface beforehand by the dental laboratory instead of additional AB since AD Gel application and AB had a similar effect on the removal of organic components of saliva. © 2018 Wiley Periodicals

Fracture of Reduced-Diameter Zirconia Dental Implants Following Repeated Insertion.

PubMed

Karl, Matthias; Scherg, Stefan; Grobecker-Karl, Tanja

Achievement of high insertion torque values indicating good primary stability is a goal during dental implant placement. The objective of this study was to evaluate whether or not two-piece implants made from zirconia ceramic may be damaged as a result of torque application. A total of 10 two-piece zirconia implants were repeatedly inserted into polyurethane foam material with increasing density and decreasing osteotomy size. The insertion torque applied was measured, and implants were checked for fractures by applying the fluorescent penetrant method. Weibull probability of failure was calculated based on the recorded insertion torque values. Catastrophic failures could be seen in five of the implants from two different batches at insertion torques ranging from 46.0 to 70.5 Ncm, while the remaining implants (all belonging to one batch) survived. Weibull probability of failure seems to be low at the manufacturer-recommended maximum insertion torque of 35 Ncm. Chipping fractures at the thread tips as well as tool marks were the only otherwise observed irregularities. While high insertion torques may be desirable for immediate loading protocols, zirconia implants may fracture when manufacturer-recommended insertion torques are exceeded. Evaluating bone quality prior to implant insertion may be useful.

Recent Advances in Dynamic Kinetic Resolution by Chiral Bifunctional (Thio)urea- and Squaramide-Based Organocatalysts.

PubMed

Li, Pan; Hu, Xinquan; Dong, Xiu-Qin; Zhang, Xumu

2016-10-14

The organocatalysis-based dynamic kinetic resolution (DKR) process has proved to be a powerful strategy for the construction of chiral compounds. In this feature review, we summarized recent progress on the DKR process, which was promoted by chiral bifunctional (thio)urea and squaramide catalysis via hydrogen-bonding interactions between substrates and catalysts. A wide range of asymmetric reactions involving DKR, such as asymmetric alcoholysis of azlactones, asymmetric Michael-Michael cascade reaction, and enantioselective selenocyclization, are reviewed and demonstrate the efficiency of this strategy. The (thio)urea and squaramide catalysts with dual activation would be efficient for more unmet challenges in dynamic kinetic resolution.

Infrared wire-grid polarizer with sol-gel zirconia grating

NASA Astrophysics Data System (ADS)

Yamada, Itsunari; Ishihara, Yoshiro

2017-05-01

The infrared wire-grid polarizer consisting of an Al grating, Si, and sol-gel derived zirconia grating film was fabricated by soft imprint process and Al shadow coating processes. A silicone mold was used because of its low surface energy, flexibility, and capability of transferring submicrosized patterns. As a result, the Al grating with a pitch of 400 nm and a depth of 100 nm was obtained on the zirconia grating film. The fabricated polarizer exhibited a polarization function with the TM transmittance greater than that of the Si substrate in the specific wavelength range of 3.6-8.5 μm, because the zirconia film acted as an antireflection film. The maximum value was 63% at a wavelength of 5.2 μm. This increment of the TM transmission spectrum results in interference within the zirconia film. Also, the extinction ratio exceeded almost 20 dB in the 3-8.8 μm wavelength range.

Masking ability of a zirconia ceramic on composite resin substrate shades.

PubMed

Tabatabaian, Farhad; Shabani, Sima; Namdari, Mahshid; Sadeghpour, Koroush

2017-01-01

Masking ability of a restorative material plays an important role to cover discolored tooth structure; however, this ability has not yet been well understood in zirconia-based restorations. This study assessed the masking ability of a zirconia ceramic on composite resin substrates with different shades. Ten zirconia disc specimens, with 0.5 mm thickness and 10 mm diameter, were fabricated by a computer-aided design/computer-aided manufacturing system. A white substrate (control) and six composite resin substrates with different shades including A1, A2, A3, B2, C2, and D3 were prepared. The substrates had a cylindrical shape with 10 mm diameter and height. The specimens were placed onto the substrates for spectrophotometric evaluation. A spectrophotometer measured the L*, a*, and b* values for the specimens. ΔE values were calculated to determine the color differences between the groups and the control and then were compared with a perceptional threshold (ΔE = 2.6). Repeated measures ANOVA and Bonferroni tests were used for data analysis ( P < 0.05). The mean and standard deviation of ΔE values for A1, A2, A3, B2, C2, and D3 groups were 6.78 ± 1.59, 8.13 ± 1.66, 9.81 ± 2.64, 9.61 ± 1.38, 9.59 ± 2.63, and 8.13 ± 1.89, respectively. A significant difference was found among the groups in the ΔE values ( P = 0.006). The ΔE values were more than the perceptional threshold in all the groups ( P < 0.0001). Within the limitations of this study, it can be concluded that the tested zirconia ceramic could not thoroughly mask different shades of the composite resin substrates. Moreover, color masking of zirconia depends on the shade of substrate.

Induction of Chirality in Two-Dimensional Nanomaterials: Chiral 2D MoS2 Nanostructures.

PubMed

Purcell-Milton, Finn; McKenna, Robert; Brennan, Lorcan J; Cullen, Conor P; Guillemeney, Lilian; Tepliakov, Nikita V; Baimuratov, Anvar S; Rukhlenko, Ivan D; Perova, Tatiana S; Duesberg, Georg S; Baranov, Alexander V; Fedorov, Anatoly V; Gun'ko, Yurii K

2018-02-27

Two-dimensional (2D) nanomaterials have been intensively investigated due to their interesting properties and range of potential applications. Although most research has focused on graphene, atomic layered transition metal dichalcogenides (TMDs) and particularly MoS 2 have gathered much deserved attention recently. Here, we report the induction of chirality into 2D chiral nanomaterials by carrying out liquid exfoliation of MoS 2 in the presence of chiral ligands (cysteine and penicillamine) in water. This processing resulted in exfoliated chiral 2D MoS 2 nanosheets showing strong circular dichroism signals, which were far past the onset of the original chiral ligand signals. Using theoretical modeling, we demonstrated that the chiral nature of MoS 2 nanosheets is related to the presence of chiral ligands causing preferential folding of the MoS 2 sheets. There was an excellent match between the theoretically calculated and experimental spectra. We believe that, due to their high aspect ratio planar morphology, chiral 2D nanomaterials could offer great opportunities for the development of chiroptical sensors, materials, and devices for valleytronics and other potential applications. In addition, chirality plays a key role in many chemical and biological systems, with chiral molecules and materials critical for the further development of biopharmaceuticals and fine chemicals, and this research therefore should have a strong impact on relevant areas of science and technology such as nanobiotechnology, nanomedicine, and nanotoxicology.

Comparative fracture strength analysis of Lava and Digident CAD/CAM zirconia ceramic crowns

PubMed Central

Kwon, Taek-Ka; Pak, Hyun-Soon; Han, Jung-Suk; Lee, Jai-Bong; Kim, Sung-Hun

2013-01-01

PURPOSE All-ceramic crowns are subject to fracture during function. To minimize this common clinical complication, zirconium oxide has been used as the framework for all-ceramic crowns. The aim of this study was to compare the fracture strengths of two computer-aided design/computer-aided manufacturing (CAD/CAM) zirconia crown systems: Lava and Digident. MATERIALS AND METHODS Twenty Lava CAD/CAM zirconia crowns and twenty Digident CAD/CAM zirconia crowns were fabricated. A metal die was also duplicated from the original prepared tooth for fracture testing. A universal testing machine was used to determine the fracture strength of the crowns. RESULTS The mean fracture strengths were as follows: 54.9 ± 15.6 N for the Lava CAD/CAM zirconia crowns and 87.0 ± 16.0 N for the Digident CAD/CAM zirconia crowns. The difference between the mean fracture strengths of the Lava and Digident crowns was statistically significant (P<.001). Lava CAD/CAM zirconia crowns showed a complete fracture of both the veneering porcelain and the core whereas the Digident CAD/CAM zirconia crowns showed fracture only of the veneering porcelain. CONCLUSION The fracture strengths of CAD/CAM zirconia crowns differ depending on the compatibility of the core material and the veneering porcelain. PMID:23755332

Comparative fracture strength analysis of Lava and Digident CAD/CAM zirconia ceramic crowns.

PubMed

Kwon, Taek-Ka; Pak, Hyun-Soon; Yang, Jae-Ho; Han, Jung-Suk; Lee, Jai-Bong; Kim, Sung-Hun; Yeo, In-Sung

2013-05-01

All-ceramic crowns are subject to fracture during function. To minimize this common clinical complication, zirconium oxide has been used as the framework for all-ceramic crowns. The aim of this study was to compare the fracture strengths of two computer-aided design/computer-aided manufacturing (CAD/CAM) zirconia crown systems: Lava and Digident. Twenty Lava CAD/CAM zirconia crowns and twenty Digident CAD/CAM zirconia crowns were fabricated. A metal die was also duplicated from the original prepared tooth for fracture testing. A universal testing machine was used to determine the fracture strength of the crowns. THE MEAN FRACTURE STRENGTHS WERE AS FOLLOWS: 54.9 ± 15.6 N for the Lava CAD/CAM zirconia crowns and 87.0 ± 16.0 N for the Digident CAD/CAM zirconia crowns. The difference between the mean fracture strengths of the Lava and Digident crowns was statistically significant (P<.001). Lava CAD/CAM zirconia crowns showed a complete fracture of both the veneering porcelain and the core whereas the Digident CAD/CAM zirconia crowns showed fracture only of the veneering porcelain. The fracture strengths of CAD/CAM zirconia crowns differ depending on the compatibility of the core material and the veneering porcelain.

In Vitro Cell Proliferation and Mechanical Behaviors Observed in Porous Zirconia Ceramics

PubMed Central

Li, Jing; Wang, Xiaobei; Lin, Yuanhua; Deng, Xuliang; Li, Ming; Nan, Cewen

2016-01-01

Zirconia ceramics with porous structure have been prepared by solid-state reaction using yttria-stabilized zirconia and stearic acid powders. Analysis of its microstructure and phase composition revealed that a pure zirconia phase can be obtained. Our results indicated that its porosity and pore size as well as the mechanical characteristics can be tuned by changing the content of stearic acid powder. The optimal porosity and pore size of zirconia ceramic samples can be effective for the increase of surface roughness, which results in higher cell proliferation values without destroying the mechanical properties. PMID:28773341

Influence of full-contour zirconia surface roughness on wear of glass-ceramics.

PubMed

Luangruangrong, Palika; Cook, N Blaine; Sabrah, Alaa H; Hara, Anderson T; Bottino, Marco C

2014-04-01

The purpose of this study was to evaluate the influence of full-contour (Y-TZP) zirconia surface roughness (glazed vs. as-machined) on the wear behavior of glass-ceramics. Thirty-two full contour Y-TZP (Diazir®) specimens (hereafter referred to as zirconia sliders) (ϕ = 2 mm, 1.5 mm in height) were fabricated using CAD/CAM and sintered according to the manufacturer's instructions. Zirconia sliders were embedded in brass holders using acrylic resin and then randomly assigned (n = 16) according to the surface treatment received, that is, as-machined or glazed. Glass-ceramic antagonists, Empress/EMP and e.max/EX, were cut into tabs (13 × 13 × 2 mm(3) ), wet-finished, and similarly embedded in brass holders. Two-body pin-on-disk wear testing was performed at 1.2 Hz for 25,000 cycles under a 3 kg load. Noncontact profilometry was used to measure antagonist height (μm) and volume loss (mm(3) ). Qualitative data of the zirconia testing surfaces and wear tracks were obtained using SEM. Statistics were performed using ANOVA with a significance level of 0.05. As-machined yielded significantly higher mean roughness values (Ra = 0.83 μm, Rq = 1.09 μm) than glazed zirconia (Ra = 0.53 μm, Rq = 0.78 μm). Regarding glass-ceramic antagonist loss, as-machined zirconia caused significantly less mean height and volume loss (68.4 μm, 7.6 mm(3) ) for EMP than the glazed group (84.9 μm, 9.9 mm(3) ), while no significant differences were found for EX. Moreover, EMP showed significantly lower mean height and volume loss than EX (p < 0.0001). SEM revealed differences on wear characteristics between the glass-ceramics tested. e.max wear was not affected by zirconia surface roughness; however, Empress wear was greater when opposing glazed zirconia. Overall, surface glazing on full-contour zirconia did not minimize glass-ceramic wear when compared with as-machined zirconia. © 2013 by the American College of Prosthodontists.

