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Sample records for phenomenon iii properties

  1. TOWARD UNDERSTANDING THE B[e] PHENOMENON. III. PROPERTIES OF THE OPTICAL COUNTERPART OF IRAS 00470+6429

    SciTech Connect

    Miroshnichenko, A. S.; Chentsov, E. L.; Klochkova, V. G.; Zharikov, S. V.; Grankin, K. N.; Kusakin, A. V.; Gandet, T. L.; Klingenberg, G.; Kildahl, S.; Rudy, R. J.; Lynch, D. K.; Venturini, C. C.; Mazuk, S.; Perry, R. B.; Bjorkman, K. S.; Gray, R. O.; Bernabei, S.; Polcaro, V. F.

    2009-07-20

    FS CMa type stars are a group of Galactic objects with the B[e] phenomenon. They exhibit strong emission-line spectra and infrared excesses, which are most likely due to recently formed circumstellar dust. The group content and identification criteria were described in the first two papers of the series. In this paper we report our spectroscopic and photometric observations of the optical counterpart of IRAS 00470+6429 obtained in 2003-2008. The optical spectrum is dominated by emission lines, most of which have P Cyg type profiles. We detected significant brightness variations, which may include a regular component, and variable spectral line profiles in both shape and position. The presence of a weak Li I 6708 A line in the spectrum suggests that the object is most likely a binary system with a B2-B3 spectral-type primary companion of a luminosity log L/L {sub sun} = 3.9 {+-} 0.3 and a late-type secondary companion. We estimate a distance toward the object to be 2.0 {+-} 0.3 kpc from the Sun.

  2. Toward Understanding the B[e] Phenomenon. III. Properties of the Optical Counterpart of IRAS 00470+6429

    NASA Astrophysics Data System (ADS)

    Miroshnichenko, A. S.; Chentsov, E. L.; Klochkova, V. G.; Zharikov, S. V.; Grankin, K. N.; Kusakin, A. V.; Gandet, T. L.; Klingenberg, G.; Kildahl, S.; Rudy, R. J.; Lynch, D. K.; Venturini, C. C.; Mazuk, S.; Puetter, R. C.; Perry, R. B.; Carciofi, A. C.; Bjorkman, K. S.; Gray, R. O.; Bernabei, S.; Polcaro, V. F.; Viotti, R. F.; Norci, L.

    2009-07-01

    FS CMa type stars are a group of Galactic objects with the B[e] phenomenon. They exhibit strong emission-line spectra and infrared excesses, which are most likely due to recently formed circumstellar dust. The group content and identification criteria were described in the first two papers of the series. In this paper we report our spectroscopic and photometric observations of the optical counterpart of IRAS 00470+6429 obtained in 2003-2008. The optical spectrum is dominated by emission lines, most of which have P Cyg type profiles. We detected significant brightness variations, which may include a regular component, and variable spectral line profiles in both shape and position. The presence of a weak Li I 6708 Å line in the spectrum suggests that the object is most likely a binary system with a B2-B3 spectral-type primary companion of a luminosity log L/L sun = 3.9 ± 0.3 and a late-type secondary companion. We estimate a distance toward the object to be 2.0 ± 0.3 kpc from the Sun. Partially based on data obtained at the 6 m BTA telescope of the Russian Academy of Sciences, 3 m IRTF, 3 m Shane telescope of the Lick Observatory, 2.7 m Harlan J. Smith and 2.1 m Otto Struve telescopes of the McDonald Observatory, 2.1 m telescope of the San Pedro Martir Observatory, 1.5 m telescope of the Loiano Observatory, and 0.8 m telescope of the Dark Sky Observatory.

  3. Increased alpha 2-macroglobulin in diabetes: a hyperglycemia related phenomenon associated with reduced antithrombin III activity.

    PubMed

    Ceriello, A; Giugliano, D; Quatraro, A; Stante, A; Dello Russo, P; Torella, R

    1989-01-01

    Increased alpha 2-macroglobulin (alpha 2M) activity and concentration, and decreased antithrombin III (ATIII) plasma concentration are reported in diabetic subjects. In diabetes an inverse correlation between ATIII activity and blood glucose, HbA1, alpha 2M activity and alpha 2M concentration, and a direct correlation between both alpha 2M activity and alpha 2M concentration with blood glucose and HbA1 are found. Moreover, a direct correlation between alpha 2M activity and alpha 2M concentration fails. In both diabetic and normal subjects induced hyperglycemia increases alpha 2M activity and alpha 2M concentration reduces ATIII activity, while ATIII concentration is not affected. These data which show that hyperglycemia may increase alpha 2M molecule levels while altering only the biological function of ATIII, provide evidence that hyperglycemia may decrease, directly, the biological function of some proteins and may condition the levels of some risk factors for the development of diabetic complications such as alpha 2M.

  4. Investigation of the abnormal Zn diffusion phenomenon in III-V compound semiconductors induced by the surface self-diffusion of matrix atoms

    NASA Astrophysics Data System (ADS)

    Tang, Liangliang; Xu, Chang; Liu, Zhuming

    2017-01-01

    Zn diffusion in III-V compound semiconductorsare commonly processed under group V-atoms rich conditions because the vapor pressure of group V-atoms is relatively high. In this paper, we found that group V-atoms in the diffusion sources would not change the shaped of Zn profiles, while the Zn diffusion would change dramatically undergroup III-atoms rich conditions. The Zn diffusions were investigated in typical III-V semiconductors: GaAs, GaSb and InAs. We found that under group V-atoms rich or pure Zn conditions, the double-hump Zn profiles would be formed in all materials except InAs. While under group III-atoms rich conditions, single-hump Zn profiles would be formed in all materials. Detailed diffusion models were established to explain the Zn diffusion process; the surface self-diffusion of matrix atoms is the origin of the abnormal Zn diffusion phenomenon.

  5. Galactic cold cores. III. General cloud properties

    NASA Astrophysics Data System (ADS)

    Juvela, M.; Ristorcelli, I.; Pagani, L.; Doi, Y.; Pelkonen, V.-M.; Marshall, D. J.; Bernard, J.-P.; Falgarone, E.; Malinen, J.; Marton, G.; McGehee, P.; Montier, L. A.; Motte, F.; Paladini, R.; Tóth, L. V.; Ysard, N.; Zahorecz, S.; Zavagno, A.

    2012-05-01

    Context. In the project galactic cold cores we are carrying out Herschel photometric observations of cold regions of the interstellar clouds as previously identified with the Planck satellite. The aim of the project is to derive the physical properties of the population of cold clumps and to study its connection to ongoing and future star formation. Aims: We examine the cloud structure around the Planck detections in 71 fields observed with the Herschel SPIRE instrument by the summer of 2011. We wish to determine the general physical characteristics of the fields and to examine the morphology of the clouds where the cold high column density clumps are found. Methods: Using the Herschel SPIRE data, we derive colour temperature and column density maps of the fields. Together with ancillary data, we examine the infrared spectral energy distributions of the main clumps. The clouds are categorised according to their large scale morphology. With the help of recently released WISE satellite data, we look for signs of enhanced mid-infrared scattering ("coreshine"), an indication of growth of the dust grains, and have a first look at the star formation activity associated with the cold clumps. Results: The mapped clouds have distances ranging from ~100 pc to several kiloparsecs and cover a range of sizes and masses from cores of less than 10 M⊙ to clouds with masses in excess of 10 000 M⊙. Most fields contain some filamentary structures and in about half of the cases a filament or a few filaments dominate the morphology. In one case out of ten, the clouds show a cometary shape or have sharp boundaries indicative of compression by an external force. The width of the filaments is typically ~0.2-0.3 pc. However, there is significant variation from 0.1 pc to 1 pc and the estimates are sensitive to the methods used and the very definition of a filament. Enhanced mid-infrared scattering, coreshine, was detected in four clouds with six additional tentative detections. The

  6. Biochemical and Structural Properties of Mouse Kynurenine Aminotransferase III

    SciTech Connect

    Han, Q.; Robinson, H; Cai, T; Tagle, D; Li, J

    2009-01-01

    Kynurenine aminotransferase III (KAT III) has been considered to be involved in the production of mammalian brain kynurenic acid (KYNA), which plays an important role in protecting neurons from overstimulation by excitatory neurotransmitters. The enzyme was identified based on its high sequence identity with mammalian KAT I, but its activity toward kynurenine and its structural characteristics have not been established. In this study, the biochemical and structural properties of mouse KAT III (mKAT III) were determined. Specifically, mKAT III cDNA was amplified from a mouse brain cDNA library, and its recombinant protein was expressed in an insect cell protein expression system. We established that mKAT III is able to efficiently catalyze the transamination of kynurenine to KYNA and has optimum activity at relatively basic conditions of around pH 9.0 and at relatively high temperatures of 50 to 60C. In addition, mKAT III is active toward a number of other amino acids. Its activity toward kynurenine is significantly decreased in the presence of methionine, histidine, glutamine, leucine, cysteine, and 3-hydroxykynurenine. Through macromolecular crystallography, we determined the mKAT III crystal structure and its structures in complex with kynurenine and glutamine. Structural analysis revealed the overall architecture of mKAT III and its cofactor binding site and active center residues. This is the first report concerning the biochemical characteristics and crystal structures of KAT III enzymes and provides a basis toward understanding the overall physiological role of mammalian KAT III in vivo and insight into regulating the levels of endogenous KYNA through modulation of the enzyme in the mouse brain.

  7. Biochemical and structural properties of mouse kynurenine aminotransferase III.

    PubMed

    Han, Qian; Robinson, Howard; Cai, Tao; Tagle, Danilo A; Li, Jianyong

    2009-02-01

    Kynurenine aminotransferase III (KAT III) has been considered to be involved in the production of mammalian brain kynurenic acid (KYNA), which plays an important role in protecting neurons from overstimulation by excitatory neurotransmitters. The enzyme was identified based on its high sequence identity with mammalian KAT I, but its activity toward kynurenine and its structural characteristics have not been established. In this study, the biochemical and structural properties of mouse KAT III (mKAT III) were determined. Specifically, mKAT III cDNA was amplified from a mouse brain cDNA library, and its recombinant protein was expressed in an insect cell protein expression system. We established that mKAT III is able to efficiently catalyze the transamination of kynurenine to KYNA and has optimum activity at relatively basic conditions of around pH 9.0 and at relatively high temperatures of 50 to 60 degrees C. In addition, mKAT III is active toward a number of other amino acids. Its activity toward kynurenine is significantly decreased in the presence of methionine, histidine, glutamine, leucine, cysteine, and 3-hydroxykynurenine. Through macromolecular crystallography, we determined the mKAT III crystal structure and its structures in complex with kynurenine and glutamine. Structural analysis revealed the overall architecture of mKAT III and its cofactor binding site and active center residues. This is the first report concerning the biochemical characteristics and crystal structures of KAT III enzymes and provides a basis toward understanding the overall physiological role of mammalian KAT III in vivo and insight into regulating the levels of endogenous KYNA through modulation of the enzyme in the mouse brain.

  8. III-nitride nanowires : growth, properties, and applications.

    SciTech Connect

    Armstrong, Andrew M.; Arslan, Ilke; Upadhya, Prashanth C.; Li, Qiming; Wang, George T.; Talin, Albert Alec; Prasankumar, Rohit P.; Lin, Yong; Huang, Jian Yu

    2010-06-01

    Nanowires based on the III nitride materials system have attracted attention as potential nanoscale building blocks in optoelectronics, sensing, and electronics. However, before such applications can be realized, several challenges exist in the areas of controlled and ordered nanowire synthesis, fabrication of advanced nanowire heterostructures, and understanding and controlling the nanowire electrical and optical properties. Here, recent work is presented involving the aligned growth of GaN and III-nitride core-shell nanowires, along with extensive results providing insights into the nanowire properties obtained using advanced electrical, optical and structural characterization techniques.

  9. Intercrystalline distal-effect on the afterglow phenomenon in photoluminescent SrAl2O4:Ce(III), Ln nanotube growth

    NASA Astrophysics Data System (ADS)

    Khaled Zurba, Nadia; Bdikin, Igor; Kholkin, Andrei; Golberg, Dmitri; Ferreira, José M. F.

    2010-08-01

    We report a new method for the synthesis of photoluminescent SrAl2O4:Ce3 + , Dy3 + , Eu2 + nanotubes, PL-SNT:Ce(III), Ln, using solid-state reaction and post-annealing approach. This new optical nanotubular structure was characterized by HRTEM, SEM, AFM, EDX, steady-state and time-resolved PL spectroscopy. A series of f-f and f-d-transitions with light emission in structured bands peaking at 488 nm arising from the polymorphism of the host lattice was correlated with an intercrystalline distal-effect on the afterglow phenomenon.

  10. Electrical properties of dislocations in III-Nitrides

    SciTech Connect

    Cavalcoli, D.; Minj, A.; Pandey, S.; Cavallini, A.

    2014-02-21

    Research on GaN, AlN, InN (III-N) and their alloys is achieving new heights due their high potential applications in photonics and electronics. III-N semiconductors are mostly grown epitaxially on sapphire, and due to the large lattice mismatch and the differences in the thermal expansion coefficients, the structures usually contain many threading dislocations (TDs). While their structural properties have been widely investigated, their electrical characteristics and their role in the transport properties of the devices are still debated. In the present contribution we will show conductive AFM studies of TDs in GaN and Al/In GaN ternary alloys to evidence the role of strain, different surface polarity and composition on their electrical properties. Local I-V curves measured at TDs allowed us to clarify their role in the macroscopic electrical properties (leakage current, mobilities) of III-N based devices. Samples obtained by different growers (AIXTRON, III-V Lab) were studied. The comparison between the results obtained in the different alloys allowed us to understand the role of In and Al on the TDs electrical properties.

  11. Hyperglycemia-conditioned increase in alpha-2-macroglobulin in healthy normal subjects: a phenomenon correlated with deficient antithrombin III activity.

    PubMed

    Ceriello, A; Quatraro, A; Dello Russo, P; Marchi, E; Barbanti, M; Giugliano, D

    1989-01-01

    Induced hyperglycemia in normal subjects increases alpha 2-macroglobulin (alpha 2M) activity and alpha 2M concentration and reduces antithrombin III (ATIII) activity, while it does not affect ATIII plasma concentration. Hyperglycemia-determined variations in ATIII activity and alpha 2M molecules are correlated in an inverse and parallel fashion. A compensatory role for the increase in alpha 2M in the regulation of the coagulation system may be hypothesized. Moreover, these data provide evidence that hyperglycemia may decrease, directly, the biological function of some proteins and may influence the levels of some risk factors for the development of complications in diabetes.

  12. Properties of the SW Sextantis Stars: Clues to the Underlying Phenomenon

    NASA Astrophysics Data System (ADS)

    Hoard, D. W.; Szkody, P.

    1996-12-01

    The SW Sextantis stars are a recently identified subclass of novalike cataclysmic variable (CV). These ~10 systems have orbital periods in the range ~ 3--4 hr; they also share a number of peculiar characteristics that set them apart from other CVs. For example, (1) an unusually high level of excitation in their spectra (including prominent He ii lambda4686 emission); (2) velocity curves of their emission lines that imply non-uniform emission from the accretion disk; (3) single-peaked emission lines in contrast to the expected double-peaked lines typically observed in high inclination disk systems; and (4) their Balmer and He i lines have orbital-phase-dependent profiles characterized by the appearance of a strong absorption feature at specific phases. Since the novalike CVs are thought to be systems with a constant high mass transfer rate, we are investigating the possible origin of the SW Sex phenomenon in the structure of the prominent accretion disks in these CVs. We present a compilation of new and published data on the SW Sex stars comparing the values of system parameters (such as inclination, component masses, etc.) and a number of observational properties (such as optical and UV line intensities, X-ray flux, etc.). Clues to the geometry of these CVs can be inferred by comparing characteristics among the entire group. For example, the orbital phases(s) at which the absorption feature appears in the Balmer and He i emission lines may depend on the inclination of the system. This relationship, in turn, can be used to deduce the relative vertical extent of the structures in the disk responsible for the absorption.