A sol-powder coating technique for fabrication of yttria stabilised zirconia

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

Wattanasiriwech, Darunee; Wattanasiriwech, Suthee; Stevens, Ron

Yttria stabilised zirconia has been prepared using a simple sol-powder coating technique. The polymeric yttria sol, which was prepared using 1,3 propanediol as a network modifier, was homogeneously mixed with nanocrystalline zirconia powder and it showed a dual function: as a binder which promoted densification and a phase modifier which stabilised zirconia in the tetragonal and cubic phases. Thermal analysis and X-ray diffraction revealed that the polymeric yttria sol which decomposed at low temperature into yttrium oxide could change the m {sup {yields}} t phase transformation behaviour of the zirconia, possibly due to the small particle size and very highmore » surface area of both yttria and zirconia particles allowing rapid alloying. The sintered samples exhibited three crystalline phases: monoclinic, tetragonal and cubic, in which cubic and tetragonal are the major phases. The weight fractions of the individual phases present in the selected specimens were determined using quantitative Rietveld analysis.« less

Chiral separation of norlaudanosoline, laudanosoline, laudanosine, chlorthalidone, and three benzoin derivatives using amino acid based molecular micelles.

PubMed

Billiot, Fereshteh H; Billiot, Eugene J; Ng, Yuen Kwun; Warner, Isiah M

2006-02-01

In this study, 18 polymeric single amino acid and dipeptide surfactants are examined, and their performances, in terms of enantioselectivity, are compared for norlaudanosoline, laudanosoline, laudanosine, chlorthalidone, benzoin, benzoin methyl, and benzoin ethyl enantiomers. Several aspects of amino acid-based polymeric surfactants including comparison of single amino acid versus dipeptide, amino acid order, steric effect, and effect of the position of the chiral center of dipeptide surfactants on the chiral selectivity of these optically active compounds are discussed.

Three dimensional chiral plasmon rulers based on silver nanorod trimers.

PubMed

Han, Chunrui; Yang, Lechen; Ye, Piao; Parrott, Edward P J; Pickwell-Macpherson, Emma; Tam, Wing Yim

2018-04-16

The symmetry dependences of plasmon excitation modes are studied in 3D silver nanorod trimers. The degenerate plasmon modes split into chiral modes by breaking the inversion and mirror symmetry of the nanorod trimer through translation and/or rotation of the middle rod. With a translation operation, successive evolution of the circular dichroism (CD) spectrum can be achieved through gradual breaking of the inversion symmetry. An additional rotation operation produces even dramatic spectral changes due to breaking a quasi-mirror symmetry resulted from the same angular distance of the middle rod to the top and bottom rods. Especially, pairs of new chiral modes can be excited due to the contact of the middle rod with the top-bottom rod pair. The spectral changes in the simulations, which are also demonstrated experimentally, envision the 3D chiral nanorod trimer system as plasmon ruler for spatial configuration retrieval and dynamic bio-process analysis at the single molecule level.

Evaluation of an amide-based stationary phase for supercritical fluid chromatography

PubMed Central

Borges-Muñoz, Amaris C.; Colón, Luis A.

2017-01-01

A relatively new stationary phase containing a polar group embedded in a hydrophobic backbone (i.e., ACE® C18-amide) was evaluated for use in supercritical fluid chromatography. The amide-based column was compared with columns packed with bare silica, C18 silica, and a terminal-amide silica phase. The system was held at supercritical pressure and temperature with a mobile phase composition of CO2 and methanol as cosolvent. The linear solvation energy relationship model was used to evaluate the behavior of these stationary phases, relating the retention factor of selected probes to specific chromatographic interactions. A five-component test mixture, consisting of a group of drug-like molecules was separated isocratically. The results show that the C18-amide stationary phase provided a combination of interactions contributing to the retention of the probe compounds. The hydrophobic interactions are favorable; however, the electron donating ability of the embedded amide group shows a large positive interaction. Under the chromatographic conditions used, the C18-amide column was able to provide baseline resolution of all the drug-like probe compounds in a text mixture, while the other columns tested did not. PMID:27396487

Enantioselective determination of 3-n-butylphthalide (NBP) in human plasma by liquid chromatography on a teicoplanin-based chiral column coupled with tandem mass spectrometry.

PubMed

Diao, Xingxing; Ma, Zhiyu; Lei, Peng; Zhong, Dafang; Zhang, Yifan; Chen, Xiaoyan

2013-11-15

A novel and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated to determine the exposure of 3-n-butylphthalide (NBP) enantiomers in human plasma. The NBP enantiomers were extracted from human plasma using methyl tert-butyl ether. The baseline separation of R-(+)-NBP and S-(-)-NBP was achieved within 11.0min using a teicoplanin-based Astec Chirobiotic T column (250mm×4.6mm i.d., 5μm) under isocratic conditions at a flow rate of 0.6mL/min. The selection of the chiral stationary phase and the effect of the mobile phase composition on the resolution of the enantiomers were discussed. The selectivity, linearity, precision, accuracy, matrix effect, recovery, and stability were evaluated under optimized conditions. The LC-MS/MS method using 200μL of human plasma was linear over the concentration range of 5.00-400ng/mL for each enantiomer. The lower limit of quantification (LLOQ) for both enantiomers was 5.00ng/mL. The intra- and inter-assay precision values of the replicated quality control samples were within 8.0% for each enantiomer. The mean accuracy values for the quality control samples were within ±6.1% of the nominal values for R-(+)-NBP and S-(-)-NBP. No chiral inversion was observed during sample storage, preparation, and analysis. The method proved suitable for enantioselective pharmacokinetic studies of NBP after an oral administration of a therapeutic dose of racemic NBP. Copyright © 2013 Elsevier B.V. All rights reserved.

Periodic chiral structures

NASA Technical Reports Server (NTRS)

Jaggard, Dwight L.; Engheta, Nader; Pelet, Philippe; Liu, John C.; Kowarz, Marek W.; Kim, Yunjin

1989-01-01

The electromagnetic properties of a structure that is both chiral and periodic are investigated using coupled-mode equations. The periodicity is described by a sinusoidal perturbation of the permittivity, permeability, and chiral admittance. The coupled-mode equations are derived from physical considerations and used to examine bandgap structure and reflected and transmitted fields. Chirality is observed predominantly in transmission, whereas periodicity is present in both reflection and transmission.

The Effect of Zirconia in Hydroxyapatite on Staphylococcus epidermidis Growth.

PubMed

Siswomihardjo, Widowati; Sunarintyas, Siti; Tontowi, Alva Edy

2012-01-01

Synthetic hydroxyapatite (HA) has been widely used and developed as the material for bone substitute in medical applications. The addition of zirconia is needed to improve the strength of hydroxyapatite as the bone substitute. One of the drawbacks in the use of biomedical materials is the occurrence of biomaterial-centred infections. The recent method of limiting the presence of microorganism on biomaterials is by providing biomaterial-bound metal-containing compositions. In this case, S. epidermidis is the most common infectious organism in biomedical-centred infection. Objective. This study was designed to evaluate the effect of zirconia concentrations in hydroxyapatite on the growth of S. epidermidis. Methods and Materials. The subjects of this study were twenty hydroxyapatite discs, divided into four groups in which one was the control and the other three were the treatment groups. Zirconia powder with the concentrations of 20%, 30%, and 40% was added into the three different treatment groups. Scanning electron microscope analysis was performed according to the hydroxyapatite and hydroxyapatite-zirconia specimens. All discs were immersed into S. epidermidis culture for 24 hours and later on they were soaked into a medium of PBS. The cultured medium was spread on mannitol salt agar. After incubation for 24 hours at 37°C , the number of colonies was measured with colony counter. Data obtained were analyzed using the ANOVA followed by the pairwise comparison. Result. The statistical analysis showed that different concentrations of zirconia powder significantly influenced the number of S. epidermidis colony (P < 0.05) . Conclusion. The addition of zirconia into hydroxyapatite affected the growth of S. epidermidis. Hydroxyapatite with 20% zirconia proved to be an effective concentration to inhibit the growth of S. epidermidis colony.

Bioactive and Thermally Compatible Glass Coating on Zirconia Dental Implants

PubMed Central

Kirsten, A.; Hausmann, A.; Weber, M.; Fischer, J.

2015-01-01

The healing time of zirconia implants may be reduced by the use of bioactive glass coatings. Unfortunately, existing glasses are either bioactive like Bioglass 45S5 but thermally incompatible with the zirconia substrate, or they are thermally compatible but exhibit only a very low level of bioactivity. In this study, we hypothesized that a tailored substitution of alkaline earth metals and alkaline metals in 45S5 can lead to a glass composition that is both bioactive and thermally compatible with zirconia implants. A novel glass composition was analyzed using x-ray fluorescence spectroscopy, dilatometry, differential scanning calorimetry, and heating microscopy to investigate its chemical, physical, and thermal properties. Bioactivity was tested in vitro using simulated body fluid (SBF). Smooth and microstructured glass coatings were applied using a tailored spray technique with subsequent thermal treatment. Coating adhesion was tested on implants that were inserted in bovine ribs. The cytocompatibility of the coating was analyzed using L929 mouse fibroblasts. The coefficient of thermal expansion of the novel glass was shown to be slightly lower (11.58·10–6 K–1) than that of the zirconia (11.67·10–6 K–1). After storage in SBF, the glass showed reaction layers almost identical to the bioactive glass gold standard, 45S5. A process window between 800 °C and 910 °C was found to result in densely sintered and amorphous coatings. Microstructured glass coatings on zirconia implants survived a minimum insertion torque of 60 Ncm in the in vitro experiment on bovine ribs. Proliferation and cytotoxicity of the glass coatings was comparable with the controls. The novel glass composition showed a strong adhesion to the zirconia substrate and a significant bioactive behavior in the SBF in vitro experiments. Therefore, it holds great potential to significantly reduce the healing time of zirconia dental implants. PMID:25421839

The Effect of Zirconia in Hydroxyapatite on Staphylococcus epidermidis Growth

PubMed Central

Siswomihardjo, Widowati; Sunarintyas, Siti; Tontowi, Alva Edy

2012-01-01

Synthetic hydroxyapatite (HA) has been widely used and developed as the material for bone substitute in medical applications. The addition of zirconia is needed to improve the strength of hydroxyapatite as the bone substitute. One of the drawbacks in the use of biomedical materials is the occurrence of biomaterial-centred infections. The recent method of limiting the presence of microorganism on biomaterials is by providing biomaterial-bound metal-containing compositions. In this case, S. epidermidis is the most common infectious organism in biomedical-centred infection. Objective. This study was designed to evaluate the effect of zirconia concentrations in hydroxyapatite on the growth of S. epidermidis. Methods and Materials. The subjects of this study were twenty hydroxyapatite discs, divided into four groups in which one was the control and the other three were the treatment groups. Zirconia powder with the concentrations of 20%, 30%, and 40% was added into the three different treatment groups. Scanning electron microscope analysis was performed according to the hydroxyapatite and hydroxyapatite-zirconia specimens. All discs were immersed into S. epidermidis culture for 24 hours and later on they were soaked into a medium of PBS. The cultured medium was spread on mannitol salt agar. After incubation for 24 hours at 37°C , the number of colonies was measured with colony counter. Data obtained were analyzed using the ANOVA followed by the pairwise comparison. Result. The statistical analysis showed that different concentrations of zirconia powder significantly influenced the number of S. epidermidis colony (P < 0.05) . Conclusion. The addition of zirconia into hydroxyapatite affected the growth of S. epidermidis. Hydroxyapatite with 20% zirconia proved to be an effective concentration to inhibit the growth of S. epidermidis colony. PMID:22919390

In vitro assessment of cutting efficiency and durability of zirconia removal diamond rotary instruments.

PubMed

Kim, Joon-Soo; Bae, Ji-Hyeon; Yun, Mi-Jung; Huh, Jung-Bo

2017-06-01

Recently, zirconia removal diamond rotary instruments have become commercially available for efficient cutting of zirconia. However, research of cutting efficiency and the cutting characteristics of zirconia removal diamond rotary instruments is limited. The purpose of this in vitro study was to assess and compare the cutting efficiency, durability, and diamond rotary instrument wear pattern of zirconia diamond removal rotary instruments with those of conventional diamond rotary instruments. In addition, the surface characteristics of the cut zirconia were assessed. Block specimens of 3 mol% yttrium cation-doped tetragonal zirconia polycrystal were machined 10 times for 1 minute each using a high-speed handpiece with 6 types of diamond rotary instrument from 2 manufacturers at a constant force of 2 N (n=5). An electronic scale was used to measure the lost weight after each cut in order to evaluate the cutting efficiency. Field emission scanning electron microscopy was used to evaluate diamond rotary instrument wear patterns and machined zirconia block surface characteristics. Data were statistically analyzed using the Kruskal-Wallis test, followed by the Mann-Whitney U test (α=.05). Zirconia removal fine grit diamond rotary instruments showed cutting efficiency that was reduced compared with conventional fine grit diamond rotary instruments. Diamond grit fracture was the most dominant diamond rotary instrument wear pattern in all groups. All machined zirconia surfaces were primarily subjected to plastic deformation, which is evidence of ductile cutting. Zirconia blocks machined with zirconia removal fine grit diamond rotary instruments showed the least incidence of surface flaws. Although zirconia removal diamond rotary instruments did not show improved cutting efficiency compared with conventional diamond rotary instruments, the machined zirconia surface showed smoother furrows of plastic deformation and fewer surface flaws. Copyright © 2016 Editorial Council

Shear bond strength of indirect composite material to monolithic zirconia.

PubMed

Sari, Fatih; Secilmis, Asli; Simsek, Irfan; Ozsevik, Semih

2016-08-01

This study aimed to evaluate the effect of surface treatments on bond strength of indirect composite material (Tescera Indirect Composite System) to monolithic zirconia (inCoris TZI). Partially stabilized monolithic zirconia blocks were cut into with 2.0 mm thickness. Sintered zirconia specimens were divided into different surface treatment groups: no treatment (control), sandblasting, glaze layer & hydrofluoric acid application, and sandblasting + glaze layer & hydrofluoric acid application. The indirect composite material was applied to the surface of the monolithic zirconia specimens. Shear bond strength value of each specimen was evaluated after thermocycling. The fractured surface of each specimen was examined with a stereomicroscope and a scanning electron microscope to assess the failure types. The data were analyzed using one-way analysis of variance (ANOVA) and Tukey LSD tests (α=.05). Bond strength was significantly lower in untreated specimens than in sandblasted specimens (P<.05). No difference between the glaze layer and hydrofluoric acid application treated groups were observed. However, bond strength for these groups were significantly higher as compared with the other two groups (P<.05). Combined use of glaze layer & hydrofluoric acid application and silanization are reliable for strong and durable bonding between indirect composite material and monolithic zirconia.

An harmonic smile resulted from the use of ceramic prosthesis with zirconia structure: a case report.

PubMed

Tavarez, Rudys Rodolfo de Jesus; Goncalves, Leticia Machado; Dias, Ana Paula; Dias, Anna Claudia Pereira; Malheiros, Adriana Santos; Silva, Alice Carvalho; Bandeca, Matheus Coelho

2014-06-01

The rehabilitation of patients requiring an esthetic smile demands a multidisciplinary approach. This clinical report describes a treatment plan for recovery aesthetics' smile of anterior teeth using ceramic prosthesis with zirconia structure. Initially, a review of aesthetic parameters, diagnostic waxing, mock-up and provisional restorations was performed. A contextual assessment of aesthetic, proportion and shape of teeth was done to recreate a natural looking for teeth in consonance with the smile line. Subsequently, based on these parameters, fixed prostheses of the upper anterior teeth using ceramic restorations with zirconia infrastructures were performed. The use of ceramic restorations with zirconia structures associated with a careful treatment plan allows the professional to integrate esthetic and function for satisfactory clinical results. How to cite the article: Tavarez RR, Gonçalves LM, Dias AP, Dias AC, Malheiros AS, Silva AC, Bandeca MC. An harmonic smile resulted from the use of ceramic prosthesis with zirconia structure: A case report. J Int Oral Health 2014;6(3):90-2.

Chirality in adsorption on solid surfaces.

PubMed

Zaera, Francisco

2017-12-07

In the present review we survey the main advances made in recent years on the understanding of chemical chirality at solid surfaces. Chirality is an important topic, made particularly relevant by the homochiral nature of the biochemistry of life on Earth, and many chiral chemical reactions involve solid surfaces. Here we start our discussion with a description of surface chirality and of the different ways that chirality can be bestowed on solid surfaces. We then expand on the studies carried out to date to understand the adsorption of chiral compounds at a molecular level. We summarize the work published on the adsorption of pure enantiomers, of enantiomeric mixtures, and of prochiral molecules on chiral and achiral model surfaces, especially on well-defined metal single crystals but also on other flat substrates such as highly ordered pyrolytic graphite. Several phenomena are identified, including surface reconstruction and chiral imprinting upon adsorption of chiral agents, and the enhancement or suppression of enantioselectivity seen in some cases upon adsorption of enantiomixtures of chiral compounds. The possibility of enhancing the enantiopurity of adsorbed layers upon the addition of chiral seeds and the so-called "sergeants and soldiers" phenomenon are presented. Examples are provided where the chiral behavior has been associated with either thermodynamic or kinetic driving forces. Two main approaches to the creation of enantioselective surface sites are discussed, namely, via the formation of supramolecular chiral ensembles made out of small chiral adsorbates, and by adsorption of more complex chiral molecules capable of providing suitable chiral environments for reactants by themselves, via the formation of individual adsorbate:modifier adducts on the surface. Finally, a discussion is offered on the additional effects generated by the presence of the liquid phase often required in practical applications such as enantioselective crystallization, chiral

Chirality in molecular collision dynamics

NASA Astrophysics Data System (ADS)

Lombardi, Andrea; Palazzetti, Federico

2018-02-01

Chirality is a phenomenon that permeates the natural world, with implications for atomic and molecular physics, for fundamental forces and for the mechanisms at the origin of the early evolution of life and biomolecular homochirality. The manifestations of chirality in chemistry and biochemistry are numerous, the striking ones being chiral recognition and asymmetric synthesis with important applications in molecular sciences and in industrial and pharmaceutical chemistry. Chiral discrimination phenomena, due to the existence of two enantiomeric forms, very well known in the case of interaction with light, but still nearly disregarded in molecular collision studies. Here we review some ideas and recent advances about the role of chirality in molecular collisions, designing and illustrating molecular beam experiments for the demonstration of chiral effects and suggesting a scenario for a stereo-directional origin of chiral selection.

Enantioselective CE method for pharmacokinetic studies on ibuprofen and its chiral metabolites with reference to genetic polymorphism.

PubMed

Główka, Franciszek; Karaźniewicz, Marta

2007-08-01

A stereospecific CE method was elaborated for the quantification of ibuprofen enantiomers and their major phase I metabolites: 2'-hydroxy-ibuprofen and 2'-carboxy-ibuprofen in plasma and urine. Optimal temperature and pH of BGE were established to obtain complete separation of eight ibuprofen chiral compounds and (+)-S indobufen, applied as an internal standard, during one analytical run. After isolation from biological matrices using SPE on an octadecyl stationary phase, the analytes were separated and resolved up to 10 min in a silica capillary filled with BGE, consisting of heptakis 2,3,6-tri-O-methyl-beta-CD in triethanolamine-phosphate buffer, pH 5.0. Complete enantioseparation of the all analytes confirmed specificity of the method. The calibration curves were linear in the range of 0.1-25.0 mg/L for IBP enantiomers and their chiral metabolites in 0.5 mL of plasma and 1.0-200.0 mg/L in 0.05 mL of urine. Following SPE procedure, recovery of the chiral analytes from the two media was in the ranges of 82-87%, 90-95% and 70-76% for ibuprofen, 2'-hydroxy-ibuprofen and 2'-carboxy-ibuprofen enantiomers, respectively. The validated method was successfully applied in pharmacokinetic investigations of IBP enantiomers as well as free chiral metabolites in reference to the genetic polymorphism of CYP450 2C isoenzymes.

Fracture resistance and reliability of new zirconia posts.

PubMed

Oblak, Cedomir; Jevnikar, Peter; Kosmac, Tomaz; Funduk, Nenad; Marion, Ljubo

2004-04-01

The radicular portion of zirconia endodontic posts often need to be reshaped to achieve a definitive form and may be airborne-particle abraded to improve adhesion during luting. Therefore, the surface of the tetragonal zirconia ceramics may be transformed and damaged, influencing the mechanical properties of the material. This study compared the fracture resistance of prefabricated zirconia posts with a new retentive post-head after different surface treatments. Experimental zirconia posts of 2 different diameters, 1.3 mm and 1.5 mm, were produced from commercially available zirconia powder. A cylindro-conical outline form was used for the root portion of the system and a post-head with 3 retentive rings was designed. Sixty posts of each diameter were divided into 3 groups (n=20). Group 1 was ground with a coarse grit diamond bur; Group 2 was airborne-particle abraded with 110-microm fused alumina particles, and Group 3 was left as-received (controls). Posts were luted into the root-shaped artificial canals with the Clearfil adhesive system and Panavia 21 adhesive resin luting agent. The posts were loaded in a universal testing machine at an inclination of 45 degrees with the constant cross-head speed of 1 mm/min. The fracture load (N) necessary to cause post fracture was recorded, and the statistical significance of differences among groups was analyzed with 1-way ANOVA followed by the Fischer LSD test (alpha=.05). The variability was analyzed using Weibull statistics. Load to fracture values of all zirconia posts depended primarily on post diameter. Mean fracture loads (SD) in Newtons were 518.4 (+/-101.3), 993.6 (+/-224.1), and 622.7 (+/-110.3) for Groups 1 through 3, respectively, for thicker posts, and 385.9 (+/-110.3), 627.0 (+/-115.1), and 451.2 (+/-81.4) for Groups 1 through 3, respectively, for thinner posts. Airborne-particle-abraded posts exhibited significantly higher resistance to fracture (P<.05) than those in the other 2 groups for diameters 1.3 mm

[Evaluation of alumina effects on the mechanical property and translucency of nano-zirconia all-ceramics].