  13. Time-dependent spectral-feature variations of stars displaying the B[e] phenomenon. III. HD 50138

    NASA Astrophysics Data System (ADS)

    Jeřábková, T.; Korčáková, D.; Miroshnichenko, A.; Danford, S.; Zharikov, S. V.; Kříček, R.; Zasche, P.; Votruba, V.; Šlechta, M.; Škoda, P.; Janík, J.

    2016-02-01

    Context. B[e] stars are anomalous objects around which extended circumstellar matter is present. The observed properties of the central star are significantly affected by the surrounding material. Therefore, the use of standard synthetic spectra is disputable in this case and our capability to study these objects is limited. One of the possibilities is to analyse variations of the spectral features. Long-term spectroscopic observations are required for this, but are not found in the literature. For our study we choose the B[e] star HD 50138 of the FS CMa type because of the indication that this star is a post-main-sequence star, although still not highly evolved. Therefore, it can be a good object for testing evolutionary models. Currently, HD 50138 is the most extensively observed FS CMa star which makes it an ideal object for modelling. Our observations fill the gap in the available data. Aims: To describe the variability of HD 50138 we have monitored this star spectroscopically over the last twenty years. To search for the periodicity on short-term scales, series of night-to-night observations were also obtained. We were able to obtain 130 spectra from four different telescopes - 1.06 m at Ritter Observatory (échelle, R ~ 26 000, 32 spectra, 1994-2003), the Perek 2 m telescope at Ondřejov Observatory (slit, R ~ 12 500, 56 spectra, 2004-2013), the 2.12 m telescope at Observatorio Astronomico Nacional San Pedro Martir (échelle, R ~ 18 000, 16 spectra, 2005-2013), and the 0.81 m telescope at Three College Observatory (échelle, R ~ 12 000, 26 spectra, 2013-2014). Methods: We describe and analyse variations of the chosen lines. The measurements of the equivalent widths and radial velocities of the Hα, Hβ, and [O i] λλ 6300, 6364 Å lines are presented. The set of obtained spectra allows us to describe the changes on timescales from days to years. Results: The long-term quasi-periodic trend was found in the variations of the Hα equivalent width and confirmed

  14. [Raynaud's phenomenon].

    PubMed

    Piérard-Franchimont, C; Piérard, G E; Hermanns-Lê, T

    2012-12-01

    Raynaud's phenomenon is a vascular acrosyndrome caused by a variety of diseases. There is a distinction between the idiopathic Raynaud's disease, the secondary types and the suspicious idiopathic Raynaud's phenomenon.

  15. The synthesis, structure, magnetic and luminescent properties of a new tetranuclear dysprosium (III) cluster

    SciTech Connect

    Chen, Yen-Han; Tsai, Yun-Fan; Lee, Gene-Hsian; Yang, En-Che

    2012-01-15

    The synthesis and characterization of [Dy{sub 4}(dhampH{sub 3}){sub 4}(NO{sub 3}){sub 2}](NO{sub 3}){sub 2} (1), a new tetranuclear dysprosium (III) complex, is described. The compound was characterized by its X-ray structure, magnetic properties as well as the luminescent spectra. The compound crystallizes in a P1-bar space group with a zig-zag linear form of geometry. The ac magnetic susceptibilities of the molecule indicate that it is a magnetic molecule with a slow magnetization relaxation. The molecule also exhibits an emission spectrum that was confirmed to be ligand based. These results indicate that this molecule has both a slow magnetization relaxation (that could be potentially a SMM) and luminescent properties. - Graphical Abstract: A new tetranuclear dysprosium (III) complex [Dy{sub 4}(dhampH{sub 3}){sub 4}(NO{sub 3}){sub 2}](NO{sub 3}){sub 2} is synthesized and reported in this paper. This molecule has luminescence and can potentially act as a SMM. Highlights: Black-Right-Pointing-Pointer A new designed ligand (dhampH{sub 5}) was syntheisized. Black-Right-Pointing-Pointer A new tetra-dysprosium cluster [Dy{sub 4}(dhampH{sub 3}){sub 4}(NO{sub 3}){sub 2}](NO{sub 3}){sub 2} was made. Black-Right-Pointing-Pointer Slow magnetization relaxation phenomenon was observed. Black-Right-Pointing-Pointer Ligand-based luminescence was observed.

  16. Exceptional Oxygen Sensing Properties of New Blue Light-Excitable Highly Luminescent Europium(III) and Gadolinium(III) Complexes

    PubMed Central

    Borisov, Sergey M.; Fischer, Roland; Saf, Robert; Klimant, Ingo

    2016-01-01

    New europium(III) and gadolinium(III) complexes bearing 8-hydroxyphenalenone antenna combine efficient absorption in the blue part of the spectrum and strong emission in polymers at room temperature. The Eu(III) complexes show characteristic red luminescence whereas the Gd(III) dyes are strongly phosphorescent. The luminescence quantum yields are about 20% for the Eu(III) complexes and 50% for the Gd(III) dyes. In contrast to most state-of-the-art Eu(III) complexes the new dyes are quenched very efficiently by molecular oxygen. The luminescence decay times of the Gd(III) complexes exceed 1 ms which ensures exceptional sensitivity even in polymers of moderate oxygen permeability. These sensors are particularly suitable for trace oxygen sensing and may be good substitutes for Pd(II) porphyrins. The photophysical and sensing properties can be tuned by varying the nature of the fourth ligand. The narrow-band emission of the Eu(III) allows efficient elimination of the background light and autofluorescence and is also very attractive for use e.g. in multi-analyte sensors. The highly photostable indicators incorporated in nanoparticles are promising for imaging applications. Due to the straightforward preparation and low cost of starting materials the new dyes represent a promising alternative to the state-of-the-art oxygen indicators particularly for such applications as e.g. food packaging. PMID:27158252

  17. Structural and electronic properties of monolayer group III monochalcogenides

    NASA Astrophysics Data System (ADS)

    Demirci, S.; Avazlı, N.; Durgun, E.; Cahangirov, S.

    2017-03-01

    We investigate the structural, mechanical, and electronic properties of the two-dimensional hexagonal structure of group III-VI binary monolayers, M X (M =B , Al, Ga, In and X =O , S, Se, Te) using first-principles calculations based on the density functional theory. The structural optimization calculations and phonon spectrum analysis indicate that all of the 16 possible binary compounds are thermally stable. In-plane stiffness values cover a range depending on the element types and can be as high as that of graphene, while the calculated bending rigidity is found to be an order of magnitude higher than that of graphene. The obtained electronic band structures show that M X monolayers are indirect band-gap semiconductors. The calculated band gaps span a wide optical spectrum from deep ultraviolet to near infrared. The electronic structure of oxides (M O ) is different from the rest because of the high electronegativity of oxygen atoms. The dispersions of the electronic band edges and the nature of bonding between atoms can also be correlated with electronegativities of constituent elements. The unique characteristics of group III-VI binary monolayers can be suitable for high-performance device applications in nanoelectronics and optics.

  18. Thermal and optical properties of Tb(III), Eu(III) and Tb(III)/Eu(III) co-complexed silicone fluorinated acrylate copolymer

    NASA Astrophysics Data System (ADS)

    Zhai, Yinfeng; Xie, Hongde; Cai, Haijun; Cai, Peiqing; Seo, Hyo Jin

    2015-07-01

    Tb(III), Eu(III) and Tb(III)/Eu(III) activated silicone fluorinated acrylate (SFA) have been successfully synthesized using the method of semi-continuous emulsion polymerization. The copolymers are characterized by flourier transform infrared (FT-IR), thermal gravity analysis (TGA), photoluminescence excitation (PLE) and emission (PL) spectroscopy. The copolymer containing Tb(III) and Eu(III) ions display green and red luminescent colors under UV light excitation, respectively. The TGA curves show the thermal decomposition temperatures of the copolymers are up to about 300 °C. The PL spectra show a strong green emission at 546 nm (5D4 → 7F5) of Tb(III) complexed copolymers, and show a prominent red emission at 615 nm (5D0 → 7F2) of Eu(III) complexed copolymers. Different concentrations of Eu(III) and Tb(III) ions are introduced into the copolymer and the energy transfer from Tb(III) to Eu(III) ions in the copolymer was found. Thus, based on the results it can be suggested that SFA:Eu(III), SFA:Tb(III) and SFA:Tb(III)/Eu(III) can be used potentially as luminescent materials.

  19. [Raynaud's phenomenon].

    PubMed

    Saavedra Salinas, Miguel Ángel; Carrillo Vázquez, Sandra Miriam

    2006-11-01

    Raynaud's phenomenon is characterized by repeated daily attacks of ischemia followed by reperfusion at the acrallevel. It is a frequent syndrome found in medical practice; and it can be considered as primary or secondary to other conditions, including rheumatic autoimmune diseases. Current classification had clinical and therapeutic implications. Careful clinical evaluation is the most reliable and reproducible method in the diagnosis of Raynaud's phenomenon. Several risk factors had been associated in the genesis of Raynaud's phenomenon; however, its pathogenesis remains elusive although recently, considerable progress in disease mechanism had been described. Such advances are directing new lines of therapy.

  20. Aloe vera phenomenon: a review of the properties and modern uses of the leaf parenchyma gel

    SciTech Connect

    Grindlay, D.; Reynolds, T.

    1986-06-01

    The mucilaginous gel from the parenchymatous cells in the leaf pulp of Aloe vera has been used since early times for a host of curative purposes. This gel should be distinguished clearly from the bitter yellow exudate originating from the bundle sheath cells, which is used for its purgative effects. Aloe vera gel has come to play a prominent role as a contemporary folk remedy, and numerous optimistic, and in some cases extravagant, claims have been made for its medicinal properties. Modern clinical use of the gel began in the 1930s, with reports of successful treatment of X-ray and radium burns, which led to further experimental studies using laboratory animals in the following decades. The reports of these experiments and the numerous favourable case histories did not give conclusive evidence, since although positive results were usually described, much of the work suffered from poor experimental design and insufficiently large test samples. In addition some conflicting or inconsistent results were obtained. With the recent resurgence of interest in Aloe vera gel, however, new experimental work has indicated the possibility of distinct physiological effects. Chemical analysis has shown the gel to contain various carbohydrate polymers, notably either glucomannans or pectic acid, along with a range of other organic and inorganic components. Although many physiological properties of the gel have been described, there is no certain correlation between these and the identified gel components. 154 references.

  1. Raynaud's Phenomenon

    MedlinePlus

    ... form. It is common for patients with a connective tissue disease to have Raynaud’s phenomenon. It occurs in ... enlarged or malformed, the patient may have a connective tissue disease. Antinuclear antibody (ANA) test. In this blood ...

  2. Characterization of the biochemical properties of Campylobacter jejuni RNase III

    PubMed Central

    Haddad, Nabila; Saramago, Margarida; Matos, Rute G.; Prévost, Hervé; Arraiano, Cecília M.

    2013-01-01

    Campylobacter jejuni is a foodborne bacterial pathogen, which is now considered as a leading cause of human bacterial gastroenteritis. The information regarding ribonucleases in C. jejuni is very scarce but there are hints that they can be instrumental in virulence mechanisms. Namely, PNPase (polynucleotide phosphorylase) was shown to allow survival of C. jejuni in refrigerated conditions, to facilitate bacterial swimming, cell adhesion, colonization and invasion. In several microorganisms PNPase synthesis is auto-controlled in an RNase III (ribonuclease III)-dependent mechanism. Thereby, we have cloned, overexpressed, purified and characterized Cj-RNase III (C. jejuni RNase III). We have demonstrated that Cj-RNase III is able to complement an Escherichia coli rnc-deficient strain in 30S rRNA processing and PNPase regulation. Cj-RNase III was shown to be active in an unexpectedly large range of conditions, and Mn2+ seems to be its preferred co-factor, contrarily to what was described for other RNase III orthologues. The results lead us to speculate that Cj-RNase III may have an important role under a Mn2+-rich environment. Mutational analysis strengthened the function of some residues in the catalytic mechanism of action of RNase III, which was shown to be conserved. PMID:24073828

  3. Characterization of the biochemical properties of Campylobacter jejuni RNase III.

    PubMed

    Haddad, Nabila; Saramago, Margarida; Matos, Rute G; Prévost, Hervé; Arraiano, Cecília M

    2013-11-25

    Campylobacter jejuni is a foodborne bacterial pathogen, which is now considered as a leading cause of human bacterial gastroenteritis. The information regarding ribonucleases in C. jejuni is very scarce but there are hints that they can be instrumental in virulence mechanisms. Namely, PNPase (polynucleotide phosphorylase) was shown to allow survival of C. jejuni in refrigerated conditions, to facilitate bacterial swimming, cell adhesion, colonization and invasion. In several microorganisms PNPase synthesis is auto-controlled in an RNase III (ribonuclease III)-dependent mechanism. Thereby, we have cloned, overexpressed, purified and characterized Cj-RNase III (C. jejuni RNase III). We have demonstrated that Cj-RNase III is able to complement an Escherichia coli rnc-deficient strain in 30S rRNA processing and PNPase regulation. Cj-RNase III was shown to be active in an unexpectedly large range of conditions, and Mn2+ seems to be its preferred co-factor, contrarily to what was described for other RNase III orthologues. The results lead us to speculate that Cj-RNase III may have an important role under a Mn2+-rich environment. Mutational analysis strengthened the function of some residues in the catalytic mechanism of action of RNase III, which was shown to be conserved.

  4. Chemical Properties And Toxicity of Chromium(III) Nutritional Supplements

    SciTech Connect

    Levina, A.; Lay, P.A.

    2009-05-19

    The status of Cr(III) as an essential micronutrient for humans is currently under question. No functional Cr(III)-containing biomolecules have been definitively described as yet, and accumulated experience in the use of Cr(III) nutritional supplements (such as [Cr(pic){sub 3}], where pic = 2-pyridinecarboxylato) has shown no measurable benefits for nondiabetic people. Although the use of large doses of Cr(III) supplements may lead to improvements in glucose metabolism for type 2 diabetics, there is a growing concern over the possible genotoxicity of these compounds, particularly of [Cr(pic){sub 3}]. The current perspective discusses chemical transformations of Cr(III) nutritional supplements in biological media, with implications for both beneficial and toxic actions of Cr(III) complexes, which are likely to arise from the same biochemical mechanisms, dependent on concentrations of the reactive species. These species include: (1) partial hydrolysis products of Cr(III) nutritional supplements, which are capable of binding to biological macromolecules and altering their functions; and (2) highly reactive Cr(VI/V/IV) species and organic radicals, formed in reactions of Cr(III) with biological oxidants. Low concentrations of these species are likely to cause alterations in cell signaling (including enhancement of insulin signaling) through interactions with the active centers of regulatory enzymes in the cell membrane or in the cytoplasm, while higher concentrations are likely to produce genotoxic DNA lesions in the cell nucleus. These data suggest that the potential for genotoxic side-effects of Cr(III) complexes may outweigh their possible benefits as insulin enhancers, and that recommendations for their use as either nutritional supplements or antidiabetic drugs need to be reconsidered in light of these recent findings.