PubMed

Jiang, Li; Zhao, Yong-qi; Zhang, Jing-chao; Liao, Yun-mao; Li, Wei

2010-06-01

To study the effects of alumina content on sintered density, mechanical property and translucency of zirconia nanocomposite all-ceramics. Specimens of zirconia nanocomposite all-ceramics were divided into five groups based on their alumina content which are 0% (control group), 2.5%, 5.0%, 7.5% and 10.0% respectively. The sintered densities were measured using Archimedes' method. Specimens' bending strengths were measured with three-point bending test (ISO 6872). The visible light transmittances were measured with spectrophotometric arrangements and the fractured surfaces were observed using scanning electron microscope (SEM). The control group of pure zirconia could be sintered to the theoretical density under pressure-less sintering condition. The bending strength was (1100.27 ± 54.82) MPa, the fracture toughness was (4.96 ± 0.35) MPa×m(1/2) and the transmittance could reach 17.03%. The sintered density and transmittance decreased as alumina content increased from 2.5% to 10%. However, the fracture toughness only increased slightly. In all four alumina groups, the additions of alumina had no significant effect on samples' bending strengths (P > 0.05). When the content of alumina was 10%, fracture toughness of specimens reached (6.13 ± 0.44) MPa×m(1/2) while samples' transmittance declined to 6.21%. SEM results showed that alumina particles had no significant effect on the grain size and distribution of tetragonal zirconia polycrystals. Additions of alumina to yttria-tetragonal zirconia polycrystals could influence its mechanical property and translucency. Additions of the other phase to zirconia ceramics should meet the clinical demands of strength and esthetics.

Chiral Magnetic Effect in Condensed Matters

NASA Astrophysics Data System (ADS)

Li, Qiang

The chiral magnetic effect is the generation of electrical current induced by chirality imbalance in the presence of magnetic field. It is a macroscopic manifestation of the quantum chiral anomaly in systems possessing charged chiral fermions. In quark-gluon plasma containing nearly massless quarks, the chirality imbalance is sourced by the topological transitions. In condensed matter systems, the chiral quasiparticles emerge in the 3D Dirac and Weyl semimetals having a linear dispersion relation. Recently, the chiral magnetic effect was discovered in a 3D Dirac semimetal - zirconium pentatelluride, ZrTe5, in which a large negative magnetoresistance is observed when magnetic field is parallel with the current. It is now reported in more than a dozen Dirac and Weyl semimetals. Broadly speaking, the chiral magnetic effect can exist in a variety of condensed matters. In some cases, a material may be transformed into a Weyl semimetal by magnetic field, exhibiting the chiral magnetic effect. In other cases, the chiral magnetic current may be generated in magnetic Dirac semimetals without external magnetic field, or in asymmetric Weyl semimetals without electric field where only a magnetic field and the source of chiral quasipartiles would be necessary. In the limit of conserved quasiparticle chirality, charge transport by the chiral magnetic current is non-dissipative. The powerful notion of chirality, originally discovered in high-energy and nuclear physics, holds promise in new ways of transmitting and processing information and energy. At the same time, chiral materials have opened a fascinating possibility to study the quantum dynamics of relativistic field theory in condensed matter experiments.

Finite Element Analysis of IPS Empress II Ceramic Bridge Reinforced by Zirconia Bar

PubMed Central

Kermanshah, H.; Bitaraf, T.; Geramy, A.

2012-01-01

Objective: The aim of this study was to determine the effect of trenched zirconia bar on the von Mises stress distribution of IPS –Empress II core ceramics. Materials and Methods: The three-dimensional model including a three-unit bridge from the second premolar to the second molar was designed. The model was reinforced with zirconia bar (ZB), zirconia bar with vertical trench (VZB) and zirconia bar with horizontal trench (HZB) (cross sections of these bars were circular). The model without zirconia bar was designed as the control. The bridges were loaded by 200 N and 500 N on the occlusal surface at the middle of the pontic component and von Mises stresses were evaluated along a defined path. Results: In the connector area, von Mises stress in MPa were approximately identical in the specimens with ZB (at molar connector (MC): 4.75 and at premolar connector (PC): 6.40) and without ZB (MC: 5.50, PC: 6.68), and considerable differences were not recognized. Whereas, Von-Mises stress (MPa) in the specimens with horizontal trenched Zirconia bar (HZB) (MC: 3.91, PC: 2.44) and Vertical trenched Zirconia bar (VZB) (MC: 2.53, PC: 2.56) was decreased considerably. Conclusion: Embeded trenched zirconia bar could reinforce IPS-Empress II at the connector area which is a main failure region in all ceramic fixed partial dentures. PMID:23323181

Finite Element Analysis of IPS Empress II Ceramic Bridge Reinforced by Zirconia Bar.

PubMed

Kermanshah, H; Bitaraf, T; Geramy, A

2012-01-01

The aim of this study was to determine the effect of trenched zirconia bar on the von Mises stress distribution of IPS -Empress II core ceramics. The three-dimensional model including a three-unit bridge from the second premolar to the second molar was designed. The model was reinforced with zirconia bar (ZB), zirconia bar with vertical trench (VZB) and zirconia bar with horizontal trench (HZB) (cross sections of these bars were circular). The model without zirconia bar was designed as the control. The bridges were loaded by 200 N and 500 N on the occlusal surface at the middle of the pontic component and von Mises stresses were evaluated along a defined path. IN THE CONNECTOR AREA, VON MISES STRESS IN MPA WERE APPROXIMATELY IDENTICAL IN THE SPECIMENS WITH ZB (AT MOLAR CONNECTOR (MC): 4.75 and at premolar connector (PC): 6.40) and without ZB (MC: 5.50, PC: 6.68), and considerable differences were not recognized. Whereas, Von-Mises stress (MPa) in the specimens with horizontal trenched Zirconia bar (HZB) (MC: 3.91, PC: 2.44) and Vertical trenched Zirconia bar (VZB) (MC: 2.53, PC: 2.56) was decreased considerably. Embeded trenched zirconia bar could reinforce IPS-Empress II at the connector area which is a main failure region in all ceramic fixed partial dentures.

Concerns of Hydrothermal Degradation in CAD/CAM Zirconia

PubMed Central

Kim, J.-W.; Covel, N.S.; Guess, P.C.; Rekow, E.D.; Zhang, Y.

2010-01-01

Zirconia-based restorations are widely used in prosthetic dentistry; however, their susceptibility to hydrothermal degradation remains elusive. We hypothesized that CAD/CAM machining and subsequent surface treatments, i.e., grinding and/or grit-blasting, have marked effects on the hydrothermal degradation behavior of Y-TZP. CAD/CAM-machined Y-TZP plates (0.5 mm thick), both with and without subsequent grinding with various grit sizes or grit-blasting with airborne alumina particles, were subjected to accelerated aging tests in a steam autoclave. Results showed that the CAD/CAM-machined surfaces initially exhibited superior hydrothermal degradation resistance, but deteriorated at a faster rate upon prolonged autoclave treatment compared with ground and grit-blasted surfaces. The accelerated hydrothermal degradation of CAD/CAM surfaces is attributed to the CAD/CAM machining damage and the absence of surface compressive stresses in the fully sintered material. Clinical relevance for surface treatments of zirconia frameworks in terms of hydrothermal and structural stabilities is addressed. PMID:19966039

Bayesian inference based on stationary Fokker-Planck sampling.

PubMed

Berrones, Arturo

2010-06-01

A novel formalism for bayesian learning in the context of complex inference models is proposed. The method is based on the use of the stationary Fokker-Planck (SFP) approach to sample from the posterior density. Stationary Fokker-Planck sampling generalizes the Gibbs sampler algorithm for arbitrary and unknown conditional densities. By the SFP procedure, approximate analytical expressions for the conditionals and marginals of the posterior can be constructed. At each stage of SFP, the approximate conditionals are used to define a Gibbs sampling process, which is convergent to the full joint posterior. By the analytical marginals efficient learning methods in the context of artificial neural networks are outlined. Offline and incremental bayesian inference and maximum likelihood estimation from the posterior are performed in classification and regression examples. A comparison of SFP with other Monte Carlo strategies in the general problem of sampling from arbitrary densities is also presented. It is shown that SFP is able to jump large low-probability regions without the need of a careful tuning of any step-size parameter. In fact, the SFP method requires only a small set of meaningful parameters that can be selected following clear, problem-independent guidelines. The computation cost of SFP, measured in terms of loss function evaluations, grows linearly with the given model's dimension.

Surface Modification of Zirconia Substrate by Calcium Phosphate Particles Using Sol-Gel Method.

PubMed

Jin, So Dam; Um, Sang Cheol; Lee, Jong Kook

2015-08-01

Surface modification with a biphasic composition of hydroxyapatite (HA) and tricalcium phosphate (TCP) was performed on a zirconia substrate using a sol-gel method. An initial calcium phosphate sol was prepared by mixing a solution of Ca(NO3)2 · 4H20 and (C2H5O)3P(O), while both porous and dense zirconia were used as substrates. The sol-gel coating was performed using a spin coater. The coated porous zirconia substrate was re-sintered at 1350 °C 2 h, while coated dense zirconia substrate was heat-treated at 750 °C 1 h. The microstructure of the resultant HA/TCP coatings was found to be dependent on the type of zirconia substrate used. With porous zirconia as a starting substrate, numerous isolated calcium phosphate particles (TCP and HA) were uniformly dispersed on the surface, and the particle size and covered area were dependent on the viscosity of the calcium phosphate sol. Conversely, when dense zirconia was used as a starting substrate, a thick film of nano-sized HA particles was obtained after heat treatment, however, substantial agglomeration and cracking was also observed.

Deposition of crystalline hydroxyapatite nano-particle on zirconia ceramic: a potential solution for the poor bonding characteristic of zirconia ceramics to resin cement.

PubMed

Azari, Abbas; Nikzad, Sakineh; Yazdani, Arash; Atri, Faezeh; Fazel Anvari-Yazdi, Abbas

2017-07-01

The poor bonding strength of zirconia to different dental substrates is one of the challenging issues in restorative dentistry. Hydroxyapatite is an excellent biocompatible material with fine bonding properties. In this study, it was hypothesized that hydroxyapatite coating on zirconia would improve its bond strength. Forty-five zirconia blocks were prepared and randomly divided into three groups: hydroxyapatite coating, sandblasting, and no preparation (control). The blocks were bonded to cement and the micro-shear bond strength was measured following load application. The bond strength values were analyzed with the Kruskal-Wallis test in 3 groups and paired comparisons were made using the Mann-Whitney U test. The failure patterns of the specimens were studied by a stereomicroscope and a scanning electron microscope and then analyzed by the chi-square test (significance level = 0.05). Deposition of hydroxyapatite on the zirconia surface significantly improved its bond strength to the resin cement in comparison with the control specimens (p < 0.0001). Also, the bond strength was similar to the sandblasted group (p = 0.34). The sandblasted and control group only showed adhesive failure, but the hydroxyapatite coated group had mixed failures, indicating the better quality of bonding (p < 0.0001). As a final point, hydroxyapatite coating on the zirconia surface improved the bond strength quality and values.

An aptamer-based fluorescence bio-sensor for chiral recognition of arginine enantiomers

NASA Astrophysics Data System (ADS)

Yuan, Haiyan; Huang, Yunmei; Yang, Jidong; Guo, Yuan; Zeng, Xiaoqing; Zhou, Shang; Cheng, Jiawei; Zhang, Yuhui

2018-07-01

In this study, a novel aptamer - based fluorescence bio-sensor (aptamer-AuNps) was developed for chiral recognition of arginine (Arg) enantiomers based on aptamer and gold nanoparticles (AuNps). Carboxyfluorescein (FAM) labeled aptamers (Apt) were absorbed on AuNps and their fluorescence intensity could be significantly quenched by AuNps based on fluorescence resonance energy transfer (FRET). Once D-Arg or L-Arg were added into the above solution, the aptamer specifically bind to Arg enantiomers and released from AuNps, so the fluorescence intensity of D-Arg system and L-Arg system were all enhanced. The affinity of Apt to L-Arg is tighter to D-Arg, so the enhanced fluorescence signals of L-Arg system was stronger than D-Arg system. What's more, the enhanced fluorescence were directly proportional to the concentration of D-Arg and L-Arg ranging from 0-300 nM and 0-400 nM with related coefficients of 0.9939 and 0.9952, respectively. Furthermore, the method was successfully applied to detection L-Arg in human urine samples with satisfactory results. Eventually, a simple "OR" logic gate with D-Arg &L-Arg as inputs and AuNps aggregation state as outputs was fabricated, which can help us understand the chiral recognition process deeply.

Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia

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

Cai, Qiuxia; Lopez-Ruiz, Juan A.; Cooper, Alan R.

The effect of aqueous phase on the acetic acid ketonization over monoclinic zirconia has been investigated using first-principles based density functional theory (DFT) calculations. To capture the aqueous phase chemistry over the solid zirconia catalyst surface, the aqueous phase is represented by 111 explicit water molecules with a liquid water density of 0.93 g/cm3 and the monoclinic zirconia is modeled by the most stable surface structure . The dynamic nature of aqueous phase/ interface was studied using ab initio molecular dynamics simulation, indicating that nearly half of the surface Zr sites are occupied by either adsorbed water molecules or hydroxylmore » groups at 550 K. DFT calculations show that the adsorption process of acetic acid from the liquid water phase to the surface is nearly thermodynamically neutral with a Gibbs free energy of -2.3 kJ/mol although the adsorption strength of acetic acid on the surface in aqueous phase is much stronger than in vapor phase. Therefore it is expected that the adsorption of acetic acid will dramatically affects aqueous phase ketonization reactivity over the monoclinic zirconia catalyst. Using the same ketonization mechanism via the β-keto acid intermediate, we have compared acetic acid ketonization to acetone in both vapor and aqueous phases. Our DFT calculation results show although the rate-determining step of the β-keto acid formation via the C-C coupling is not pronouncedly affected, the presence of liquid water molecules will dramatically affect dehydrogenation and hydrogenation steps via proton transfer mechanism. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time and advanced catalyst characterization use was granted by a user proposal at the William R. Wiley

Photoexcitation circular dichroism in chiral molecules

NASA Astrophysics Data System (ADS)

Beaulieu, S.; Comby, A.; Descamps, D.; Fabre, B.; Garcia, G. A.; Géneaux, R.; Harvey, A. G.; Légaré, F.; Mašín, Z.; Nahon, L.; Ordonez, A. F.; Petit, S.; Pons, B.; Mairesse, Y.; Smirnova, O.; Blanchet, V.

2018-05-01

Chiral effects appear in a wide variety of natural phenomena and are of fundamental importance in science, from particle physics to metamaterials. The standard technique of chiral discrimination—photoabsorption circular dichroism—relies on the magnetic properties of a chiral medium and yields an extremely weak chiral response. Here, we propose and demonstrate an orders of magnitude more sensitive type of circular dichroism in neutral molecules: photoexcitation circular dichroism. This technique does not rely on weak magnetic effects, but takes advantage of the coherent helical motion of bound electrons excited by ultrashort circularly polarized light. It results in an ultrafast chiral response and the efficient excitation of a macroscopic chiral density in an initially isotropic ensemble of randomly oriented chiral molecules. We probe this excitation using linearly polarized laser pulses, without the aid of further chiral interactions. Our time-resolved study of vibronic chiral dynamics opens a way to the efficient initiation, control and monitoring of chiral chemical change in neutral molecules at the level of electrons.

Maltodextrins as chiral selectors in CE: molecular structure effect of basic chiral compounds on the enantioseparation.

PubMed

Tabani, Hadi; Fakhari, Ali Reza; Nojavan, Saeed

2014-10-01

Prediction of chiral separation for a compound using a chiral selector is an interesting and debatable work. For this purpose, in this study 23 chiral basic drugs with different chemical structures were selected as model solutes and the influence of their chemical structures on the enantioseparation in the presence of maltodextrin (MD) as chiral selector was investigated. For chiral separation, a 100-mM phosphate buffer solution (pH 3.0) containing 10% (w/v) MD with dextrose equivalent (DE) of 4-7 as chiral selector at the temperature of 25°C and voltage of 20 kV was used. Under this condition, baseline separation was achieved for nine chiral compounds and partial separation was obtained for another six chiral compounds while no enantioseparation was obtained for the remaining eight compounds. The results showed that the existence of at least two aromatic rings or cycloalkanes and an oxygen or nitrogen atom or -CN group directly bonded to the chiral center are necessary for baseline separation. With the obtained results in this study, chiral separation of a chiral compound can be estimated with MD-modified capillary electrophoresis before analysis. This prediction will minimize the number of preliminary experiments required to resolve enantiomers and will save time and cost. © 2014 Wiley Periodicals, Inc.

High-performance liquid chromatographic enantioseparation of monoterpene-based 2-amino carboxylic acids on macrocyclic glycopeptide-based phases.

PubMed

Sipos, László; Ilisz, István; Pataj, Zoltán; Szakonyi, Zsolt; Fülöp, Ferenc; Armstrong, Daniel W; Péter, Antal

2010-10-29

The enantiomers of five monoterpene-based 2-amino carboxylic acids were directly separated on chiral stationary phases containing macrocyclic glycopeptide antibiotics such as teicoplanin (Astec Chirobiotic T and T2) and teicoplanin aglycone (Chirobiotic TAG) as chiral selectors. The effects of pH, the mobile phase composition, the structure of the analyte and temperature on the separations were investigated. Experiments were performed at constant mobile phase compositions in the temperature range 10-40°C to study the effects of temperature and thermodynamic parameters on separations. Apparent thermodynamic parameters and T(iso) values were calculated from plots of ln k or ln α versus 1/T. Some mechanistic aspects of the chiral recognition process are discussed with respect to the structures of the analytes. It was found that the enantioseparations were in most cases enthalpy driven. The sequence of elution of the enantiomers was determined in all cases. Copyright © 2010 Elsevier B.V. All rights reserved.

Evaluation of a conditioning method to improve core-veneer bond strength of zirconia restorations.

PubMed

Teng, Jili; Wang, Hang; Liao, Yunmao; Liang, Xing

2012-06-01

The high strength and fracture toughness of zirconia have supported its extensive application in esthetic dentistry. However, the fracturing of veneering porcelains remains one of the primary causes of failure. The purpose of this study was to evaluate, with shear bond strength testing, the effect of a simple and novel surface conditioning method on the core-veneer bond strength of a zirconia ceramic system. The shear bond strength of a zirconia core ceramic to the corresponding veneering porcelain was tested by the Schmitz-Schulmeyer method. Thirty zirconia core specimens (10 × 5 × 5 mm) were layered with a veneering porcelain (5 × 3 × 3 mm). Three different surface conditioning methods were evaluated: polishing with up to 1200 grit silicon carbide paper under water cooling, airborne-particle abrasion with 110 μm alumina particles, and modification with zirconia powder coating before sintering. A metal ceramic system was used as a control group. All specimens were subjected to shear force in a universal testing machine at a crosshead speed of 0.5 mm/min. The shear bond strength values were analyzed with 1-way ANOVA and Tukey's post hoc pairwise comparisons (α=.05). The fractured specimens were examined with a scanning electron microscope to observe the failure mode. The mean (SD) shear bond strength values in MPa were 47.02 (6.4) for modified zirconia, 36.66 (8.6) for polished zirconia, 39.14 (6.5) for airborne-particle-abraded zirconia, and 46.12 (7.1) for the control group. The mean bond strength of the control (P=.028) and modified zirconia groups (P=.014) was significantly higher than that of the polished zirconia group. The airborne-particle-abraded group was not significantly different from any other group. Scanning electron microscopy evaluation showed that cohesive fracture in the veneering porcelain was the predominant failure mode of modified zirconia, while the other groups principally fractured at the interface. Modifying the zirconia surface

Static three-dimensional topological solitons in fluid chiral ferromagnets and colloids

NASA Astrophysics Data System (ADS)

Ackerman, Paul J.; Smalyukh, Ivan I.

2017-04-01

Three-dimensional (3D) topological solitons are continuous but topologically nontrivial field configurations localized in 3D space and embedded in a uniform far-field background, that behave like particles and cannot be transformed to a uniform state through smooth deformations. Many topologically nontrivial 3D solitonic fields have been proposed. Yet, according to the Hobart-Derrick theorem, physical systems cannot host them, except for nonlinear theories with higher-order derivatives such as the Skyrme-Faddeev model. Experimental discovery of such solitons is hindered by the need for spatial imaging of the 3D fields, which is difficult in high-energy physics and cosmology. Here we experimentally realize and numerically model stationary topological solitons in a fluid chiral ferromagnet formed by colloidal dispersions of magnetic nanoplates. Such solitons have closed-loop preimages--3D regions with a single orientation of the magnetization field. We discuss localized structures with different linking of preimages quantified by topological Hopf invariants. The chirality is found to help in overcoming the constraints of the Hobart-Derrick theorem, like in two-dimensional ferromagnetic solitons, dubbed `baby skyrmions'. Our experimental platform may lead to solitonic condensed matter phases and technological applications.

Comparison of peri-implant bone formation around injection-molded and machined surface zirconia implants in rabbit tibiae

PubMed Central

Kim, Hong-Kyun; Woo, Kyung mi; Shon, Won-Jun; Ahn, Jin-Soo; Cha, Seunghee; Park, Young-Seok

2017-01-01

The aim of this study was to compare osseointegration and surface characteristics of zirconia implants made by the powder injection molding (PIM) technique and made by the conventional milling procedure in rabbit tibiae. Surface characteristics of 2 types of implant were evaluated. Sixteeen rabbits received 2 types of external hex implants with similar geometry, machined zirconia implants and PIM zirconia implants, in the tibiae. Removal torque tests and histomorphometric analyses were performed. The roughness of PIM zirconia implants was higher than that of machined zirconia implants. The PIM zirconia implants exhibited significantly higher bone-implant contact and removal torque values than the machined zirconia implants (P < 0.001). The osseointegration of the PIM zirconia implant is promising, and PIM, using the roughened mold etching technique, can produce substantially rough surfaces on zirconia implants. PMID:26235717

Dynamic control of chirality in phosphine ligands for enantioselective catalysis

PubMed Central

Zhao, Depeng; Neubauer, Thomas M.; Feringa, Ben L.

2015-01-01

Chirality plays a fundamental role in biology and chemistry and the precise control of chirality in a catalytic conversion is a key to modern synthesis most prominently seen in the production of pharmaceuticals. In enantioselective metal-based catalysis, access to each product enantiomer is commonly achieved through ligand design with chiral bisphosphines being widely applied as privileged ligands. Switchable phosphine ligands, in which chirality is modulated through an external trigger signal, might offer attractive possibilities to change enantioselectivity in a catalytic process in a non-invasive manner avoiding renewed ligand synthesis. Here we demonstrate that a photoswitchable chiral bisphosphine based on a unidirectional light-driven molecular motor, can be used to invert the stereoselectivity of a palladium-catalysed asymmetric transformation. It is shown that light-induced changes in geometry and helicity of the switchable ligand enable excellent selectivity towards the racemic or individual enantiomers of the product in a Pd-catalysed desymmetrization reaction. PMID:25806856

Observation of chiral phonons

NASA Astrophysics Data System (ADS)

Zhu, Hanyu; Yi, Jun; Li, Ming-Yang; Xiao, Jun; Zhang, Lifa; Yang, Chih-Wen; Kaindl, Robert A.; Li, Lain-Jong; Wang, Yuan; Zhang, Xiang

2018-02-01

Chirality reveals symmetry breaking of the fundamental interaction of elementary particles. In condensed matter, for example, the chirality of electrons governs many unconventional transport phenomena such as the quantum Hall effect. Here we show that phonons can exhibit intrinsic chirality in monolayer tungsten diselenide. The broken inversion symmetry of the lattice lifts the degeneracy of clockwise and counterclockwise phonon modes at the corners of the Brillouin zone. We identified the phonons by the intervalley transfer of holes through hole-phonon interactions during the indirect infrared absorption, and we confirmed their chirality by the infrared circular dichroism arising from pseudoangular momentum conservation. The chiral phonons are important for electron-phonon coupling in solids, phonon-driven topological states, and energy-efficient information processing.