  5. Canine Antithrombin-III: Some Biochemical and Biologic Properties

    DTIC Science & Technology

    1987-06-02

    4. Radial Immunodiffusion Immunologic quantitation of AT-III in normal dog plasma was assessed by radial immunodiffusion as described by Mancini ...appears to be an almost. perfect homology to the human product. D. IMMUNOLOGIC QUANTITATrON OF CANINE AT-III The radial immunodiffusion of Mancini ... Mancini , G., Carbonara, A.Q., Hermans, J.F.: Immunochemical quantitation of antigens by single radial immunodiffusion . Internat. J. Immunochem. 2:235

  6. Deoxyribonucleic acid polymerase III of Escherichia coli. Purification and properties.

    PubMed

    Livingston, D M; Hinkle, D C; Richardson, C C

    1975-01-25

    DNA polymerase III has been purified 4,500-fold from the Escherichis coli mutant, HMS83, which lacks DNA polymerases I and II. When subjected to disc gel electrophoresis, the most purified fraction exhibits a single major protein band from which enzymatic activity may be recovered. Polyacrylamide gel electrophoresis under denaturing conditions produces two protein bands with molecular weights of 140,000 and 40,000. The sedimentation coefficient of the enzyme is 7.0 S, and the Stokes radius is 62 A. Taken together these tow parameters indicate a native molecular weight of 180,000. Purified DNA polymerase III catalyzes the polymerization of nucleotides into DNA when provided with both a DNA template and a complementary primer strand. The newly synthesized DNA is covalently attached to the 3' terminus of the primer strand. Because the extent of polymerization is only 10 to 100 nucleotides, the best substrates are native DNA molecules with small single-stranded regions. The most purified enzyme preparation is devoid of endonuclease activities. In addition to the two exonuclease activities described in the accompanying paper, purified polymerase III also catalyzes pyrophosphorolysis and the exchange of pyrophosphate into deoxynucleoside triphosphates. DNA polymerase III has also been isolated from wild type E. coli containing the other two known DNA polymerases. Futhermore, the enzyme purified from three different polC mutants exhibits altered polymerase III activity, confirming that polC is the structural gene for DNA polymerase III (Gefter, M., Hirota, Y., Kornberb, T., Wechsler, J., and Barnoux, C. (1971) Proc. Natl. Acad. Sci. U. S. A. 68, 3150-3153).

  7. Dielectric properties of polyamide 12-chromium(III) oxide nanocomposites

    NASA Astrophysics Data System (ADS)

    Zuev, Vjacheslav V.; Shapoval, Ekaterina S.; Sakhatskii, Aleksandr S.

    2016-08-01

    Broadband dielectric spectroscopy was employed to study polymer nanocomposites based on PA12 filled with of nanosized chromium(III) oxide. The experimental dielectric data were analyzed within the formalisms of complex permittivity and electric modulus. Three relaxation processes and Maxwell-Wagner-Sillars (MWS) interfacial polarizations were observed. It was found that presence of nanosized amphoteric chromium(III) oxide leads to softening of polyamide matrix that manifested in decrease of the activation energy of the α- and β-relaxation processes and glass transition temperatures. The softening of polymer matrix is the reason of the decrease of mechanical strength of polymer nanocomposites as compared with neat PA12.

  8. Investigations into the synthesis and fluorescence properties of Eu(III), Tb(III), Sm(III) and Gd(III) complexes of a novel bis-beta-diketone-type ligand.

    PubMed

    Luo, Yi-Ming; Chen, Zhe; Tang, Rui-Ren; Xiao, Lin-Xiang; Peng, Hong-Jian

    2008-02-01

    A novel bis-beta-diketon ligand, 1,1'-(2,6-bispyridyl)bis-3-phenyl-1,3-propane-dione (L), was designed and synthesized and its complexes with Eu(III), Tb(III), Sm(III) and Gd(III) ions were successfully prepared. The ligand and the corresponding metal complexes were characterized by elemental analysis, and infrared, mass and proton nuclear magnetic resonance spectroscopy. Analysis of the IR spectra suggested that each of the lanthanide metal ions coordinated to the ligand via the carbonyl oxygen atoms and the nitrogen atom of the pyridine ring. The fluorescence properties of these complexes in solid state were investigated and it was discovered that all of the lanthanide ions could be sensitized by the ligand (L) to some extent. In particular, the Tb(III) complex was an excellent green-emitter and would be a potential candidate material for applications in organic light-emitting devices (OLEDs) and medical diagnosis.

  9. Investigations into the synthesis and fluorescence properties of Eu(III), Tb(III), Sm(III) and Gd(III) complexes of a novel bis- β-diketone-type ligand

    NASA Astrophysics Data System (ADS)

    Luo, Yi-Ming; Chen, Zhe; Tang, Rui-Ren; Xiao, Lin-Xiang; Peng, Hong-Jian

    2008-02-01

    A novel bis- β-diketon ligand, 1,1'-(2,6-bispyridyl)bis-3-phenyl-1,3-propane-dione (L), was designed and synthesized and its complexes with Eu(III), Tb(III), Sm(III) and Gd(III) ions were successfully prepared. The ligand and the corresponding metal complexes were characterized by elemental analysis, and infrared, mass and proton nuclear magnetic resonance spectroscopy. Analysis of the IR spectra suggested that each of the lanthanide metal ions coordinated to the ligand via the carbonyl oxygen atoms and the nitrogen atom of the pyridine ring. The fluorescence properties of these complexes in solid state were investigated and it was discovered that all of the lanthanide ions could be sensitized by the ligand (L) to some extent. In particular, the Tb(III) complex was an excellent green-emitter and would be a potential candidate material for applications in organic light-emitting devices (OLEDs) and medical diagnosis.

  10. [Raynaud's phenomenon].

    PubMed

    Tomčík, Michal

    2016-01-01

    Raynaud's phenomenon (RP) is a very common sign which can usually be seen across all medical specialties. It is characterized by episodic color changes of acral parts of the body (palor, cyanosis, rubor) lasting from a few minutes to hours, which are usually triggered by cold temperature and/or stress. The primary RP occurs alone, without concomitant diseases, is usually benign and has favorable prognosis. Secondary RP occurs in a variety of diseases with a very variable progression and prognosis, mostly unfavorable one due to the development of ischemic tissue necrosis and gangrene. This work provides a comprehensive overview of the history, current knowledge about the epidemiology and pathogenesis and the recommended evaluation and treatment of RP.

  11. Raynaud's phenomenon.

    PubMed

    Hughes, Michael; Herrick, Ariane L

    2016-02-01

    Raynaud's phenomenon (RP) is a major cause of pain and disability in patients with autoimmune connective tissue diseases (CTDs), particularly systemic sclerosis (SSc). The clinician must perform a comprehensive clinical assessment in patients with RP to differentiate between primary (idiopathic) and secondary RP, in particular (for rheumatologists), secondary to an autoimmune CTD, as both the prognosis and treatment may differ significantly. Key investigations are nailfold capillaroscopy and testing for autoantibodies (in particular, those associated with SSc). Patients with RP and either abnormal nailfold capillaroscopy or an SSc-specific antibody (and especially with both) have a high risk of transitioning to an autoimmune CTD. Both nailfold capillaroscopy and autoantibody specificity may help the clinician in predicting organ-based complications. The management of CTD-associated RP requires a multifaceted approach to treatment, including patient education and conservative ('non-drug') measures. Patients with CTD-associated RP often require pharmacological treatment, which in the first instance is usually a calcium channel blocker, although other agents can be used. There is an increasing tendency to use phosphodiesterase type 5 inhibitors early in the treatment of CTD-associated RP. Oral therapies are commonly associated with side effects (often due to systemic vasodilation) that may result in failure of dose escalation and/or permanent discontinuation. Intravenous prostanoid therapy and surgery (e.g., botulinum toxin injection and digital sympathectomy) can be considered in severe RP. Patients with CTD-associated RP can develop a number of ischaemic digital complications (primarily ulcers and critical ischaemia), which may be associated with significant tissue loss. Future research is required to increase the understanding of the pathogenesis and natural history of RP (to drive therapeutic advances), and to explore/develop drug therapies, including those that

  12. Gadolinium(III) complexes as MRI contrast agents: ligand design and properties of the complexes.

    PubMed

    Hermann, Petr; Kotek, Jan; Kubícek, Vojtech; Lukes, Ivan

    2008-06-21

    Magnetic resonance imaging is a commonly used diagnostic method in medicinal practice as well as in biological and preclinical research. Contrast agents (CAs), which are often applied are mostly based on Gd(III) complexes. In this paper, the ligand types and structures of their complexes on one side and a set of the physico-chemical parameters governing properties of the CAs on the other side are discussed. The solid-state structures of lanthanide(III) complexes of open-chain and macrocyclic ligands and their structural features are compared. Examples of tuning of ligand structures to alter the relaxometric properties of gadolinium(III) complexes as a number of coordinated water molecules, their residence time (exchange rate) or reorientation time of the complexes are given. Influence of the structural changes of the ligands on thermodynamic stability and kinetic inertness/lability of their lanthanide(III) complexes is discussed.

  13. Modulation of homochiral Dy(III) complexes: single-molecule magnets with ferroelectric properties.

    PubMed

    Li, Xi-Li; Chen, Chun-Lai; Gao, Yu-Liang; Liu, Cai-Ming; Feng, Xiang-Li; Gui, Yang-Hai; Fang, Shao-Ming

    2012-11-12

    Homochiral Dy(III) complexes: by changing the ligand-to-metal ratio, enantiomeric pairs of a Dy(III) complex of different nuclearity could be obtained. The mono- and dinuclear complexes exhibit characteristics of single-molecule magnets and different slow magnetic relaxation processes. In addition, the dinuclear complexes exhibit ferroelectric behavior, thus representing the first chiral polynuclear lanthanide-based single-molecule magnets with ferroelectric properties.

  14. Syntheses, structures, and magnetic properties of a family of heterometallic heptanuclear [Cu5Ln2] (Ln = Y(III), Lu(III), Dy(III), Ho(III), Er(III), and Yb(III)) complexes: observation of SMM behavior for the Dy(III) and Ho(III) analogues.

    PubMed

    Chandrasekhar, Vadapalli; Dey, Atanu; Das, Sourav; Rouzières, Mathieu; Clérac, Rodolphe

    2013-03-04

    Sequential reaction of the multisite coordination ligand (LH3) with Cu(OAc)2·H2O, followed by the addition of a rare-earth(III) nitrate salt in the presence of triethylamine, afforded a series of heterometallic heptanuclear complexes containing a [Cu5Ln2] core {Ln = Y(1), Lu(2), Dy(3), Ho(4), Er(5), and Yb(6)}. Single-crystal X-ray crystallography reveals that all the complexes are dicationic species that crystallize with two nitrate anions to compensate the charge. The heptanuclear aggregates in 1-6 are centrosymmetrical complexes, with a hexagonal-like arrangement of six peripheral metal ions (two rare-earth and four copper) around a central Cu(II) situated on a crystallographic inversion center. An all-oxygen environment is found to be present around the rare-earth metal ions, which adopt a distorted square-antiprismatic geometry. Three different Cu(II) sites are present in the heptanuclear complexes: two possess a distorted octahedral coordination sphere while the remaining one displays a distorted square-pyramidal geometry. Detailed static and dynamic magnetic properties of all the complexes have been studied and revealed the single-molecule magnet behavior of the Dy(III) and Ho(III) derivatives.

  15. Synthesis and properties of polynitrophenyltetrazolatocobalt(III) complexes

    SciTech Connect

    Fronabarger, J.; Johnson, R.; Fleming, W.

    1986-01-01

    The explosive 3,5-dinitrophenyltetrazolato complex (3,5-DNP) tends to propagate in the deflagration mode which suggests its use as a pressure cartridge charge. However, the existence of 3,5-DNP as a hydrate appears to result in variations of thermomechanical properties thus rendering it undesirable for component use. The 2,4-DNP and 2,4,6-TNP analogs were synthesized. These exist in the anhydrous form under normal conditions and underwent DDT in component configuration. This negated their use in pressure cartridge applications. Synthetic procedures have been developed for 5-(2,4-dinitrophenyl)tetrazole and 5-picryltetrazole as well as for the precursor 2,4-dinitro- and 2,4,6-trinitrobenzonitriles. 6 refs.

  16. Synthesis, characterization and fluorescence properties of Eu(III) and Tb(III) complexes with novel mono-substituted β-diketone ligands and 1,10-phenanthroline

    NASA Astrophysics Data System (ADS)

    Luo, Yi-Ming; Li, Jun; Xiao, Lin-Xiang; Tang, Rui-Ren; Tang, Xin-Cun

    2009-05-01

    Two novel pyridine-2,6-dicarboxylic acid derivatives of mono-β-diketone, methyl 6-benzoylacetyl-2-pyridinecarboxylate (MBAP) and 6-benzoylacetyl-2-pyridinecarboxylic acid (BAPA) and their Eu(III) and Tb(III) complexes were synthesized and characterized by elemental analysis, FT-IR, 1H NMR and TG-DTG. Moreover, their Eu(III) and Tb(III) complexes using 1,10-phenanthroline as a secondary ligand were prepared and characterized. The luminescence properties of these complexes in solid state were investigated in detail. The results suggested that Tb(III) complexes exhibit more efficient luminescence than Eu(III) complexes, the fluorescence intensity of Ln(III) complexes with BAPA is about twice as strong as that of Ln(III) complexes with MBAP, the fluorescence of mono-β-diketone complexes using 1,10-phenanthroline as a secondary ligand was prominently higher than that of complexes without adding 1,10-phenanthroline, and the ligand BAPA is an excellent sensitizer to Eu(III) and Tb(III) ion.

  17. Synthesis, characterization and fluorescence properties of Eu(III) and Tb(III) complexes with novel mono-substituted beta-diketone ligands and 1,10-phenanthroline.

    PubMed

    Luo, Yi-Ming; Li, Jun; Xiao, Lin-Xiang; Tang, Rui-Ren; Tang, Xin-Cun

    2009-05-01

    Two novel pyridine-2,6-dicarboxylic acid derivatives of mono-beta-diketone, methyl 6-benzoylacetyl-2-pyridinecarboxylate (MBAP) and 6-benzoylacetyl-2-pyridinecarboxylic acid (BAPA) and their Eu(III) and Tb(III) complexes were synthesized and characterized by elemental analysis, FT-IR, (1)H NMR and TG-DTG. Moreover, their Eu(III) and Tb(III) complexes using 1,10-phenanthroline as a secondary ligand were prepared and characterized. The luminescence properties of these complexes in solid state were investigated in detail. The results suggested that Tb(III) complexes exhibit more efficient luminescence than Eu(III) complexes, the fluorescence intensity of Ln(III) complexes with BAPA is about twice as strong as that of Ln(III) complexes with MBAP, the fluorescence of mono-beta-diketone complexes using 1,10-phenanthroline as a secondary ligand was prominently higher than that of complexes without adding 1,10-phenanthroline, and the ligand BAPA is an excellent sensitizer to Eu(III) and Tb(III) ion.

  18. Ribulose diphosphate carboxylase/oxygenase. III. Isolation and properties.

    PubMed

    Ryan, F J; Tolbert, N E

    1975-06-10

    Similarities in properties of ribulose diphosphate carboxylase and oxygenase activities further substantiate the hypothesis that the same protein catalyzes both reactions. The Km (ribulose diphosphate) is 0.33 mM for the ribulose diphosphate oxygenase, when assayed in air with an oxygen electrode. Maximum activity is obtained with 10 to 35 mM MgCl2. Higher MgCl2 concentrations are inhibitory, but they shift the pH optimum from 9.3 or 9.4 to 8.7 or 9.0. MnCl2 is an effective cofactor of the oxygenase and some activity is obtained with CoCl2. Both the ribulose diphosphate carboxylase and oxygenase activity of the purified protein from spinach leaves are slowly inactivated by storage at 0 degrees and reactivated in 10 min at 50 degrees, provided both 25 mM MgCl2 and 1 mM dithiothreitol are present. The sulfhydryl groups of the enzyme which react rapidly with 5,5'-dithiobis(2-nitrobenzoic acid) are approximately 4 at pH 7.8 and 11 at pH 9.4. At both pH values ribulose diphosphate prevents two of these sulfhydryl groups from reacting with this reagent. About 50% inhibition of the oxygenase activity at pH 9.0 occurs with 50 mM bicarbonate in the presence of 3 mM ribulose diphosphate, and from variations in these parameters the inhibition is attributed to the CO2 species. The purified enzyme of acrylamide gels prevented the reduction of nitroblue tetrazolium in the presence of the superoxide radical, but the enzyme in solution did not react as a superoxide dismutase.