Meta-Chirality: Fundamentals, Construction and Applications

PubMed Central

Ma, Xiaoliang; Pu, Mingbo; Li, Xiong; Guo, Yinghui; Gao, Ping; Luo, Xiangang

2017-01-01

Chiral metamaterials represent a special type of artificial structures that cannot be superposed to their mirror images. Due to the lack of mirror symmetry, cross-coupling between electric and magnetic fields exist in chiral mediums and present unique electromagnetic characters of circular dichroism and optical activity, which provide a new opportunity to tune polarization and realize negative refractive index. Chiral metamaterials have attracted great attentions in recent years and have given rise to a series of applications in polarization manipulation, imaging, chemical and biological detection, and nonlinear optics. Here we review the fundamental theory of chiral media and analyze the construction principles of some typical chiral metamaterials. Then, the progress in extrinsic chiral metamaterials, absorbing chiral metamaterials, and reconfigurable chiral metamaterials are summarized. In the last section, future trends in chiral metamaterials and application in nonlinear optics are introduced. PMID:28513560

Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer.

PubMed

Sarkar, Aritra; Dhiman, Shikha; Chalishazar, Aditya; George, Subi J

2017-10-23

Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fracture loads and failure modes of customized and non-customized zirconia abutments.

PubMed

Moris, Izabela Cristina Maurício; Chen, Yung-Chung; Faria, Adriana Cláudia Lapria; Ribeiro, Ricardo Faria; Fok, Alex Sui-Lun; Rodrigues, Renata Cristina Silveira

2018-05-05

This study aimed to evaluate the fracture load and pattern of customized and non-customized zirconia abutments with Morse-taper connection. 18 implants were divided into 3 groups according to the abutments used: Zr - with non-customized zirconia abutments; Zrc - with customized zirconia abutments; and Ti - with titanium abutments. To test their load capacity, a universal test machine with a 500-kgf load cell and a 0.5-mm/min speed were used. After, one implant-abutment assembly from each group was analyzed by Scanning Electron Microscopy (SEM). For fractographic analysis, the specimens were transversely sectioned above the threads of the abutment screw in order to examine their fracture surfaces using SEM. A significant difference was noted between the groups (Zr=573.7±11.66N, Zrc=768.0±8.72N and Ti=659.1±7.70N). Also, the zirconia abutments fractured while the titanium abutments deformed plastically. Zrc presented fracture loads significantly higher than Zr (p=0.009). All the zirconia abutments fractured below the implant platform, starting from the area of contact between the abutment and implant and propagating to the internal surface of the abutment. All the zirconia abutments presented complete cleavage in the mechanical test. Fractography detected differences in the position and pattern of fracture between the two groups with zirconia abutments, probably because of the different diameters in the transmucosal region. Customization of zirconia abutments did not affect their fracture loads, which were comparable to that of titanium and much higher than the maximum physiological limit for the anterior region of the maxilla. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

Translucency of zirconia copings made with different CAD/CAM systems.

PubMed

Baldissara, Paolo; Llukacej, Altin; Ciocca, Leonardo; Valandro, Felipe L; Scotti, Roberto

2010-07-01

Zirconia cores are reported to be less translucent than glass, lithium disilicate, or alumina cores. This could affect the esthetic appearance and the clinical choices made when using zirconia-based restorations. The purpose of this in vitro study was to evaluate the translucency of zirconia copings for single crowns fabricated using different CAD/CAM systems, using lithium disilicate glass ceramic as a control. Using impressions made from a stainless steel complete-crown master die, 9 stone cast replicas were fabricated, numbered, and distributed into 8 ceramic ZrO(2) CAD/CAM system groups (Lava Frame 0.3 and 0.5, IPS e.max ZirCAD, VITA YZ, Procera AllZircon, Digizon, DC Zircon, and Cercon Base) and to a lithium disilicate glass-ceramic control group (IPS e.max Press) using a simple computer-generated randomization method. From each die, the manufacturer's authorized milling centers supplied 5 copings per group without applying any dying technique to the ceramic base material. The copings were prepared to allow for a 40-mum cement layer and were of different thicknesses according to system specifications. Translucency was measured by the direct transmission method with a digital photoradiometer mounted in a dark chamber. The light source was a 150-W halogen lamp beam. Measurements were repeated 3 times for each specimen. Data obtained were analyzed using 1-way ANOVA and the Bonferroni multiple comparison test (alpha=.05). Among ZrO(2) copings, Lava (0.3 mm and 0.5 mm thick) showed the highest (P<.05) values of translucency measured as light flow units (3.572 + or - 018 x 10(3) lx and 3.181 + or - 0.13 x 10(3) lx, respectively). These values represent 71.7% and 63.9%, respectively, of the glass-ceramic control group (4.98 x 10(3) lx). All ZrO(2) copings demonstrated different levels of light transmission, with the 2 Lava specimens showing the highest values. Translucency of zirconia copings was significantly lower (P=.001) than that of the lithium disilicate glass

30 CFR 57.4561 - Stationary diesel equipment underground.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Stationary diesel equipment underground. 57... Fire Prevention and Control Installation/construction/maintenance § 57.4561 Stationary diesel equipment underground. Stationary diesel equipment underground shall be— (a) Supported on a noncombustible base; and (b...

Multistep hierarchical self-assembly of chiral nanopore arrays

PubMed Central

Kim, Hanim; Lee, Sunhee; Shin, Tae Joo; Korblova, Eva; Walba, David M.; Clark, Noel A.; Lee, Sang Bok; Yoon, Dong Ki

2014-01-01

A series of simple hierarchical self-assembly steps achieve self-organization from the centimeter to the subnanometer-length scales in the form of square-centimeter arrays of linear nanopores, each one having a single chiral helical nanofilament of large internal surface area and interfacial interactions based on chiral crystalline molecular arrangements. PMID:25246585

Thermodynamic properties of some metal oxide-zirconia systems

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.

1989-01-01

Metal oxide-zirconia systems are a potential class of materials for use as structural materials at temperatures above 1900 K. These materials must have no destructive phase changes and low vapor pressures. Both alkaline earth oxide (MgO, CaO, SrO, and BaO)-zirconia and some rare earth oxide (Y2O3, Sc2O3, La2O3, CeO2, Sm2O3, Gd2O3, Yb2O3, Dy2O3, Ho2O3, and Er2O3)-zirconia system are examined. For each system, the phase diagram is discussed and the vapor pressure for each vapor species is calculated via a free energy minimization procedure. The available thermodynamic literature on each system is also surveyed. Some of the systems look promising for high temperature structural materials.

Tetragonal zirconia quantum dots in silica matrix prepared by a modified sol-gel protocol

NASA Astrophysics Data System (ADS)

Verma, Surbhi; Rani, Saruchi; Kumar, Sushil

2018-05-01

Tetragonal zirconia quantum dots (t-ZrO2 QDs) in silica matrix with different compositions ( x)ZrO2-(100 - x)SiO2 were fabricated by a modified sol-gel protocol. Acetylacetone was added as a chelating agent to zirconium propoxide to avoid precipitation. The powders as well as thin films were given thermal treatment at 650, 875 and 1100 °C for 4 h. The silica matrix remained amorphous after thermal treatment and acted as an inert support for zirconia quantum dots. The tetragonal zirconia embedded in silica matrix transformed into monoclinic form due to thermal treatment ≥ 1100 °C. The stability of tetragonal phase of zirconia is found to enhance with increase in silica content. A homogenous dispersion of t-ZrO2 QDs in silica matrix was indicated by the mapping of Zr, Si and O elements obtained from scanning electron microscope with energy dispersive X-ray analyser. The transmission electron images confirmed the formation of tetragonal zirconia quantum dots embedded in silica. The optical band gap of zirconia QDs (3.65-5.58 eV) was found to increase with increase in zirconia content in silica. The red shift of PL emission has been exhibited with increase in zirconia content in silica.

Shear bond strength of indirect composite material to monolithic zirconia

PubMed Central

2016-01-01

PURPOSE This study aimed to evaluate the effect of surface treatments on bond strength of indirect composite material (Tescera Indirect Composite System) to monolithic zirconia (inCoris TZI). MATERIALS AND METHODS Partially stabilized monolithic zirconia blocks were cut into with 2.0 mm thickness. Sintered zirconia specimens were divided into different surface treatment groups: no treatment (control), sandblasting, glaze layer & hydrofluoric acid application, and sandblasting + glaze layer & hydrofluoric acid application. The indirect composite material was applied to the surface of the monolithic zirconia specimens. Shear bond strength value of each specimen was evaluated after thermocycling. The fractured surface of each specimen was examined with a stereomicroscope and a scanning electron microscope to assess the failure types. The data were analyzed using one-way analysis of variance (ANOVA) and Tukey LSD tests (α=.05). RESULTS Bond strength was significantly lower in untreated specimens than in sandblasted specimens (P<.05). No difference between the glaze layer and hydrofluoric acid application treated groups were observed. However, bond strength for these groups were significantly higher as compared with the other two groups (P<.05). CONCLUSION Combined use of glaze layer & hydrofluoric acid application and silanization are reliable for strong and durable bonding between indirect composite material and monolithic zirconia. PMID:27555895

Elaboration of Alumina-Zirconia Composites: Role of the Zirconia Content on the Microstructure and Mechanical Properties

PubMed Central

Naglieri, Valentina; Palmero, Paola; Montanaro, Laura; Chevalier, Jérôme

2013-01-01

Alumina-zirconia (AZ) composites are attractive structural materials, which combine the high hardness and Young’s modulus of the alumina matrix with additional toughening effects, due to the zirconia dispersion. In this study, AZ composites containing different amounts of zirconia (in the range 5–20 vol %) were prepared by a wet chemical method, consisting on the surface coating of alumina powders by mixing them with zirconium salt aqueous solutions. After spray-drying, powders were calcined at 600 °C for 1 h. Green bodies were then prepared by two methods: uniaxial pressing of spray-dried granules and slip casting of slurries, obtained by re-dispersing the spray dried granulates. After pressureless sintering at 1500 °C for 1 h, the slip cast samples gave rise to fully dense materials, characterized by a quite homogeneous distribution of ZrO2 grains in the alumina matrix. The microstructure, phase composition, tetragonal to monoclinic transformation behavior and mechanical properties were investigated and are here discussed as a function of the ZrO2 content. The material containing 10 vol % ZrO2 presented a relevant hardness and exhibited the maximum value of KI0, mainly imputable to the t → m transformation at the crack tip. PMID:28809262

Effect of high intensity ultrasound on the mesostructure of hydrated zirconia

NASA Astrophysics Data System (ADS)

Kopitsa, G. P.; Baranchikov, A. E.; Ivanova, O. S.; Yapryntsev, A. D.; Grigoriev, S. V.; Pranzas, P. Klaus; Ivanov, V. K.