  19. Synthesis and iron(III) binding properties of 3-hydroxypyrid-4-ones derived from kojic acid.

    PubMed

    Molenda, J J; Basinger, M A; Hanusa, T P; Jones, M M

    1994-08-01

    In an attempt to reduce the toxicity of the 3-hydroxypyrid-4-ones, the more hydrophilic derivatives of kojic acid were explored and compared to the standard, 1,2-dimethyl-3-hydroxypyrid-4-one, L1. The synthesis and iron(III) binding properties of these chelators are described. Neither these compounds nor the clinically effective 1,2-dimethyl-3-hydroxypyrid-4 one is able to completely remove all of the iron(III) from the Fe(III)EDTA complex in sodium acetate buffered solutions, when the 3-hydroxypyrid-4-one: Fe(III) ratio is 6:1. The ability of these compounds to enhance the urinary excretion of iron in rats indicates that the behavior of the 3-hydroxypyrid-4-ones derived from kojic acid is comparable to the analogous derivatives of maltol and ethyl maltol. The structure of the iron(III) complex of 3-hydroxy-6-hydroxymethyl-1-methylpyrid-4-one was determined by x-ray diffraction and found to be similar to the previously reported structure of the iron(III) complex of L1.

  20. Synthesis, crystal structure and magnetic properties of a novel heterobimetallic rhenium(IV)-dysprosium(III) chain.

    PubMed

    Pejo, Carolina; Guedes, Guilherme P; Novak, Miguel A; Speziali, Nivaldo L; Chiozzone, Raúl; Julve, Miguel; Lloret, Francesc; Vaz, Maria G F; González, Ricardo

    2015-06-08

    The use of the mononuclear rhenium(IV) precursor [ReBr5 (H2 pydc)](-) (H2 pydc=3,5-pyridinedicarboxylic acid) as a metalloligand towards dysprosium(III) afforded the first heterobimetallic Re(IV) -Dy(III) complex. Crystal structures and static and dynamic magnetic properties of both rhenium-containing species are reported herein. The 5d-4f compound shows an extended 1D structure and the AC magnetic measurements reveal frequency dependence at low temperature suggesting slow relaxation of the magnetization.

  1. Magnetic resonance properties of Gd(III)-bound lipid-coated microbubbles and their cavitation fragments.

    PubMed

    Feshitan, Jameel A; Boss, Michael A; Borden, Mark A

    2012-10-30

    Gas-filled microbubbles are potentially useful theranostic agents for magnetic resonance imaging-guided focused ultrasound surgery (MRIgFUS). Previously, MRI at 9.4 T was used to measure the contrast properties of lipid-coated microbubbles with gadolinium (Gd(III)) bound to lipid headgroups, which revealed that the longitudinal molar relaxivity (r(1)) increased after microbubble fragmentation. This behavior was attributed to an increase in water proton exchange with the Gd(III)-bound lipid fragments caused by an increase in the lipid headgroup area that accompanied the lipid shell monolayer-to-bilayer transition. In this article, we explore this mechanism by comparing the changes in r(1) and its transverse counterpart, r(2)*, after the fragmentation of microbubbles consisting of Gd(III) bound to two different locations on the lipid monolayer shell: the phosphatidylethanolamine (PE) lipid headgroup region or the distal region of the poly(ethylene glycol) (PEG) brush. Nuclear magnetic resonance (NMR) at 1.5 T was used to measure the contrast properties of the various microbubble constructs because this is the most common field strength used in clinical MRI. Results for the lipid-headgroup-labeled Gd(III) microbubbles revealed that r(1) increased after microbubble fragmentation, whereas r(2)* was unchanged. An analysis of PEG-labeled Gd(III) microbubbles revealed that both r(1) and r(2)* decreased after microbubble fragmentation. Further analysis revealed that the microbubble gas core enhanced the transverse MR signal (T(2)*) in a concentration-dependent manner but minimally affected the longitudinal (T(1)) signal. These results illustrate a new method for the use of NMR to measure the biomembrane packing structure and suggest that two mechanisms, proton-exchange enhancement by lipid membrane relaxation and magnetic field inhomogeneity imposed by the gas/liquid interface, may be used to detect and differentiate Gd(III)-labeled microbubbles and their cavitation

  2. What Is Raynaud's Phenomenon?

    MedlinePlus

    ... Phenomenon PDF Version Size: 59 KB November 2014 What Is Raynaud’s Phenomenon? Fast Facts: An Easy-to- ... use tools that vibrate, such as a jackhammer. What Are the Symptoms of Raynaud’s Phenomenon? The body ...

  3. Synthesis, structure and physical properties of luminescent Pr(III) β-diketonate complexes

    NASA Astrophysics Data System (ADS)

    Pereira, V. M.; Costa, A. L.; Feldl, J.; Maria, T. M. R.; Seixas de Melo, J. S.; Martín-Ramos, P.; Martín-Gil, J.; Ramos Silva, M.

    2017-02-01

    Near infrared lanthanide(III)-based light conversion molecular devices (LCMDs) are emerging as a promising class of materials for organic light-emitting diodes (OLEDs) in some niche technologies. Three of these molecular materials -two highly coordinated Pr3+β-diketonate monomers and a dimer- are presented and their structure and properties are discussed. Particular emphasis is placed on the solid-to-solid transformation observed for the homodinuclear compound.

  4. Photo-controllable thermoelectric properties with reversibility and photo-thermoelectric effects of tungsten trioxide accompanied by its photochromic phenomenon

    SciTech Connect

    Azuma, Chiori; Kawano, Takuto; Kakemoto, Hirofumi; Irie, Hiroshi

    2014-11-07

    The addition of photo-controllable properties to tungsten trioxide (WO{sub 3}) is of interest for developing practical applications of WO{sub 3} as well as for interpreting such phenomena from scientific viewpoints. Here, a sputtered crystalline WO{sub 3} thin film generated thermoelectric power due to ultraviolet (UV) light-induced band-gap excitation and was accompanied by a photochromic reaction resulting from generating W{sup 5+} ions. The thermoelectric properties (electrical conductivity (σ) and Seebeck coefficient (S)) and coloration of WO{sub 3} could be reversibly switched by alternating the external stimulus between UV light irradiation and dark storage. After irradiating the film with UV light, σ increased, whereas the absolute value of S decreased, and the photochromic (coloration) reaction was detected. Notably, the opposite behavior was exhibited by WO{sub 3} after dark storage, and this reversible cycle could be repeated at least three times. Moreover, photo-thermoelectric effects (photo-conductive effect (photo-conductivity, σ{sub photo}) and photo-Seebeck effect (photo-Seebeck coefficient, S{sub photo})) were also detected in response to visible-light irradiation of the colored WO{sub 3} thin films. Under visible-light irradiation, σ{sub photo} and the absolute value of S{sub photo} increased and decreased, respectively. These effects are likely attributable to the excitation of electrons from the mid-gap visible light absorption band (W{sup 5+} state) to the conduction band of WO{sub 3}. Our findings demonstrate that the simultaneous, reversible switching of multiple properties of WO{sub 3} thin film is achieved by the application of an external stimulus and that this material exhibits photo-thermoelectric effects when irradiated with visible-light.

  5. The Aloe vera phenomenon: a review of the properties and modern uses of the leaf parenchyma gel.

    PubMed

    Grindlay, D; Reynolds, T

    1986-06-01

    The mucilaginous gel from the parenchymatous cells in the leaf pulp of Aloe vera has been used since early times for a host of curative purposes. This gel should be distinguished clearly from the bitter yellow exudate originating from the bundle sheath cells, which is used for its purgative effects. Aloe vera gel has come to play a prominent role as a contemporary folk remedy, and numerous optimistic, and in some cases extravagant, claims have been made for its medicinal properties. Modern clinical use of the gel began in the 1930s, with reports of successful treatment of X-ray and radium burns, which led to further experimental studies using laboratory animals in the following decades. The reports of these experiments and the numerous favourable case histories did not give conclusive evidence, since although positive results were usually described, much of the work suffered from poor experimental design and insufficiently large test samples. In addition some conflicting or inconsistent results were obtained. With the recent resurgence of interest in Aloe vera gel, however, new experimental work has indicated the possibility of distinct physiological effects. Chemical analysis has shown the gel to contain various carbohydrate polymers, notably either glucomannans or pectic acid, along with a range of other organic and inorganic components. Although many physiological properties of the gel have been described, there is no certain correlation between these and the identified gel components.

  6. Tuning the cellular uptake properties of luminescent heterobimetallic iridium(III)-ruthenium(II) DNA imaging probes.

    PubMed

    Wragg, Ashley; Gill, Martin R; Turton, David; Adams, Harry; Roseveare, Thomas M; Smythe, Carl; Su, Xiaodi; Thomas, Jim A

    2014-10-20

    The synthesis of two new luminescent dinuclear Ir(III)-Ru(II) complexes containing tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine (tpphz) as the bridging ligand is reported. Unlike many other complexes incorporating cyclometalated Ir(III) moieties, these complexes display good water solubility, allowing the first cell-based study on Ir(III)-Ru(II) bioprobes to be carried out. Photophysical studies indicate that emission from each complex is from a Ru(II) excited state and both complexes display significant in vitro DNA-binding affinities. Cellular studies show that each complex is rapidly internalised by HeLa cells, in which they function as luminescent nuclear DNA-imaging agents for confocal microscopy. Furthermore, the uptake and nuclear targeting properties of the complex incorporating cyclometalating 2-(4-fluorophenyl)pyridine ligands around its Ir(III) centre is enhanced in comparison to the non-fluorinated analogue, indicating that fluorination may provide a route to promote cell uptake of transition-metal bioprobes.

  7. Synthesis and optical properties of macrocyclic lanthanide(III) chelates as new reagents for luminescent biolabeling.

    PubMed

    Deslandes, Sébastien; Galaup, Chantal; Poole, Robert; Mestre-Voegtlé, Béatrice; Soldevila, Stéphanie; Leygue, Nadine; Bazin, Hervé; Lamarque, Laurent; Picard, Claude

    2012-11-14

    The convenient and efficient synthesis of two macrocyclic ligands (15- and 18-membered) based on a dipyrido-6,7,8,9-tetrahydrophenazine (dpqc) or 2,2':6',2''-terpyridine (tpy) heterocycle and a DTTA (diethylenetriaminetriacetic acid) skeleton is described. In these ligands the DTTA skeleton contains an additional extracyclic functionality (NH(2) group) suitable for covalent attachment to bioactive molecules. These octa- and nonadentate ligands form very stable and luminescent neutral lanthanide complexes in aqueous solutions at physiological pH. The corresponding Eu(III) and Tb(III) complexes are characterized by a maximum absorption wavelength compatible with nitrogen laser excitation (337 nm) and attractive lifetimes and quantum yields. Further introduction of a maleimide bioconjugatable handle in the Eu(III) complexes was investigated and a valuable luminescence brightness above 1500 dm(3) mol(-1) cm(-1) at 337 nm was obtained with the corresponding Eu(III) tpy-derivative. Finally, these two luminescent chelates were grafted onto thiol residues of a model antibody (Mab GSS11) without loss of their luminescent properties.

  8. Spectral and temporal luminescent properties of Eu(III) in humic substance solutions from different origins

    NASA Astrophysics Data System (ADS)

    Brevet, Julien; Claret, Francis; Reiller, Pascal E.

    2009-10-01

    Although a high heterogeneity of composition is awaited for humic substances, their complexation properties do not seem to greatly depend on their origins. The information on the difference in the structure of these complexes is scarce. To participate in the filling of this lack, a study of the spectral and temporal evolution of the Eu(III) luminescence implied in humic substance (HS) complexes is presented. Seven different extracts, namely Suwannee River fulvic acid (SRFA) and humic acid (SRHA), and Leonardite HA (LHA) from the International Humic Substances Society (USA), humic acid from Gorleben (GohyHA), and from the Kleiner Kranichsee bog (KFA, KHA) from Germany, and purified commercial Aldrich HA (PAHA), were made to contact with Eu(III). Eu(III)-HS time-resolved luminescence properties were compared with aqueous Eu 3+ at pH 5. Using an excitation wavelength of 394 nm, the typical bi-exponential luminescence decay for Eu(III)-HS complexes is common to all the samples. The components τ1 and τ2 are in the same order of magnitude for all the samples, i.e., 40 ≤ τ1 (μs) ≤ 60, and 145 ≤ τ2 (μs) ≤ 190, but significantly different. It is shown that different spectra are obtained from the different groups of samples. Terrestrial extract on the one hand, i.e. LHA/GohyHA, plus PAHA, and purely aquatic extracts on the other hand, i.e., SRFA/SRHA/KFA/KHA, induce inner coherent luminescent properties of Eu(III) within each group. The 5D 0 → 7F 2 transition exhibits the most striking differences. A slight blue shift is observed compared to aqueous Eu 3+ ( λmax = 615.4 nm), and the humic samples share almost the same λmax ≈ 614.5 nm. The main differences between the samples reside in a shoulder around λ ≈ 612.5 nm, modelled by a mixed Gaussian-Lorentzian band around λ ≈ 612 nm. SRFA shows the most intense shoulder with an intensity ratio of I612.5/ I614.7 = 1.1, KFA/KHA/SRHA share almost the same ratio I612.5/ I614.7 = 1.2-1.3, whilst the LHA

  9. Spectral and temporal luminescent properties of Eu(III) in humic substance solutions from different origins.

    PubMed

    Brevet, Julien; Claret, Francis; Reiller, Pascal E

    2009-10-01

    Although a high heterogeneity of composition is awaited for humic substances, their complexation properties do not seem to greatly depend on their origins. The information on the difference in the structure of these complexes is scarce. To participate in the filling of this lack, a study of the spectral and temporal evolution of the Eu(III) luminescence implied in humic substance (HS) complexes is presented. Seven different extracts, namely Suwannee River fulvic acid (SRFA) and humic acid (SRHA), and Leonardite HA (LHA) from the International Humic Substances Society (USA), humic acid from Gorleben (GohyHA), and from the Kleiner Kranichsee bog (KFA, KHA) from Germany, and purified commercial Aldrich HA (PAHA), were made to contact with Eu(III). Eu(III)-HS time-resolved luminescence properties were compared with aqueous Eu(3+) at pH 5. Using an excitation wavelength of 394 nm, the typical bi-exponential luminescence decay for Eu(III)-HS complexes is common to all the samples. The components tau(1) and tau(2) are in the same order of magnitude for all the samples, i.e., 40 properties of Eu(III) within each group. The (5)D(0) --> (7)F(2) transition exhibits the most striking differences. A slight blue shift is observed compared to aqueous Eu(3+) (lambda(max) = 615.4 nm), and the humic samples share almost the same lambda(max) approximately 614.5 nm. The main differences between the samples reside in a shoulder around lambda approximately 612.5 nm, modelled by a mixed Gaussian-Lorentzian band around lambda approximately 612 nm. SRFA shows the most intense shoulder with an intensity ratio of I(612.5)/I(614.7) = 1.1, KFA

  10. Optical and Electrical Properties of III-Nitrides and Related Materials

    SciTech Connect

    Jiang, Hongxing; Lin, Jingyu

    2016-01-22

    Among the members of the III-nitride material system, boron-nitride (BN) is the least studied and understood. Its extraordinary physical properties, such as ultra-high chemical stability, thermal conductivity, electrical resistivity, band gap (Eg ~ 6 eV), and optical absorption near the band gap make hexagonal BN (h-BN) the material of choice for emerging applications such as deep ultraviolet (DUV) optoelectronic devices. Moreover, h-BN has a close lattice match to graphene and is the most suitable substrate and dielectric/separation layer for graphene electronics and optoelectronics. Similar to graphene, low dimensional h-BN is expected to possess rich new physics. Other potential applications include super-capacitors and electron emitters. However, our knowledge concerning the semiconducting properties of h-BN is very scarce. The project aims to extend our studies to the “newest” family member of the III-nitride material system, h-BN, and to address issues that have not yet been explored but are expected to profoundly influence our understanding on its fundamental properties and device applications. During the supporting period, we have improved the growth processes of h-BN epilayers by metal organic chemical vapor deposition (MOCVD), investigated the fundamental material properties, and identified several unique features of h-BN as well as critical issues that remain to be addressed.

  11. Conferring Phosphorogenic Properties on Iridium(III)-Based Bioorthogonal Probes through Modification with a Nitrone Unit.

    PubMed

    Lee, Lawrence Cho-Cheung; Lau, Jonathan Chun-Wai; Liu, Hua-Wei; Lo, Kenneth Kam-Wing

    2016-01-18

    The use of bioorthogonal probes that display fluorogenic or phosphorogenic properties is advantageous to the labeling and imaging of biomolecules in live cells and organisms. Herein we present the design of three iridium(III) complexes containing a nitrone moiety as novel phosphorogenic bioorthogonal probes. These probes were non-emissive owing to isomerization of the C=N group but showed significant emission enhancement upon cycloaddition reaction with strained cyclooctynes. Interestingly, the connection of the nitrone ligand to the cationic iridium(III) center led to accelerated reaction kinetics. These nitrone complexes were also identified as phosphorogenic bioorthogonal labels and imaging reagents for cyclooctyne-modified proteins. These findings contribute to the development of phosphorogenic bioorthogonal probes and imaging reagents.

  12. Theoretical studies on the photophysical properties of some Iridium (III) complexes used for OLED

    NASA Astrophysics Data System (ADS)

    Urinda, Sharmistha; Das, Goutam; Pramanik, Anup; Sarkar, Pranab

    2016-09-01

    The structural and photophysical properties of four heteroleptic Iridium (III) complexes, based on 1-phenylpyrazole ligand, have been investigated theoretically. The effect of chemical substitution on the absorption and the emission spectra of the complexes has been studied and compared with the experimental data. We observe a significant structural change in the lowest triplet excited state as compared to the ground singlet state. We compute the emission wavelength of the complexes by considering the spin-orbit coupling. Using these understandings, we predict two new complexes having deeper blue emission which are supposed to be better efficient OLED materials.

  13. Fluorescence and DNA-binding properties of neodymium(III) and praseodymium(III) complexes containing 1,10-phenanthroline

    NASA Astrophysics Data System (ADS)

    Khorasani-Motlagh, Mozhgan; Noroozifar, Meissam; Mirkazehi-Rigi, Sohaila

    2011-09-01

    The binding of neodymium(III) and praseodymium(III) complexes containing 1,10-phenanthroline, [M(phen) 2Cl 3·OH 2] (M = Nd ( 1), Pr ( 2)), to DNA has been investigated by absorption, emission, and viscosity measurements. The complexes show absorption decreasing in charge transfer band, fluorescence decrement when bound to DNA. The binding constant Kb has been determined by absorption measurement for both complexes and found to be (6.76 ± 0.12) × 10 4 for 1 and (1.83 ± 0.15) × 10 4 M -1, for 2. The fluorescence of [M(phen) 2Cl 3·OH 2] (M = Nd ( 1), Pr ( 2)) has been studied in detail. The results of fluorescence titration reveal that DNA has the strong ability to quenching the intrinsic fluorescence of Nd(III) and Pr(III) complexes through the static quenching procedure. The binding site number n, apparent binding constant Kb and the Stern-Volmer constant kSV are determined. Thermodynamic parameters, enthalpy change (Δ H°) and entropy change (Δ S°), are calculated according to relevant fluorescent data and Van't Hoff equation. The experimental data suggest that the complexes bind to DNA by non-intercalative mode. Major groove binding is the preferred mode of interaction for [M(phen) 2Cl 3·OH 2] (M = Nd ( 1), Pr ( 2)) with DNA.

  14. Fluorescence and DNA-binding properties of neodymium(III) and praseodymium(III) complexes containing 1,10-phenanthroline.

    PubMed

    Khorasani-Motlagh, Mozhgan; Noroozifar, Meissam; Mirkazehi-Rigi, Sohaila

    2011-09-01

    The binding of neodymium(III) and praseodymium(III) complexes containing 1,10-phenanthroline, [M(phen)2Cl3·OH2] (M=Nd (1), Pr (2)), to DNA has been investigated by absorption, emission, and viscosity measurements. The complexes show absorption decreasing in charge transfer band, fluorescence decrement when bound to DNA. The binding constant Kb has been determined by absorption measurement for both complexes and found to be (6.76±0.12)×10(4) for 1 and (1.83±0.15)×10(4)M(-1), for 2. The fluorescence of [M(phen)2Cl3·OH2] (M=Nd (1), Pr (2)) has been studied in detail. The results of fluorescence titration reveal that DNA has the strong ability to quenching the intrinsic fluorescence of Nd(III) and Pr(III) complexes through the static quenching procedure. The binding site number n, apparent binding constant Kb and the Stern-Volmer constant kSV are determined. Thermodynamic parameters, enthalpy change (ΔH°) and entropy change (ΔS°), are calculated according to relevant fluorescent data and Van't Hoff equation. The experimental data suggest that the complexes bind to DNA by non-intercalative mode. Major groove binding is the preferred mode of interaction for [M(phen)2Cl3·OH2] (M=Nd (1), Pr (2)) with DNA.

  15. Thermodynamic stability, kinetic inertness and relaxometric properties of monoamide derivatives of lanthanide(III) DOTA complexes.

    PubMed

    Tei, Lorenzo; Baranyai, Zsolt; Gaino, Luca; Forgács, Attila; Vágner, Adrienn; Botta, Mauro

    2015-03-28

    A complete thermodynamic and kinetic solution study on lanthanide(III) complexes with monoacetamide (DOTAMA, L1) and monopropionamide (DOTAMAP, L2) derivatives of DOTA (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) was undertaken with the aim to elucidate their stability and inertness in aqueous media. The stability constants of GdL1 and GdL2 are comparable, whereas a more marked difference is found in the kinetic inertness of the two complexes. The formation of the Eu(III) and Ce(III) complexes takes place via the formation of the protonated intermediates which can deprotonate and transform into the final complex through a OH(-) assisted pathway. GdL2 shows faster rates of acid catalysed decomplexation with respect to GdL1, which has a kinetic inertness comparable to GdDOTA. Nevertheless, GdL2 is one order of magnitude more inert than GdDO3A. A novel DOTAMAP-based bifunctional chelating ligand and its deoxycholic acid derivative (L5) were also synthesized. Since the coordinated water molecule in GdL2 is characterized by an exchange rate ca. two orders of magnitude greater than in GdL1, the relaxivity of the macromolecular derivatives of L5 should not be limited by the slow water exchange process. The relaxometric properties of the supramolecular adduct of GdL5 with human serum albumin (HSA) were investigated in aqueous solution by measuring the magnetic field dependence of the (1)H relaxivity which, at 20 MHz and 298 K, shows a 430% increase over that of the unbound GdL5 chelate. Thus, Gd(III) complexes with DOTAMAP macrocyclic ligands can represent good candidates for the development of stable and highly effective bioconjugate systems for molecular imaging applications.

  16. Magnetocaloric properties of manganese(III) porphyrins bearing 2,6-di-tert-butylphenol groups

    NASA Astrophysics Data System (ADS)

    Korolev, V. V.; Lomova, T. N.; Maslennikova, A. N.; Korolev, D. V.; Shpakovsky, D. B.; Zhang, Jianwei; Milaeva, E. R.

    2016-03-01

    Magnetocaloric effect (MCE) and heat capacity during the magnetization of (5,10,15,20-tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphynato) manganese (III) chloride (1), (5-(4-hydroxyphenyl)-10,15,20-tris(3,5-di-tert-butyl-4-hydroxyphenyl)porphynato) manganese (III) chloride (2), and (5-(4-palmitoyloxyphenyl)-10,15,20-tris(3,5-di-tert-butyl-4-hydroxyphenyl)porphynato) manganese (III) chloride (3) in their aqueous suspensions were determined by the microcalorimetric method over the temperature range of 278-320 K and in magnetic fields from 0 to 1 T. MCE was positive for all complexes studied, i.e. the magnetic field impression under adiabatic conditions led to an increase in temperature of the complexes suspensions. MCE increased with an increase in the magnetic field induction at all temperatures studied. Dependences of MCE on temperature had weak maxima at 298 K at all magnetic induction values. The disturbance of the intermolecular hydrogen-bonding of hydroxyl groups is one of probable reasons for such dependences type. MCE values increased under the palmitoyl substituent incorporation into one of the phenol groups at all temperatures. The heat capacity of the studied complexes rose slightly with temperature growth. Dependences of the heat capacity on temperature showed that the magnetic component of the heat capacity did not appear due to the presence of the manganese atom acting as a paramagnetic center in complexes 1, 2, and 3. The relation between the complexes structure and their magnetothermal properties was analyzed. It was justified that the changes of magnetothermal properties were caused by electronic substitution effects and, to an even greater degree, by the conditions of intermolecular hydrogen bonds formation in the paramagnetic materials.

  17. III-Nitride nanowire lasers: fabrication and control of optical properties (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Wang, George T.

    2016-09-01

    III-nitride nanowires have attracted increasing interest as potential ultracompact and low-power nanoscale lasers in the UV-visible wavelengths. In order to maximize the potential of nanowire lasers, a greater understanding and control over their properties, including mode control, polarization control, wavelength tuning, and beam shaping, is necessary. Here, we discuss the fabrication of III-nitride based single nanowire and nanowire photonic crystal lasers using a top-down approach, and present multiple methods for controlling their optical properties. The nanowires were fabricated by a two-step process composed of a lithographic dry etch followed by a selective, wet chemical etch of the nanowire sidewalls. This technique allows for high quality nanowires with straight and smooth nonpolar m-plane sidewalls and with controllable height, pitch and diameter. Precisely engineered axial nanowire heterostructures can be formed from planar heterostructures, while radial nanowire heterostructures can be formed via regrowth on the etched nanowires. This work was performed, in part, at the Center for Integrated Nanotechnologies, a U.S. Department of Energy, Office of Basic Energy Sciences user facility. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  18. First-principles investigations of III-nitride bulk and surface properties

    NASA Astrophysics Data System (ADS)

    Dreyer, Cyrus Eduard

    The III-nitride semiconductors, including AlN, InN, GaN, and BN have been demonstrated as technologically exciting materials for a wide range of device applications. With band gaps that span the visible range, GaN, InN, and InGaN alloys are used for high efficiency light emitting diodes for general lighting, as well as laser diodes for optical storage. The wide gaps, large band offsets, and polarization fields in AlN, GaN, and AlGaN alloys are promising for high-frequency, high-power transistors with applications in power conversion and radio frequency amplifiers. Despite the plethora of attractive material parameters of the III-nitride materials there are several issues that significantly limit the efficiency of devices and range of possible applications. In this study, we use first-principles electronic structure calculations to explore several of these properties relevant to understanding growth, processing, and device design. Arguably the most detrimental issue in this material system is the lack of widely available, cost-effective substrates for the growth of films and devices. Heteroepitaxy, as well as the lattice mismatch between the layers of different III-nitride alloys in heterostructures, results in residual stresses in films and devices. Such stress will alter the electronic structure of the materials, so it is necessary for device design to be able to quantify these effects. We explore the influence of strain on the effective mass of carriers in GaN and AlN, a parameter that is tied to the conductivity. In addition, films under tensile strain can crack if the strain energy is sufficient. We explore the propensity for AlN, GaN, and AlGaN to crack on different crystallographic planes. There has been significant work done to overcome the issue of residual strains in III-nitride films, both through the growth of bulk crystals for substrates, and the growth of structures such as nanowires that avoid many of the thickness and alloy-content limitations of

  19. Structures and Luminescent Properties of Two 2D Coordination Polymers Containing Tb(III) or Dy(III) Ions.

    PubMed

    An, Xiaoping; Wang, Hongsheng; Li, Gongchun

    2014-03-01

    Two 2D rare earth terbium and dysprosium coordination polymers with 2,4-pyridinedicarboxylate and oxalate anions have been synthesized by hydrothermal method, the formula is {[RE(pda)(ox)0.5(H2O)4]·2H2O}n (RE = Tb (1) and Dy (2); H2pda = 2,4-pyridinedicarboxylic acid; ox = oxalate anion). The two complexes are isomorphic and crystallized in monoclinic system, P21/c space group. Each pda anion connects two rare earth ions with 2- carboxyl group and the nitrogen atom but the 4- carboxyl group does not coordinate with rare earth ions. Each ox anion connects two rare earth ions by μ 2-bridge way. Both the complexes exhibit intense characteristic luminescence of Tb(III) or Dy(III) ion with excitation of UV-rays.

  20. The structures of CyMe4-BTBP complexes of americium(iii) and europium(iii) in solvents used in solvent extraction, explaining their separation properties.

    PubMed

    Ekberg, Christian; Löfström-Engdahl, Elin; Aneheim, Emma; Foreman, Mark R StJ; Geist, Andreas; Lundberg, Daniel; Denecke, Melissa; Persson, Ingmar

    2015-11-14

    Separation of trivalent actinoid (An(iii)) and lanthanoid (Ln(iii)) ions is extremely challenging due to their similar ionic radii and chemical properties. Poly-aromatic nitrogen compounds acting as tetradentate chelating ligands to the metal ions in the extraction, have the ability to sufficiently separate An(iii) from Ln(iii). One of these compounds, 6,6'-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-benzol[1,2,4]triazin-3-yl)[2,2]bipyridine, CyMe4-BTBP, has proven to be resistant towards acidic environments and strong radiation from radioactive decomposition. EXAFS studies of the dicomplexes of CyMe4-BTBP with americium(iii) and europium(iii) in nitrobenzene, cyclohexanone, 1-hexanol, 1-octanol and malonamide (DMDOHEMA) in 1-octanol have been carried out to get a deeper understanding of the parameters responsible for the separation. The predominating complexes independent of solvent used are [Am(CyMe4-BTBP)2(NO3)](2+) and [Eu(CyMe4-BTBP)2](3+), respectively, which are present as outer-sphere ion-pairs with nitrate ions in the studied solvents with low relative permittivity. The presence of a nitrate ion in the first coordination sphere of the americium(iii) complex compensates the charge density of the complex considerably in comparison when only outer-sphere ion-pairs are formed as for the [Eu(CyMe4-BTBP)2](3+) complex. The stability and solubility of a complex in a solvent with low relative permittivity increase with decreasing charge density. The [Am(CyMe4-BTBP)2(NO3)](2+) complex will therefore be increasingly soluble and stabilized over the [Eu(CyMe4-BTBP)2](3+) complex in solvents with decreasing relative permittivity of the solvent. The separation of americium(iii) from europium(iii) with CyMe4-BTBP as extraction agent will increase with decreasing relative permittivity of the solvent, and thereby also with decreasing solubility of CyMe4-BTBP. The choice of solvent is therefore a balance of a high separation factor and sufficient solubility of the CyMe4-BTBP

  1. Cr(III), Fe(III) and Co(III) complexes of tetradentate (ONNO) Schiff base ligands: Synthesis, characterization, properties and biological activity

    NASA Astrophysics Data System (ADS)

    Keskioğlu, Eren; Gündüzalp, Ayla Balaban; Çete, Servet; Hamurcu, Fatma; Erk, Birgül

    2008-08-01

    A series of metal complexes were synthesized from equimolar amounts of Schiff bases: 1,4-bis[3-(2-hydroxy-1-naphthaldimine)propyl]piperazine (bappnaf) and 1,8-bis[3-(2-hydroxy-1-naphthaldimine)- p-menthane (damnaf) with metal chlorides. All of synthesized compounds were characterized by elemental analyses, spectral (UV-vis, IR, 1H- 13C NMR, LC-MS) and thermal (TGA-DTA) methods, magnetic and conductance measurements. Schiff base complexes supposed in tetragonal geometry have the general formula [M(bappnaf or damnaf)]Cl· nH 2O, where M = Cr(III), Co(III) and n = 2, 3. But also Fe(III) complexes have octahedral geometry by the coordination of two water molecules and the formula is [Fe(bappnaf or damnaf)(H 2O) 2]Cl. The changes in the selected vibration bands in FT-IR indicate that Schiff bases behave as (ONNO) tetradentate ligands and coordinate to metal ions from two phenolic oxygen atoms and two azomethine nitrogen atoms. Conductance measurements suggest 1:1 electrolytic nature of the metal complexes. The synthesized compounds except bappnaf ligand have the antimicrobial activity against the bacteria: Escherichia coli (ATCC 11230), Yersinia enterocolitica (ATCC 1501), Bacillus magaterium (RSKK 5117), Bacillus subtilis (RSKK 244), Bacillus cereus (RSKK 863) and the fungi: Candida albicans (ATCC 10239). These results have been considerably interest in piperazine derivatives due to their significant applications in antimicrobial studies.