2012-02-01

We report structural changes in amorphous hydrated zirconia caused by high intensity ultrasonic treatment studied by means of small-angle neutron scattering (SANS) and X-ray diffraction (XRD). It was established that sonication affects the mesostructure of ZrO2×xH2O gels (i.e. decreases their homogeneity, increases surface fractal dimension and the size of monomer particles). Ultrasound induced structural changes in hydrated zirconia governs its thermal behaviour, namely decreases the rate of tetragonal to monoclinic zirconia phase transition.

Comparison of edge chipping resistance of PFM and veneered zirconia specimens

PubMed Central

Quinn, Janet B.; Sundar, Veeraraghavan; Parry, Edward E.; Quinn, George D.

2011-01-01

Objectives To investigate the chipping resistance of veneered zirconia specimens and compare it to the chipping resistance of porcelain fused to metal (PFM) specimens. Methods Veneered zirconia and PFM bar specimens were prepared in clinically relevant thicknesses. The specimen edges were chipped with different magnitude forces, producing chips of various sizes. The range of sizes included small chips that did not penetrate all the way through the veneers to the substrates, and also chips that were very large and reached the zirconia or metal substrates. The relationship between force magnitude and chip size (edge distance) was graphed. The resulting curves were compared for the veneered zirconia and PFM specimens. Knoop hardness vs. force graphs for the veneers and substrates were also obtained. Results The zirconia and PFM veneer chipping data followed a power law (coefficient of determination, R2 > 0.93) as expected from the literature. The curves overlapped within the combined data scatter, indicating similar resistance to chipping. The chips made in both types of specimens detached and did not penetrate into the substrate when they reached the veneer/substrate intersections. The hardness–load curves for the veneers and substrates all exhibited an indentation size effect (ISE) at low loads. The Knoop hardness values with uncertainties of ±one standard deviation at 4 N loads for the metal, zirconia, and the metal and zirconia veneers are: (2.02 ± 0.08, 12.01 ± 0.39, 4.24 ± 0.16 and 4.36 ± 0.02 GPa), respectively, with no statistically significant difference between the veneers (Tukey pairwise comparison at 0.95 family confidence). Significance This work indicates that a similar resistance to chipping might be expected for veneered zirconia and PFM restorations, in spite of the large difference in substrate hardness. Differences in susceptibility to chip spalling were not detected, but the chips in both specimen types detached off the sides in a similar

Zirconia based superhydrophobic coatings on cotton fabrics exhibiting excellent durability for versatile use

PubMed Central

Das, Indranee; De, Goutam

2015-01-01

A fluorinated silyl functionalized zirconia was synthesized by the sol-gel method to fabricate an extremely durable superhydrophobic coating on cotton fabrics by simple immersion technique. The fabric surfaces firmly attached with the coating material through covalent bonding, possessed superhydrophobicity with high water contact angle ≈163 ± 1°, low hysteresis ≈3.5° and superoleophilicity. The coated fabrics were effective to separate oil/water mixture with a considerably high separation efficiency of 98.8 wt% through ordinary filtering. Presence of highly stable (chemically and mechanically) superhydrophobic zirconia bonded with cellulose makes such excellent water repelling ability of the fabrics durable under harsh environment conditions like high temperature, strong acidic or alkaline solutions, different organic solvents and mechanical forces including extensive washings. Moreover, these coated fabrics retained self-cleanable superhydrophobic property as well as high water separation efficiency even after several cycles, launderings and abrasions. Therefore, such robust superhydrophobic ZrO2 coated fabrics have strong potential for various industrial productions and uses. PMID:26678754

A colorimetric chiral sensor based on chiral crown ether for the recognition of the two enantiomers of primary amino alcohols and amines.

PubMed

Cho, Eun Na Rae; Li, Yinan; Kim, Hee Jin; Hyun, Myung Ho

2011-04-01

A new colorimetric chiral sensor material consisting of three different functional sites such as chromophore (2,4-dinitrophenylazophenol dye), binding site (crown ether), and chiral barrier (3,3'-diphenyl-1,1'-binaphthyl group) was prepared and applied to the recognition of the two enantiomers of primary amino alcohols and amines. Among five primary amino alcohols and two primary amines tested, the two enantiomers of phenylalaninol show the highest difference in the absorption maximum wavelength (Δλ(max)=43.5 nm) and in the association constants (K(S)/K(R)=2.51) upon complexation with the colorimetric chiral sensor material and, consequently, the two enantiomers of phenylalaninol were clearly distinguished from each other by the color difference. Copyright © 2010 Wiley-Liss, Inc.

Spin Chirality of Cu3 and V3 Nanomagnets. 1. Rotation Behavior of Vector Chirality, Scalar Chirality, and Magnetization in the Rotating Magnetic Field, Magnetochiral Correlations.

PubMed

Belinsky, Moisey I

2016-05-02

The rotation behavior of the vector chirality κ, scalar chirality χ, and magnetization M in the rotating magnetic field H1 is considered for the V3 and Cu3 nanomagnets, in which the Dzialoshinsky-Moriya coupling is active. The polar rotation of the field H1 of the given strength H1 results in the energy spectrum characterized by different vector and scalar chiralities in the ground and excited states. The magnetochiral correlations between the vector and scalar chiralities, energy, and magnetization in the rotating field were considered. Under the uniform polar rotation of the field H1, the ground-state chirality vector κI performs sawtooth oscillations and the magnetization vector MI performs the sawtooth oscillating rotation that is accompanied by the correlated transformation of the scalar chirality χI. This demonstrates the magnetochiral effect of the joint rotation behavior and simultaneous frustrations of the spin chiralities and magnetization in the rotating field, which are governed by the correlation between the chiralities and magnetization.

Photo-Acoustic Spectroscopy Reveals Extrinsic Optical Chirality in GaAs-Based Nanowires Partially Covered with Gold

NASA Astrophysics Data System (ADS)

Petronijevic, E.; Leahu, G.; Belardini, A.; Centini, M.; Li Voti, R.; Hakkarainen, T.; Koivusalo, E.; Rizzo Piton, M.; Suomalainen, S.; Guina, M.; Sibilia, C.

2018-04-01

We report on the extrinsic chirality behavior of GaAs-based NWs asymmetrically hybridized with Au. The samples are fabricated by a recently developed, lithography-free self-organized GaAs growth, with the addition of AlGaAs shell and GaAs supershell. The angled Au flux is then used to cover three-out-of-six sidewalls with a thin layer of Au. Oblique incidence and proper sample orientation can lead to circular dichroism. We characterize this chiral behavior at 532 {nm} and 980 {nm} by means of photo-acoustic spectroscopy, which directly measures the difference in absorption for the circularly polarized light of the opposite headedness. For the first time to our knowledge, circular dichroism is observed in both the amplitude and the phase of the photo-acoustic signal. We strongly believe that such samples can be used for chiral applications, spanning from circularly polarized light emission, to the enantioselectivity applications.

The transformed-stationary approach: a generic and simplified methodology for non-stationary extreme value analysis

NASA Astrophysics Data System (ADS)

Mentaschi, Lorenzo; Vousdoukas, Michalis; Voukouvalas, Evangelos; Sartini, Ludovica; Feyen, Luc; Besio, Giovanni; Alfieri, Lorenzo

2016-09-01

possible. In particular, the transformation can be carried out by means of simple statistical techniques such as low-pass filters based on the running mean and the standard deviation, and the fitting procedure is a stationary one with a few degrees of freedom and is easy to implement and control. An open-source MATLAB toolbox has been developed to cover this methodology, which is available at https://github.com/menta78/tsEva/ (Mentaschi et al., 2016).

On gravitational chirality as the genesis of astrophysical jets

NASA Astrophysics Data System (ADS)

Tucker, R. W.; Walton, T. J.

2017-02-01

It has been suggested that single and double jets observed emanating from certain astrophysical objects may have a purely gravitational origin. We discuss new classes of plane-fronted and pulsed gravitational wave solutions to the equation for perturbations of Ricci-flat spacetimes around Minkowski metrics, as models for the genesis of such phenomena. These solutions are classified in terms of their chirality and generate a family of non-stationary spacetime metrics. Particular members of these families are used as backgrounds in analysing time-like solutions to the geodesic equation for test particles. They are found numerically to exhibit both single and double jet-like features with dimensionless aspect ratios suggesting that it may be profitable to include such backgrounds in simulations of astrophysical jet dynamics from rotating accretion discs involving electromagnetic fields.

Enhanced structural stability of nanoporous zirconia under irradiation of He

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

Yang, Tengfei; Huang, Xuejun; Wang, Chenxu

2012-01-01

This work reports a greatly enhanced tolerance for He irradiation-induced swelling in nanocrystalline zirconia film with interconnected nanoporous structure (hereinafter referred as to NC-C). Compared to bulk yttria-stabilized zirconia (YSZ) and another nanocrystalline zirconia film only with discrete nano voids (hereinafter referred as to NC-V), the NC-C film reveals good tolerance for irradiation of high-fluence He. No appreciable surface blistering can be found even at the highest fluence of 6 1017 cm2 in NCC film. From TEM analysis of as-irradiated samples, the enhanced tolerance for volume swelling in NCC film is attributed to the enhanced diffusion mechanism of deposited Hemore » via widely distributed nano channels. Furthermore, the growth of grain size is quite small for both nanocrystalline zirconia films after irradiation, which is ascribed to the decreasing of area of grain boundary due to loose structure and low energy of primary knock-on atoms for He ions.« less

Evaluation of a new carbon/zirconia-based sorbent for the cleanup of food extracts in multiclass analysis of pesticides and environmental contaminants

USDA-ARS?s Scientific Manuscript database

A novel carbon/zirconia based material, SupelTM QuE Verde (Verde), was evaluated in a filter-vial dispersive solid phase extraction (d-SPE) cleanup of QuEChERS extracts of pork, salmon, kale, and avocado for residual analysis of pesticides and environmental contaminants. Low pressure (LP) GC-MS/MS w...

Effects of multiple firings on the microstructure of zirconia and veneering ceramics.

PubMed

Alkurt, Murat; Yeşil Duymus, Zeynep; Gundogdu, Mustafa

2016-01-01

The aim of study was to evaluate the effects of multiple firings on the microstructures of zirconia and two ceramics. Vita VM9 (VMZ) and Cerabien ZR (C-Z) ceramics on a zirconia framework and zirconia without veneering ceramic (WO-Z) were evaluated. Firing methods included firing two, five, and ten times (n=10). The effects of multiple firings on the surface hardness of the materials were evaluated using a Vickers hardness (HV) tester. Data were analyzed by two-way ANOVA and Tukey's test (α=0.05). After firing five and ten times, the hardness of VM-Z and C-Z increased significantly (p<0.001). The HVs of the Cerabien ZR and Vita VM9 veneering ceramics were similar (p>0.05). In the XRD analysis, zirconia had similar tetragonal (t)-monoclinic (m) phase transformations of Y-TZP after the different firing times. Clinically, multiple firings did not affect the microstructure of zirconia, but the structures of the two ceramics were affected.

Bioactive and thermally compatible glass coating on zirconia dental implants.