  2. Steric and Electronic Influence of Aryl Isocyanides on the Properties of Iridium(III) Cyclometalates.

    PubMed

    Maity, Ayan; Le, Linh Q; Zhu, Zhuan; Bao, Jiming; Teets, Thomas S

    2016-03-07

    Cyclometalated iridium complexes with efficient phosphorescence and good electrochemical stability are important candidates for optoelectronic devices. Isocyanide ligands are strong-field ligands: when attached to transition metals, they impart larger HOMO-LUMO energy gaps, engender higher oxidative stability at the metal center, and support rugged organometallic complexes. Aryl isocyanides offer more versatile steric and electronic control by selective substitution at the aryl ring periphery. Despite a few reports of alkyl isocyanide of cyclometalated iridium(III), detailed studies on analogous aryl isocyanide complexes are scant. We report the synthesis, photophysical properties, and electrochemical properties of 11 new luminescent cationic biscyclometalated bis(aryl isocyanide)iridium(III) complexes. Three different aryl isocyanides--2,6-dimethylphenyl isocyanide (CNAr(dmp)), 2,6-diisopropylphenyl isocyanide (CNAr(dipp)), and 2-naphthyl isocyanide (CNAr(nap))--were combined with four cyclometalating ligands with differential π-π* energies--2-phenylpyridine (ppy), 2,4-difluorophenylpyridine (F2ppy), 2-benzothienylpyridine (btp), and 2-phenylbenzothiazole (bt). Five of them were crystallographically characterized. All new complexes show wide redox windows, with reduction potentials falling in a narrow range of -2.02 to -2.37 V and oxidation potentials spanning a wider range of 0.97-1.48 V. Efficient structured emission spans from the blue region for [(F2ppy)2Ir(CNAr)2]PF6 to the orange region for [(btp)2Ir(CNAr)2]PF6, demonstrating that isocyanide ligands can support redox-stable luminescent complexes with a range of emission colors. Emission quantum yields were generally high, reaching a maximum of 0.37 for two complexes, whereas btp-ligated complexes had quantum yields below 1%. The structure of the CNAr ligand has a minimal effect on the photophysical properties, which are shown to arise from ligand-centered excited states with very little contribution from

  3. Synthesis, structural characterization and photoluminescence properties of a novel La(III) complex

    NASA Astrophysics Data System (ADS)

    Köse, Muhammet; Ceyhan, Gökhan; Atcı, Emine; McKee, Vickie; Tümer, Mehmet

    2015-05-01

    In this study, a novel La(III) complex [La(H2L)2(NO3)3(MeOH)] of a Schiff base ligand was synthesized and characterized by spectroscopic and analytical methods. Single crystals of the complex suitable for X-ray diffraction study were obtained by slow diffusion of diethyl ether into a MeOH solution of the complex which was found to crystallise as [La(H2L)2(NO3)3(MeOH)]ṡ2MeOHṡH2O. The structure was solved in monoclinic crystal system, P21/n space group with unit cell parameters a = 10.5641(11), b = 12.6661(16), c = 16.0022(17) Å, α = 67.364(2), β = 83.794(2)°, γ = 70.541(2)°, V = 1862.9(4) Å3 and Z = 2 with R final value of 0.526. In the complex, the La(III) ion is ten-coordinated by O atoms, five of which come from three nitrate ions, four from the two Schiff base ligands and one from MeOH oxygen atom. The Schiff base ligands in the structure are in a zwitter ion form with the phenolic H transferred to the imine N atom. Thermal properties of the La(III) complex were examined by thermogravimetric analysis and the complex was found to be thermally stable up to 310 °C. The Schiff base ligand and its La(II) complex were screened for their in vitro antimicrobial activity against Bacillus megaterium, Staphylococcus aureus, Bacillus subtilis, Micrococcus luteus (Gram positive bacteria), Klebsiella pneumonia, Escherichia coli, Enterobacter aerogenes, Pseudomonas aeruginosa (Gram negative bacteria), Candida albicans,Yarrowia lipolytica (fungus) and Saccharomyces cerevisiae (yeast). The complex shows more antimicrobial activity than the free ligand.

  4. Hydrolysis and cytotoxic properties of osmium(II)/(III)-DMSO-azole complexes. Short communication.

    PubMed

    Egger, Alexander; Cebrián-Losantos, Berta; Stepanenko, Iryna N; Krokhin, Artem A; Eichinger, Rene; Jakupec, Michael A; Arion, Vladimir B; Keppler, Bernhard K

    2008-08-01

    The antiproliferative properties of the osmium(II) complexes cis,fac-[Os(II)Cl(2)(DMSO)(3)(L)] and trans,cis,cis-[Os(II)Cl(2)(DMSO)(2)(L)(2)] (L = 1H-pyrazole, 1H-imidazole) were studied in three human cancer cell lines, namely 41M (ovary), SK-BR-3 (breast), and SW480 (colon). Their activities were compared with those of osmium(III) and ruthenium(III) NAMI-A type complexes on HT-29 (colon) and SK-BR-3 cancer cell lines. While IC(50) values of all the Os(II) complexes were found to be >1000 microM in all cell lines, Os and Ru-NAMI-A type complexes showed remarkable antiproliferative activity. The marginal in vitro cytotoxicity of the Os(II) compounds is presumably attributed to their resistance to hydrolysis. However, the Os-NAMI-A complexes, which are also kinetically stable in aqueous solution, showed reasonable antiproliferative activity in vitro when compared with the analogous Ru compounds and with the Os(II)-DMSO-azole species, indicating that hydrolysis might be not a prerequisite for the antitumor activity of Os-NAMI-A type complexes.

  5. Electro-optical properties characterization of fish type III antifreeze protein.

    PubMed

    Salvay, Andrés G; Santos, Javier; Howard, Eduardo I

    2007-12-01

    Antifreeze proteins (AFPs) are ice-binding proteins that depress the freezing point of water in a non-colligative manner without a significant modification of the melting point. Found in the blood and tissues of some organisms (such as fish, insects, plants, and soil bacteria), AFPs play an important role in subzero temperature survival. Fish Type III AFP is present in members of the subclass Zoarcoidei. AFPIII are small 7-kDa-or 14-kDa tandem-globular proteins. In the present work, we study the behavior of several physical properties, such as the low-frequency dielectric permittivity spectrum, circular dichroism, and electrical conductivity of Fish Type III AFP solutions measured at different concentrations. The combination of the information obtained from these measurements could be explained through the formation of AFP molecular aggregates or, alternatively, by the existence of some other type of interparticle interactions. Thermal stability and electro-optical behavior, when proteins are dissolved in deuterated water, were also investigated.

  6. Spectroscopic properties of neodymium(III)-containing polyoxometalates in aqueous solution.

    PubMed

    But, Slawomir; Lis, Stefan; Deun, Rik Van; Parac-Vogt, Tatjana N; Görller-Walrand, Christiane; Binnemans, Koen

    2005-11-01

    The spectroscopic properties of the neodymium(III)-containing polyoxometalates (POMs) [Nd(PW(11)O(39))(2)](11-), [Nd(PMo(2)W(9)O(39))(2)](11-), [Nd(PMo(4)W(7)O(39))(2)](11-), [Nd(PMo(6)W(5)O(39))(2)](11-), [Nd(SiMo(2)W(9)O(39))(2)](13-), [Nd(P(2)W(17)O(61))(2)](17-), [NdW(10)O(36)](9-), [NdP(5)W(30)O(110)](12-) and [NdAs(4)W(40)O(140)](25-) are described. Absorption spectra of aqueous solutions of the complexes have been recorded and the transition intensities are parameterised in terms of the Judd-Ofelt intensity parameters Omega(lambda) (lambda=2, 4, 6). Marked differences were found between the luminescence lifetimes of the complexes of the type Nd(POM) and those of the type Nd(POM)(2), due to a better shielding of the neodymium(III) ions from the bulk water molecules in the latter type of complexes.

  7. Proton and gallium(III) binding properties of a biologically active salicylidene acylhydrazide.

    PubMed

    Hakobyan, Shoghik; Boily, Jean-François; Ramstedt, Madeleine

    2014-09-01

    Bacterial biofilm formation causes a range of problems in our society, especially in health care. Salicylidene acylhydrazides (hydrazones) are promising antivirulence drugs targeting secretion systems used during bacterial infection of host cells. When mixed with the gallium ion they become especially potent as bacterial and biofilm growth-suppressing agents, although the mechanisms through which this occurs are not fully understood. At the base of this uncertainty lies the nature of hydrazone-metal interactions. This study addresses this issue by resolving the equilibrium speciation of hydrazone-gallium aqueous solutions. The protonation constants of the target 2-oxo-2-[N-(2,4,6-trihydroxy-benzylidene)-hydrazino]-acetamide (ME0163) hydrazone species and of its 2,4,6-trihydroxybenzaldehyde and oxamic acid hydrazide building blocks were determined by UV-visible spectrophotometry to achieve this goal. These studies show that the hydrazone is an excessively strong complexing agent for gallium and that its antivirulence properties are predominantly ascribed to monomeric 1:1Ga-ME0163 complexes of various Ga hydrolysis and ME0163 protonation states. The chelation of Ga(III) to the hydrazone also increased the stability of the compounds against acid-induced hydrolysis, making this group of compounds very interesting for biological applications where the Fe-antagonist action of both Ga(III) and the hydrazone can be combined for enhanced biological effect.

  8. Synthesis, spectral and electrochemical properties of Al(III) and Zn(II) complexes with flavonoids

    NASA Astrophysics Data System (ADS)

    Souza, Rubens F. V. de; De Giovani, Wagner F.

    2005-07-01

    The synthesis, electrochemical and spectral (UV-vis, 1H NMR, IR, fluorescence) properties as well as thermal behaviors of Al(III) and Zn(II) complexes with the flavonoids quercetin (H 2L 1), rutin (H 2L 2) and galangin (HL 3) are presented. The complexes may be formulated as [Al 2(L 1)(H 2O) 8]Cl 4, [Al 3(L 2) 2(H 2O) 12]Cl 5, [Al(L 3)(H 2O) 4]Cl 2, [Zn 2(L 1)(H 2O) 4]Cl 2, [Zn 3(L 2) 2(H 2O) 6]Cl 2 and [Zn(L 3)(H 2O) 2]Cl. The higher fluorescence intensities of the complexes related to the free flavonoids, are attributed to the coordination of the ligands to the small, highly charged Al(III) and Zn(II) ions. The coordination effectively increases the rigidity of the ligand structure and increases the fluorescence quantum yield by reducing the probability of non-radiative energy dissipation process. Antioxidant activities of the compounds were also investigated under an electrochemical point of view. The cyclic voltammetric data show a considerable decrease of the oxidation potentials of the complexes related to that of the free flavonoids. Thus, the flavonoid-metal complexes are more effective antioxidants than the free flavonoids.

  9. Electro-Optical Properties Characterization of Fish Type III Antifreeze Protein

    PubMed Central

    Salvay, Andrés G.; Santos, Javier

    2008-01-01

    Antifreeze proteins (AFPs) are ice-binding proteins that depress the freezing point of water in a non-colligative manner without a significant modification of the melting point. Found in the blood and tissues of some organisms (such as fish, insects, plants, and soil bacteria), AFPs play an important role in subzero temperature survival. Fish Type III AFP is present in members of the subclass Zoarcoidei. AFPIII are small 7-kDa—or 14-kDa tandem—globular proteins. In the present work, we study the behavior of several physical properties, such as the low-frequency dielectric permittivity spectrum, circular dichroism, and electrical conductivity of Fish Type III AFP solutions measured at different concentrations. The combination of the information obtained from these measurements could be explained through the formation of AFP molecular aggregates or, alternatively, by the existence of some other type of interparticle interactions. Thermal stability and electro-optical behavior, when proteins are dissolved in deuterated water, were also investigated. PMID:19669526

  10. Synthesis, structure, luminescent, and magnetic properties of carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2] (Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato).

    PubMed

    Ehama, Kiyomi; Ohmichi, Yusuke; Sakamoto, Soichiro; Fujinami, Takeshi; Matsumoto, Naohide; Mochida, Naotaka; Ishida, Takayuki; Sunatsuki, Yukinari; Tsuchimoto, Masanobu; Re, Nazzareno

    2013-11-04

    Carbonato-bridged Zn(II)2Ln(III)2 complexes [(μ4-CO3)2{Zn(II)L(n)Ln(III)(NO3)}2]·solvent were synthesized through atmospheric CO2 fixation reaction of [Zn(II)L(n)(H2O)2]·xH2O, Ln(III)(NO3)3·6H2O, and triethylamine, where Ln(III) = Gd(III), Tb(III), Dy(III); L(1) = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, L(2) = N,N'-bis(3-ethoxy-2-oxybenzylidene)-1,3-propanediaminato. Each Zn(II)2Ln(III)2 structure possessing an inversion center can be described as two di-μ-phenoxo-bridged {Zn(II)L(n)Ln(III)(NO3)} binuclear units bridged by two carbonato CO3(2-) ions. The Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of L(n) and one oxygen atom of a bridging carbonato ion at the axial site. Ln(III) ion is coordinated by nine oxygen atoms consisting of four from the deprotonated Schiff-base L(n), two from a chelating nitrate, and three from two carbonate groups. The temperature-dependent magnetic susceptibilities in the range 1.9-300 K, field-dependent magnetization from 0 to 5 T at 1.9 K, and alternating current magnetic susceptibilities under the direct current bias fields of 0 and 1000 Oe were measured. The magnetic properties of the Zn(II)2Ln(III)2 complexes are analyzed on the basis of the dicarbonato-bridged binuclear Ln(III)-Ln(III) structure, as the Zn(II) ion with d(10) electronic configuration is diamagnetic. ZnGd1 (L(1)) and ZnGd2 (L(2)) show a ferromagnetic Gd(III)-Gd(III) interaction with J(Gd-Gd) = +0.042 and +0.028 cm(-1), respectively, on the basis of the Hamiltonian H = -2J(Gd-Gd)ŜGd1·ŜGd2. The magnetic data of the Zn(II)2Ln(III)2 complexes (Ln(III) = Tb(III), Dy(III)) were analyzed by a spin Hamiltonian including the crystal field effect on the Ln(III) ions and the Ln(III)-Ln(III) magnetic interaction. The Stark splitting of the ground state was so evaluated, and the energy pattern indicates a strong easy axis (Ising type) anisotropy. Luminescence spectra of Zn(II)2Tb(III)2 complexes were observed, while those

  11. Synthesis, Physicochemical Properties, and Antimicrobial Studies of Iron (III) Complexes of Ciprofloxacin, Cloxacillin, and Amoxicillin

    PubMed Central

    Ajali, Uzoechi; Ukoha, Pius O.