PubMed

Kirsten, A; Hausmann, A; Weber, M; Fischer, J; Fischer, H

2015-02-01

The healing time of zirconia implants may be reduced by the use of bioactive glass coatings. Unfortunately, existing glasses are either bioactive like Bioglass 45S5 but thermally incompatible with the zirconia substrate, or they are thermally compatible but exhibit only a very low level of bioactivity. In this study, we hypothesized that a tailored substitution of alkaline earth metals and alkaline metals in 45S5 can lead to a glass composition that is both bioactive and thermally compatible with zirconia implants. A novel glass composition was analyzed using x-ray fluorescence spectroscopy, dilatometry, differential scanning calorimetry, and heating microscopy to investigate its chemical, physical, and thermal properties. Bioactivity was tested in vitro using simulated body fluid (SBF). Smooth and microstructured glass coatings were applied using a tailored spray technique with subsequent thermal treatment. Coating adhesion was tested on implants that were inserted in bovine ribs. The cytocompatibility of the coating was analyzed using L929 mouse fibroblasts. The coefficient of thermal expansion of the novel glass was shown to be slightly lower (11.58 · 10(-6) K(-1)) than that of the zirconia (11.67 · 10(-6) K(-1)). After storage in SBF, the glass showed reaction layers almost identical to the bioactive glass gold standard, 45S5. A process window between 800 °C and 910 °C was found to result in densely sintered and amorphous coatings. Microstructured glass coatings on zirconia implants survived a minimum insertion torque of 60 Ncm in the in vitro experiment on bovine ribs. Proliferation and cytotoxicity of the glass coatings was comparable with the controls. The novel glass composition showed a strong adhesion to the zirconia substrate and a significant bioactive behavior in the SBF in vitro experiments. Therefore, it holds great potential to significantly reduce the healing time of zirconia dental implants. © International & American Associations for Dental

Light-Nuclei Spectra from Chiral Dynamics

NASA Astrophysics Data System (ADS)

Piarulli, M.; Baroni, A.; Girlanda, L.; Kievsky, A.; Lovato, A.; Lusk, Ewing; Marcucci, L. E.; Pieper, Steven C.; Schiavilla, R.; Viviani, M.; Wiringa, R. B.

2018-02-01

In recent years local chiral interactions have been derived and implemented in quantum Monte Carlo methods in order to test to what extent the chiral effective field theory framework impacts our knowledge of few- and many-body systems. In this Letter, we present Green's function Monte Carlo calculations of light nuclei based on the family of local two-body interactions presented by our group in a previous paper in conjunction with chiral three-body interactions fitted to bound- and scattering-state observables in the three-nucleon sector. These interactions include Δ intermediate states in their two-pion-exchange components. We obtain predictions for the energy levels and level ordering of nuclei in the mass range A =4 - 12 , accurate to ≤2 % of the binding energy, in very satisfactory agreement with experimental data.

Experimental research on the relationship between fit accuracy and fracture resistance of zirconia abutments.

PubMed

Sui, Xinxin; Wei, Huasha; Wang, Dashan; Han, Yan; Deng, Jing; Wang, Yongliang; Wang, Junjun; Yang, Jianjun

2014-10-01

The purpose of the study was to investigate the correlation between fit accuracy and fracture resistance of zirconia abutments, as well as its feasibility for clinical applications. Twenty self-made zirconia abutments were tested with 30 Osstem GSII implants. First, 10 Osstem GSII implants were cut into two parts along the long axis and assembled with the zirconia abutments. The microgaps between the implants and the zirconia abutments were measured under a scanning electron microscope. Second, the zirconia abutments were assembled with 20 un-cut implants and photographed before and after being fixed with a central screw of 30-Ncm torque. The dental films were measured by Digora for Windows 2.6 software. Then the fracture resistance of zirconia abutments was measured using the universal testing machine at 90°. All results were analyzed using SPSS13.0 software. The average internal-hexagon microgaps between the implants and zirconia abutments were 19.38±1.34μm. The average Morse taper microgap in the implant-abutment interface was 17.55±1.68μm. The dental film showed that the Morse taper gap in the implant-abutment interface disappeared after being fixed with a central screw of 30-Ncm torque, and the average moving distance of the zirconia abutments to the implants was 0.19±0.02mm. The average fracture resistance of zirconia abutments was 282.93±17.28N. The internal-hexagon microgap between the implants and zirconia abutments was negatively related to the fracture resistance of the abutments (r1=-0.97, p<0.01). The Morse taper microgap in the implant-abutment interface was negatively related to the fracture resistance of the abutments (r2=-0.84, p<0.01). The microgap between implant and abutment was negatively related to the fracture resistance of the abutment, while the internal-hexagon microgap has better correlation than the Morse taper microgap. The closure of microgap is helpful to improve the fracture resistance of zirconia abutments. The fracture

Role of Achiral Nucleobases in Multicomponent Chiral Self-Assembly: Purine-Triggered Helix and Chirality Transfer.

PubMed

Deng, Ming; Zhang, Li; Jiang, Yuqian; Liu, Minghua

2016-11-21

Chiral self-assembly is a basic process in biological systems, where many chiral biomolecules such as amino acids and sugars play important roles. Achiral nucleobases usually covalently bond to saccharides and play a significant role in the formation of the double helix structure. However, it remains unclear how the achiral nucleobases can function in chiral self-assembly without the sugar modification. Herein, we have clarified that purine nucleobases could trigger N-(9-fluorenylmethox-ycarbonyl) (Fmoc)-protected glutamic acid to self-assemble into helical nanostructures. Moreover, the helical nanostructure could serve as a matrix and transfer the chirality to an achiral fluorescence probe, thioflavin T (ThT). Upon chirality transfer, the ThT showed not only supramolecular chirality but also circular polarized fluorescence (CPL). Without the nucleobase, the self-assembly processes cannot happen, thus providing an example where achiral molecules played an essential role in the expression and transfer of the chirality. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chiral separation of G-type chemical warfare nerve agents via analytical supercritical fluid chromatography.

PubMed

Kasten, Shane A; Zulli, Steven; Jones, Jonathan L; Dephillipo, Thomas; Cerasoli, Douglas M

2014-12-01

Chemical warfare nerve agents (CWNAs) are extremely toxic organophosphorus compounds that contain a chiral phosphorus center. Undirected synthesis of G-type CWNAs produces stereoisomers of tabun, sarin, soman, and cyclosarin (GA, GB, GD, and GF, respectively). Analytical-scale methods were developed using a supercritical fluid chromatography (SFC) system in tandem with a mass spectrometer for the separation, quantitation, and isolation of individual stereoisomers of GA, GB, GD, and GF. Screening various chiral stationary phases (CSPs) for the capacity to provide full baseline separation of the CWNAs revealed that a Regis WhelkO1 (SS) column was capable of separating the enantiomers of GA, GB, and GF, with elution of the P(+) enantiomer preceding elution of the corresponding P(-) enantiomer; two WhelkO1 (SS) columns had to be connected in series to achieve complete baseline resolution. The four diastereomers of GD were also resolved using two tandem WhelkO1 (SS) columns, with complete baseline separation of the two P(+) epimers. A single WhelkO1 (RR) column with inverse stereochemistry resulted in baseline separation of the GD P(-) epimers. The analytical methods described can be scaled to allow isolation of individual stereoisomers to assist in screening and development of countermeasures to organophosphorus nerve agents. © 2014 The Authors. Chirality published by John Wiley Periodicals, Inc.

Chiral cavity ring down polarimetry: Chirality and magnetometry measurements using signal reversals.

PubMed

Bougas, Lykourgos; Sofikitis, Dimitris; Katsoprinakis, Georgios E; Spiliotis, Alexandros K; Tzallas, Paraskevas; Loppinet, Benoit; Rakitzis, T Peter

2015-09-14

We present the theory and experimental details for chiral-cavity-ring-down polarimetry and magnetometry, based on ring cavities supporting counterpropagating laser beams. The optical-rotation symmetry is broken by the presence of both chiral and Faraday birefringence, giving rise to signal reversals which allow rapid background subtractions. We present the measurement of the specific rotation at 800 nm of vapors of α-pinene, 2-butanol, and α-phellandrene, the measurement of optical rotation of sucrose solutions in a flow cell, the measurement of the Verdet constant of fused silica, and measurements and theoretical treatment of evanescent-wave optical rotation at a prism surface. Therefore, these signal-enhancing and signal-reversing methods open the way for ultrasensitive polarimetry measurements in gases, liquids and solids, and at surfaces.

Simple Heat Treatment of Zirconia Ceramic Pre-Treated with Silane Primer to Improve Resin Bonding.

PubMed

Ha, Jung-Yun; Son, Jun Sik; Kim, Kyo-Han; Kwon, Tae-Yub

2015-01-01

Establishing a strong resin bond to dental zirconia ceramic remains difficult. Previous studies have shown that the conventional application of silane does not work well with zirconia. This paper reports that a silane pre-treatment of dental zirconia ceramic combined with subsequent heat treatment has potential as an adhesive cementation protocol for improving zirconia-resin bonding. Among the various concentrations (0.1 to 16 vol%) of experimental γ-methacryloxypropyltrimethoxysilane (γ-MPTS) primers assessed, the 1% solution was found to be the most effective in terms of the shear bond strength of the resin cement to dental zirconia ceramic. A high shear bond strength (approx. 30 MPa) was obtained when zirconia specimens were pre-treated with this primer and then heat-treated in a furnace for 60 min at 150 degrees C. Heat treatment appeared to remove the hydrophilic constituents from the silane film formed on the zirconia ceramic surface and accelerate the condensation reactions between the silanol groups of the hydrolyzed silane molecules at the zirconia/resin interface, finally making a more desirable surface for bonding with resin. This estimation was supported by Fourier transform infrared spectroscopy of the silanes prepared in this study.

[Application of plasma sprayed zirconia coating in dental implant: study in implant].

PubMed

Huang, Z F; Wang, Z F; Li, C H; Hao, D; Lan, J

2018-04-09

Objective: To investigate the osseointegration of a novel coating-plasma-sprayed zirconia in dental implant. Methods: Zirconia coating on non-thread titanium implant was prepared using plasma spraying, the implant surface morphology, surface roughness and wettability were measured. In vivo , zirconia coated implants were inserted in rabbit tibia and animals were respectively sacrificed at 2, 4, 8 and 12 weeks after implantation. The bond strength between implant and bone was measured by push-out test. The osseointegration was observed by scanning electron microscopy (SEM), micro CT and histological analyses. Quantified parameters including removal torque, and bone-implant contact (BIC) percentage were calculated. Results: The surface roughness (1.6 µm) and wettability (54.6°) of zirconia coated implant was more suitable than those of titanium implant (0.6 µm and 74.4°) for osseointegration. At 12 weeks, the push-out value of zirconia coated implant and titanium implant were (64.9±3.0) and (50.4±2.9) N, and BIC value of these two groups were (54.7±3.6)% and (41.5±3.6)%. All these differences had statistical significance. Conclusions: The surface characters of zirconia coated implant were more suitable for osseointegration and present better osseointegration than smooth titanium implant in vivo , especially at early stage.

Effect of Porosity of Alumina and Zirconia Ceramics toward Pre-Osteoblast Response

PubMed Central

Hadjicharalambous, Chrystalleni; Prymak, Oleg; Loza, Kateryna; Buyakov, Ales; Kulkov, Sergei; Chatzinikolaidou, Maria

2015-01-01

It is acknowledged that cellular responses are highly affected by biomaterial porosity. The investigation of this effect is important for the development of implanted biomaterials that integrate with bone tissue. Zirconia and alumina ceramics exhibit outstanding mechanical properties and are among the most popular implant materials used in orthopedics, but few data exist regarding the effect of porosity on cellular responses to these materials. The present study investigates the effect of porosity on the attachment and proliferation of pre-osteoblastic cells on zirconia and alumina. For each composition, ceramics of three different porosities are fabricated by sintering, and characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray powder diffraction. Cell proliferation is quantified, and microscopy is employed to qualitatively support the proliferation results and evaluate cell morphology. Cell adhesion and metabolic activity are found comparable among low porosity zirconia and alumina. In contrast, higher porosity favors better cell spreading on zirconia and improves growth, but does not significantly affect cell response on alumina. Between the highest porosity materials, cell response on zirconia is found superior to alumina. Results show that an average pore size of ~150 μm and ~50% porosity can be considered beneficial to cellular growth on zirconia ceramics. PMID:26579516