    2014-01-01

    Iron (III) complexes of ciprofloxacin, amoxicillin, and cloxacillin were synthesized and their aqueous solubility profiles, relative stabilities, and antimicrobial properties were evaluated. The complexes showed improved aqueous solubility when compared to the corresponding ligands. Relative thermal and acid stabilities were determined spectrophotometrically and the results showed that the complexes have enhanced thermal and acid stabilities when compared to the pure ligands. Antimicrobial studies showed that the complexes have decreased activities against most of the tested microorganisms. Ciprofloxacin complex, however, showed almost the same activity as the corresponding ligand. Job's method of continuous variation suggested 1 : 2 metals to ligand stoichiometry for ciprofloxacin complex but 1 : 1 for cloxacillin complex. PMID:25505991

  12. Electronic structure and spectral properties of terbium(III) nitrate complex with hexamethylphosphoramide.

    PubMed

    Kharchenko, Valerii I; Kurbatov, Ilya A; Cherednichenko, Alexander I; Mirochnik, Anatoly G; Zhikhareva, Polina A

    2017-03-05

    Spectral properties of terbium(III) nitrate complex with hexamethylphosphoramide have been studied by quantum-chemical methods within the density functional theory and methods of luminescent and X-ray photoelectron spectroscopy. Analysis of the luminescence excitation spectrum of the complex has indicated the absence of intramolecular transfer of electronic excitation energy from the ligand levels to the resonance levels of the rare earth central ion, so luminescence of the complex is associated with the electronic f-f-transitions of Tb(3+) ion (transitions (5)D4→(7)FJ, J=3-6). According to quantum-chemical modeling of the excited singlet and triplet levels of the complex, the excitation energy transfer from the ligands onto the central ion does not occur because of the significant difference of energies of their excited states.

  13. Electronic structure and spectral properties of terbium(III) nitrate complex with hexamethylphosphoramide

    NASA Astrophysics Data System (ADS)

    Kharchenko, Valerii I.; Kurbatov, Ilya A.; Cherednichenko, Alexander I.; Mirochnik, Anatoly G.; Zhikhareva, Polina A.

    2017-03-01

    Spectral properties of terbium(III) nitrate complex with hexamethylphosphoramide have been studied by quantum-chemical methods within the density functional theory and methods of luminescent and X-ray photoelectron spectroscopy. Analysis of the luminescence excitation spectrum of the complex has indicated the absence of intramolecular transfer of electronic excitation energy from the ligand levels to the resonance levels of the rare earth central ion, so luminescence of the complex is associated with the electronic f-f-transitions of Tb3 + ion (transitions 5D4 → 7FJ, J = 3-6). According to quantum-chemical modeling of the excited singlet and triplet levels of the complex, the excitation energy transfer from the ligands onto the central ion does not occur because of the significant difference of energies of their excited states.

  14. Morphological, Thermal, and Rheological Properties of Starches from Maize Mutants Deficient in Starch Synthase III.

    PubMed

    Zhu, Fan; Bertoft, Eric; Li, Guantian

    2016-08-31

    Morphological, thermal, and rheological properties of starches from maize mutants deficient in starch synthase III (SSIII) with a common genetic background (W64A) were studied and compared with the wild type. SSIII deficiency reduced granule size of the starches from 16.7 to ∼11 μm (volume-weighted mean). Thermal analysis showed that SSIII deficiency decreased the enthalpy change of starch during gelatinization. Steady shear analysis showed that SSIII deficiency decreased the consistency coefficient and yield stress during steady shearing, whereas additional deficiency in granule-bound starch synthase (GBSS) increased these values. Dynamic oscillatory analysis showed that SSIII deficiency decreased G' at 90 °C during heating and increased it when the paste was cooled to 25 °C at 40 Hz during a frequency sweep. Additional GBSS deficiency further decreased the G'. Structural and compositional bases responsible for these changes in physical properties of the starches are discussed. This study highlighted the relationship between SSIII and some physicochemical properties of maize starch.

  15. Probing the magnetic and magnetothermal properties of M(II)-Ln(III) complexes (where M(II) = Ni or Zn; Ln(III) = La or Pr or Gd).

    PubMed

    Ahmed, Naushad; Das, Chinmoy; Vaidya, Shefali; Srivastava, Anant Kumar; Langley, Stuart K; Murray, Keith S; Shanmugam, Maheswaran

    2014-12-14

    We establish the coordination potential of the Schiff base ligand (2-methoxy-6-[(E)-2'-hydroxymethyl-phenyliminomethyl]-phenolate (H2L)) via the isolation of various M(II)-Ln(III) complexes (where M(II) = Ni or Zn and Ln(III) = La or Pr or Gd). Single crystals of these five complexes were isolated and their solid state structures were determined by single crystal X-ray diffraction. Structural determination revealed molecular formulae of [NiGd(HL)2(NO3)3] (1), [NiPr(HL)2(NO3)3] (2) and [Ni2La(HL)4(NO3)](NO3)2 (3), [Zn2Gd(HL)4(NO3)](NO3)2 (4), and [Zn2Pr(HL)4(NO3)](NO3)2 (5). Complexes and were found to be neutral heterometallic dinuclear compounds, whereas 3-5 were found to be linear heterometallic trinuclear cationic complexes. Direct current (dc) magnetic susceptibility and magnetization measurements conclusively revealed that complexes 1 and 4 possess a spin ground state of S = 9/2 and 7/2 respectively. Empirically calculated ΔχMT derived from the variable temperature susceptibility data for all complexes undoubtedly indicates that the Ni(II) ion is coupled ferromagnetically with the Gd(III) ion, and antiferromagnetically with the Pr(III) ion in 1 and 2 respectively. The extent of the exchange interaction for was estimated by fitting the magnetic susceptibility data using the parameters (g = 2.028, S = 9/2, J = 1.31 cm(-1) and zJ = +0.007), supporting the phenomenon observed in an empirical approach. Similarly using a HDVV Hamiltonian, the magnetic data of 3 and 4 were fitted, yielding parameters g = 2.177, D = 3.133 cm(-1), J = -0.978 cm(-1), (for 3) and g = 1.985, D = 0.508 cm(-1) (for 4). The maximum change in magnetic entropy (-ΔSm) estimated from the isothermal magnetization data for was found to be 5.7 J kg(-1) K(-1) (ΔB = 7 Tesla) at 7.0 K, which is larger than the -ΔSm value extracted from 4 of 3.5 J kg(-1) K(-1) (ΔB = 7 Tesla) at 15.8 K, revealing the importance of the exchange interaction in increasing the overall ground state of a molecule for

  16. Experimental and theoretical approach of photophysical properties of lanthanum(III) and erbium(III) complexes of tris(methoxymethyl)-5-oxine podant.

    PubMed

    Akbar, Rifat; Baral, Minati; Kanungo, B K

    2014-08-14

    With the aim of evaluating the coordination behavior of a novel polydentate tripodal ligand, 5-[[3-[(8-hydroxy-5-quinolyl)methoxy]-2-[(8-hydroxy-5-quinolyl)methoxymethyl]-2-methyl propoxy]methyl]quinolin-8-ol (TMOM5OX), towards La(III) and Er(III) metal ions, the detailed investigations of photophysical properties by theoritical and experimental (potentiometric, UV-visible and fluorescence spectrophotometry) methods were carried out. TMOM5OX has been found to form protonated complex [Ln(H4L)](4+) (Ln=La or Er) below pH 3.8, which consecutively deprotonates through one-proton processes with rise of pH. The formation constants (logβ) of neutral complexes have been determined to be 36.42 (LaL) and 35.76, 37.62 (for ErL and ErL2, respectively) and the pLn (pLn=-log[Ln(3+)]) values of 24.6 and 27.1 for La(III) and Er(III) ions, respectively, calculated at pH 7.4, indicating TMOM5OX is a good lanthanide synthetic chelator. The absorption spectroscopy of these complexes show marked spectral variations due to characteristic lanthanide transitions, which support the use of TMOM5OX as a sensitive optical pH based sensor to detect Ln(III) metal ions in biological systems. In addition, these complexes have also been shown to exhibit strong green fluorescence allowing simultaneous sensing within the visible region under physiological pH in competitive medium for both La(III) and Er(III) ions. The intense fluorescence from these compounds were revealed to intermittently get quenched under acidic and basic conditions due to the photoinduced intramolecular electron transfer from excited 8-hydroxyquinoline (8-HQ) moiety to metal ion, just an opposite process. This renders these compounds the OFF-ON-OFF type of pH-dependent fluorescent sensors. The complexes coordination geometries were optimized using the sparkle/PM6 model and the theoretical spectrophotometric studies were carried out in order to validate the experimental findings, based on ZINDO/S methodology at configuration

  17. Magnetic coupling in discrete cyano-bridged Mn(III)-Fe(III) motifs: synthesis, crystal structure, magnetic properties and theoretical study.

    PubMed

    Visinescu, Diana; Toma, Luminita Marilena; Cano, Joan; Fabelo, Oscar; Ruiz-Pérez, Catalina; Labrador, Ana; Lloret, Francesc; Julve, Miguel

    2010-05-28

    The preparation, crystal structures and magnetic properties of the heterobimetallic complexes of formula [Mn(III)(n-MeOsalen)(H(2)O)(mu-CN)Fe(III)(bpym)(CN)(3)]·mH(2)O with n = m = 3 (1) and n = 4 and m = 2 (2) [n-MeOsalen(2-) = N,N'-ethylenebis(n-methoxysalicylideneiminate) dianion and bpym = 2,2'-bipyrimidine] are reported. 1 and 2 are dinuclear neutral species where the cyano-bearing low-spin unit [Fe(III)(bpym)(CN)(4)](-) acts as a monodentate ligand towards the [Mn(III)(SB)(solv)(x)](+) entity (SB = tetradentate Schiff-base) through one of its four cyano groups. Adjacent heterobimetallic units are interlinked through hydrogen bonds involving the coordinated water molecule of one dinuclear unit and the phenolate oxygen atoms of the neighbouring one to afford pairs of dimers with values of the interdimer Mn···Mn distance of 4.925(20) (1) and 5.0508(25) Å (2). The analysis of the magnetic data of 1 and 2 in the temperature range 1.9-300 K shows the coexistence of weak ferro- [J = +2.95 (1) and +3.88 cm(-1) (2)] and antiferromagnetic interactions [j = -1.91 (1) and -0.70 cm(-1) (2)] through the single cyano bridge and hydrogen bonds, respectively (the Hamiltonian being of the type Ĥ = J[Ŝ(Fe)·Ŝ(Mn) + Ŝ(Fe')·Ŝ(Mn')] -jŜ(Mn)·Ŝ(Mn')). Theoretical calculations using methods based on density functional theory (DFT) have been used to substantiate the nature and magnitude of the magnetic coupling observed in 1 and 2 and also to analyze the dependence of the magnetic coupling on the structural parameters for the Fe-C-N-Mn skeleton. An extension of the calculations to selected examples of heterobimetallic Fe(III)-C-N-Mn(III) compounds with a different number of cyano groups on the low-spin iron(III) precursor has been carried out allowing us to illustrate the influence of the symmetry of the magnetic orbital of the iron center on the magnetic coupling in this heterobimetallic unit.

  18. The Comparative Characteristic of Components in the Iiib-Iii Pairs According to the Observation Data Obtained by Radio Telescope URAN-2

    NASA Astrophysics Data System (ADS)

    Brazhenko, A. I.; Melnik, V. N.; Konovalenko, A. A.; Dorovskiy, V. V.; Vashchishin, R. V.; Frantsuzenko, A. V.; Rucker, G.

    In this paper we analyze the properties of type IIIb and type III bursts in IIIb-III pairs observed by radio telescope URAN-2 at frequencies 16-32 MHz. We discuss pro and contra of harmonic phenomenon of decameter IIIb-III pairs.

  19. Luminescence properties of compounds of europium(III) with quinaldic acid and phosphor-containing neutral ligands

    NASA Astrophysics Data System (ADS)

    Kalinovskaya, I. V.

    2016-06-01

    Luminescent complex mixed-ligand compounds of europium(III) with quinaldic acid and phosphor- containing neutral ligands have been obtained. Their composition and structure have been determined. The thermal and spectral-luminescent properties of the obtained complex mixed-ligand compounds of europium( III) have been studied. It is shown that, during thermolysis, a water molecule and neutral ligand are detached in two stages with endothermic effects. It is established that quinaldinate ion is coordinated to europium(III) ion in a bidentate fashion. The Stark structure of the 5 D 0-7 F j ( j = 0, 1, 2) transitions in low-temperature luminescence spectra of complex compounds of europium(III) has been analyzed.

  20. Purification, enzymatic properties, and active site environment of a novel manganese(III)-containing acid phosphatase.

    PubMed

    Sugiura, Y; Kawabe, H; Tanaka, H; Fujimoto, S; Ohara, A

    1981-10-25

    A new manganese-containing acid phosphatase has been isolated and crystallized from sweet potato tubers. The pure enzyme contains one atom of manganese per Mr = 110,000 polypeptide and shows phosphatase activity toward various phosphate substrates. The pH optimum of the enzyme was 5.8 and the enzyme activity was inhibited by Cu2+, Zn2+, Hg2+, AsO43-, and MoO42-. This stable metalloenzyme is red-violet in color with an intense absorption band at 515 nm (epsilon - 2460). Our electronic, circular dichroism, and electron spin resonance findings strongly indicate that the Mn-valence state of the native enzyme is trivalent. When the Mn-enzyme is excited by the 5145 A line of Ar+ laser, prominent Raman lines at 1230, 1298, 1508, and 1620 cm-1 were detected. This Raman spectrum can probably be interpreted in terms of internal vibration of a coordinated tyrosine phenolate anion. The tryptophan-modified enzyme showed a positive Raman band at 370 cm-1, which is preferentially assigned to a Mn(III)-S streching mode. The modification of the Mn-enzyme by N-bromosuccinimide led to a large decrease in the fluorescence intensity of 335 nm which was dominated by its tryptophan residues within a considerable hydrophobic environment. The acid phosphatase activity was significantly decreased by the tryptophan modification. With respect to the active site donor sets, the Mn(III)-containing acid phosphatase is distinctly different from the Zn(II)-containing alkaline phosphatase. Of interest is also the appreciable similarity of some enzymatic and spectroscopic properties between the present enzyme and uteroferrin.

  1. Pathogenesis of Raynaud's phenomenon.

    PubMed

    Herrick, A L

    2005-05-01

    The pathogenesis of Raynaud's phenomenon is not fully understood. However, the last 20 yr have witnessed enormous increases in our understanding of different mechanisms which, singly or in combination, may contribute. A key point is that Raynaud's phenomenon can be either primary (idiopathic) or secondary to a number of underlying conditions, and that the pathogenesis and pathophysiology vary between these conditions. This review concentrates upon those subtypes of Raynaud's phenomenon of most interest to rheumatologists: systemic sclerosis-related Raynaud's phenomenon, primary Raynaud's phenomenon and Raynaud's phenomenon secondary to hand-arm vibration syndrome. In this review, I shall discuss the main mechanisms thought to be important in pathophysiology under the three broad headings of 'vascular', 'neural' and 'intravascular'. While these are false distinctions because all interrelate, they facilitate discussion of the key elements: the blood vessel wall (particularly the endothelium), the neural control of vascular tone, and the many circulating factors which can impair blood flow and/or cause endothelial injury. Vascular abnormalities include those of both structure and function. Neural abnormalities include deficiency of the vasodilator calcitonin gene-related peptide (released from sensory afferents), alpha(2)-adrenoreceptor activation (possibly with up-regulation of the normally 'silent' alpha(2C)-adrenoreceptor) and a central nervous system component. Intravascular abnormalities include platelet activation, impaired fibrinolysis, increased viscosity and probably oxidant stress. As our understanding of the pathophysiology of Raynaud's phenomenon increases, so do our possibilities for identifying effective treatments.

  2. Theoretical Study of Material and Device Properties of Group-III Nitrides

    NASA Astrophysics Data System (ADS)

    Yan, Qimin

    Group-III nitride semiconductors, including AlN, GaN, InN, and their alloys, are ideal materials for solid state lighting applications. Current research focuses on improving the efficiency by improvements in materials quality and novel device designs, for instance based on nonpolar and semipolar growth. The motivation for our work is to assist and guide the experimental development of high-performance solid state optoelectronic devices by performing computational studies. Our investigations range from basic structural and electronic properties of nitrides to the effects of device design on efficiency of light emission. In the area of fundamental properties, we performed a systematic study of strain effects on the electronic band structures of the group-III-nitrides (AlN, GaN and InN) using density-functional theory with an advanced hybrid functional as well as using the quasiparticle GW method. We present a complete set of deformation potentials that allows us to predict the band positions of group-III nitrides and their alloys (InGaN and AlGaN) under realistic strain conditions. We then employed the resulting first-principles deformation potentials to predict the effects of strain on transition energies and valence-band structures of c-plane, nonpolar, and semipolar InGaN alloy layers grown on GaN substrates, with particular attention to the role of strain in the polarized light emission. We also investigated the role of native defects in the optical properties of GaN and AlN, again using hybrid density-functional calculations. We established that complexes between Mg and nitrogen vacancies lead to the broad red luminescence that has often been observed in GaN. We find that isolated nitrogen vacancies can give rise to broad emission peaked at 2.18 eV. We show that isolated aluminum vacancies lead to an absorption peak at 3.43 eV and an emission peak at 2.73 eV. We also find that the complexes can give rise to absorption peaked at 3.97 eV and

  3. Deliberate synthetic control over the excited-state properties of cyclometalated iridium(III) complexes with materials applications

    NASA Astrophysics Data System (ADS)

    Lowry, Michael Scott

    Luminescence color tuning is an area of great interest to materials research due to the expanding role of emissive complexes in a variety of optoelectronic and photocatalytic applications. This thesis contains an examination of structure-property relationships with luminescent iridium(III) complexes in order to synthetically control their photophysical and electrochemical properties and to optimize their performance in diverse fields, such as organic light-emitting diodes (OLEDs), photochemical water splitting, and chiroptical materials. A combinatorial approach was developed to accelerate the discovery of useful luminophores, and over 300 heteroleptic iridium(III) complexes have been prepared and characterized for their photophysical properties. Considerable attention has been placed on interpreting the effect of structural modifications at the ligand periphery and will be discussed in the context of tailoring the luminescent behavior of novel materials. An area that has seen tremendous growth throughout the tenure of this work is the field of OLED devices. Single-layer electroluminescent device constructed with an iridium(III) complexes were observed for the first time, and the color of these devices was tuned from yellow (lambdamax = 560 nm) to blue-green (lambdamax = 500 nm) by strategically modifying the iridium(III) luminophore. A computational method for predicting the emission energy of novel materials was also developed and will be discussed. A second field into which this work has endeavored is the area of photoinduced hydrogen production, specifically the design and optimization of iridium(III) photocatalysts for reducing protons to molecular hydrogen. Seven iridium(III) complexes were examined as photosensitizers, and a material expressing a nearly 100-fold increase in its ability to catalyze hydrogen production over Ru(bpy) 32+ is reported. A final extension of this work examined the chiroptical properties of enantiomerically pure iridium(III

  4. A new phenomenon?

    NASA Astrophysics Data System (ADS)

    Ganci, S.

    2017-03-01

    This letter describes an interesting optical phenomenon engaging the reflected images of a new tube LED lamp (an array of high luminosity LEDs substituting the old fluorescent lamps) on any convex glossy black surface.

  5. Treatment of Raynaud's phenomenon.

    PubMed

    García-Carrasco, Mario; Jiménez-Hernández, Mario; Escárcega, Ricardo O; Mendoza-Pinto, Claudia; Pardo-Santos, Rodrigo; Levy, Roger; Maldonado, Claudio Galarza; Chávez, Gonzalo Pérez; Cervera, Ricard

    2008-10-01

    Raynaud's phenomenon is an episodic vasospasm of the peripheral arteries, causing pallor followed by cyanosis and redness with pain and sometimes paraesthesia, and, rarely, ulceration of the fingers and toes. Primary or idiopathic Raynaud's phenomenon (Raynaud's disease) occurs without an underlying disease. Secondary Raynaud's phenomenon (Raynaud's syndrome) occurs in association with an underlying disease. Initially conservative, non-pharmacologic approach is important for these patients, although pharmacologic therapy may ultimately be necessary. Advances in vascular physiology have showed the role of the endothelium as well as endothelium-independent mechanisms in the altered vasoregulation of Raynaud's phenomenon. This has opened promising therapeutic avenues, and it is likely that therapies targeted towards specific pathophysiologic steps become available in the near future.

  6. The Root Pressure Phenomenon

    ERIC Educational Resources Information Center

    Marsh, A. R.

    1972-01-01

    Describes experiments demonstrating that root pressure in plants is probably controlled by a circadian rhythm (biological clock). Root pressure phenomenon plays significant part in water transport in contradiction with prevalent belief. (PS)

  7. Proteomic and Properties Analysis of Botanical Insecticide Rhodojaponin III-Induced Response of the Diamondback Moth, Plutella xyllostella (L.)

    PubMed Central

    Dong, Xiaolin; Zhai, Yifan; Hu, Meiying; Zhong, Guohua; Huang, Wanjun; Zheng, Zhihua; Han, Pengfei

    2013-01-01

    Background Rhodojaponin III, as a botanical insecticide, affects a wide variety of biological processes in insects, including reduction of feeding, suspension of development, and oviposition deterring of adults in a dose-dependent manner. However, the mode of these actions remains obscure. Principal Findings In this study, a comparative proteomic approach was adopted to examine the effect of rhodojaponin III on the Plutella xyllostella (L.). Following treating 48 hours, newly emergence moths were collected and protein samples were prepared. The proteins were separated by 2-DE, and total 31 proteins were significantly affected by rhodojaponin III compared to the control identified by MALDI-TOF/TOF-MS/MS. These differentially expressed proteins act in the nervous transduction, odorant degradation and metabolic change pathways. Further, gene expression patterns in treated and untreated moths were confirmed by qRT-PCR and western blot analysis. RNAi of the chemosensory protein (PxCSP) gene resulted in oviposition significantly increased on cabbage plants treated with rhodojaponin III. Conclusions These rhodojaponin III-induced proteins and gene properties analysis would be essential for a better understanding of the potential molecular mechanism of the response to rhodojaponin III from moths of P. xylostella. PMID:23861792

  8. CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: The phenomenon of even bulk mode variance in a ferromagnetic A-A bilayer system

    NASA Astrophysics Data System (ADS)

    Zhou, Wen-Ping; Yun, Guo-Hong; Liang, Xi-Xia

    2009-12-01

    The eigenproblems of spin waves in a symmetrical ferromagnetic bilayered system with periodic boundary conditions are solved using the interface-rescaling approach (IRA). The results show that interface coupling between two sublayers would not change the excitation energy of odd bulk modes, but change excitation energy of even bulk modes. We call this peculiar phenomenon the phenomenon of even bulk mode variance (PEBMV). There are two kinds of mechanisms which cause PEBMV: phase reversal and phase translation of the magnon at the interface, corresponding, respectively, to the antiferromagnetic and ferromagnetic interface coupling cases. PEBMV embodies the selective effect of the interface on different bulk magnons.

  9. A Midlatitude Cirrus Cloud Climatology from the Facility for Atmospheric Remote Sensing. Part III: Radiative Properties

    SciTech Connect

    Sassen, K.; Comstock, Jennifer M.

    2001-08-01

    In Part III of a series of papers describing the extended time high-cloud observations from the University of Utah Facility for Atmospheric Remote Sensing (FARS) supporting the First International Satellite Cloud Climatology Project (ISCCP) Regional Experiment, the visible and infrared radiative properties of cirrus clouds over Salt Lake City, Utah, are examined. Using {approx}860 h of combined ruby (0.694 {micro}m) lidar and midinfrared (9.5-11.5 {micro}m) radiometer data collected between 1992 and 1999 from visually identified cirrus clouds, the visible optical depths {tau} and infrared layer emittance epsilon of the varieties of midlatitude cirrus are characterized. The mean and median values for the cirrus sample are 0.75 {+-} 0.91 and 0.61 for {tau}, and 0.30 {+-} 0.22 and 0.25 for epsilon. Other scattering parameters studied are the visible extinction and infrared absorption coefficients, and their ratio, and the lidar backscatter-to-extinction ratio, which has a mean value of 0.041 sr{sup -1}. Differences among cirrus clouds generated by general synoptic (e.g., jet stream), thunderstorm anvil, and orographic mechanisms are found, reflecting basic cloud microphysical effects. The authors draw parameterizations in terms of midcloud temperature T{sub m} and physical cloud thickness {Delta}z for epsilon and {tau}: both macrophysical variables are needed to adequately address the impact of the adiabatic process on ice cloud content, which modulates radiative transfer as a function of temperature. For the total cirrus dataset, the authors find epsilon = 1 -exp [-8.5 x 10{sup -5} (T{sub m} + 80 C) {Delta}z]. These parameterizations, based on a uniquely comprehensive dataset, hold the potential for improving weather and climate model predictions, and satellite cloud property retrieval methods.

  10. Spectral and electroluminescent properties of coordination compounds of terbium (III) with ibuprofen (in solid form, chloroform solutions, and polyvinylcarbazole films)

    NASA Astrophysics Data System (ADS)

    Samsonova, L. G.; Kopylova, T. N.; Degtyarenko, K. M.; Ponarin, N. V.; Meshkova, S. B.; Zheltvai, I. I.

    2015-08-01

    Spectral properties of terbium (III) complexes with composition of TbL3DL, where L is an anion of d,l-2-(4-isobutylphenyl)propanoic acid (ibuprofen) and DL is 2,2'-dipyridyl (Dipy), 1,10-phenanthroline (Phen), or triphenylphosphine oxide (TPPO), have been studied in a solid form, chloroform solutions, and polyvinylcarbazole (PVC) films. It has been demonstrated that, in PVC films, occupation of the emitting level of terbium (III) involves the participation of polymer. The emission decay lifetimes of terbium in the chloroform solutions and PVC films have been measured. The possibility of the appearance of electroluminescence of complexes in PVC films has been studied.

  11. Phthalocyanine supported dinuclear Ln(III) complexes: the solvent-induced change of magnetic properties in dysprosium(iii) analogues.

    PubMed

    Ge, Jing-Yuan; Wang, Hai-Ying; Li, Jing; Xie, Jia-Ze; Song, You; Zuo, Jing-Lin

    2017-02-24

    Three dinuclear lanthanide complexes, [Ln2(thd)4Pc]·2C6H6 (Hthd = 2,2,6,6-tetramethylheptanedione, Ln = Sm (1), Tb (2), Dy (3)), have been synthesized based on phthalocyanine (Pc). They can be reversibly transformed into [Ln2(thd)4Pc] (Ln = Sm (1'), Tb (2'), Dy (3')) via desolvation and resolvation of the lattice benzene molecules. This change generates dramatic influences on the structural and magnetic properties of the dysprosium analogue. In complex 3, one crystallographically independent metal center is observed, and it exhibits a single relaxation process of magnetization with an energy barrier of 55.7 K. Upon desolvation, the resulting complex 3' contains two types of metal centers, and shows the field-induced single-molecule magnetic behavior with two thermally activated magnetic relaxation processes. The anisotropy barriers for 3' are as high as 63.3 K and 109.6 K, respectively. This work confirms that the solvated molecules can finely tune the magnetic relaxation mechanisms.

  12. Synthesis, crystal structures, and properties of oxovanadium(IV)-lanthanide(III) heteronuclear complexes.

    PubMed

    Shi, Wei; Chen, Xiao-Yan; Zhao, Yan-Nan; Zhao, Bin; Cheng, Peng; Yu, Ao; Song, Hai-Bin; Wang, Hong-Gen; Liao, Dai-Zheng; Yan, Shi-Ping; Jiang, Zong-Hui

    2005-08-19

    A new series of oxovanadium(IV)-lanthanide(III) heteronuclear complexes [Yb(H2O)8]2[(VO)2(TTHA)](3)21 H2O (1), {[Ho(H2O)7(VO)2(TTHA)][(VO)2(TTHA)](0.5)} 8.5 H2O (2), {[Gd(H2O)7(VO)2(TTHA)][(VO)2(TTHA)](0.5)}8.5 H2O (3), {[Eu(H2O)7][(VO)2(TTHA)](1.5)} 10.5 H2O (4), and [Pr2(H2O)6(SO4)2][(VO)2(TTHA)] (5) (H6TTHA=triethylenetetraaminehexaacetic acid) were prepared by using the bulky flexible organic acid H(6)TTHA as structure-directing agent. X-ray crystallographic studies reveal that they contain the same [(VO)2(TTHA)]2- unit as building block, but the Ln3+ ion lies in different coordination environments. Although the lanthanide ions always exhibit similar chemical behavior, the structures of the complexes are not homologous. Compound 1 is composed of a [Yb(H2O)8]3+ ion and a [(VO)2(TTHA)]2- ion. Compounds 2 and 3 are isomorphous; both contain a trinuclear [Ln(H2O)7(VO)2(TTHA)]+ (Ln=Ho for 2 and Gd for 3) ion and a [(VO)2(TTHA)]2- ion. Compound 4 is an extended one-dimensional chain, in which each Eu3+ ion links two [(VO)2(TTHA)]2- ions. For 5, the structure is further assembled into a three-dimensional network with an interesting framework topology comprising V2Pr2 and V4Pr2 heterometallic lattices. Moreover, 4 and 5 are the first oxovanadium(IV)-lanthanide(III) coordination polymers and thus enlarge the realm of 3d-4f complexes. The IR, UV/Vis, and EPR spectra and the magnetic properties of the heterometallic complexes were studied. Notably, 2 shows unusual ferromagnetic interactions between the VO2+ and Ho3+ ions.

  13. Synthesis, characterization and DNA-binding properties of La(III) complex of chrysin.

    PubMed

    Zeng, Yi-Bo; Yang, Nan; Liu, Wei-Sheng; Tang, Ning

    2003-11-01

    A novel La(III) complex of chrysin (5,7-dihydroxyflavone) was synthesized and characterized by UV, IR, 1H NMR, thermogravimetry/differential thermal analysis (TG/DTA) and elementary analyses. The interactions of the La(III) complex and chrysin with calf thymus DNA were investigated by spectrophotometric methods and viscosity measurements. The intrinsic binding constants of La(III) complex and chrysin are 1.29 x 10(6) and 5.44 x 10(5) M(-1), respectively. Experimental results indicated that La(III) complex and chrysin can both bind to DNA by intercalation modes, but the binding affinity of La(III) complex is much higher than that of chrysin. Comparative antitumor activities of La(III) complex and chrysin were tested by MTT and SRB methods. The results show that at the concentration of 10 microM for chrysin and La(III) complex, the inhibitory ratios of La(III) complex against the tested tumor cells were higher than those of chrysin.

  14. Fluorescence studies, DNA binding properties and antimicrobial activity of a dysprosium(III) complex containing 1,10-phenanthroline.

    PubMed

    Khorasani-Motlagh, Mozhgan; Noroozifar, Meissam; Moodi, Asieh; Niroomand, Sona

    2013-10-05

    Luminescence and binding properties of dysprosium(III) complex containing 1,10-phenanthroline (phen), [Dy(phen)2(OH2)3Cl]Cl2⋅H2O with DNA has been studied by electronic absorption, emission spectroscopy and viscosity measurement. The thermodynamic studies suggest that the interaction process to be endothermic and entropically driven, which indicates that the dysprosium(III) complex might interact with DNA by a non intercalation binding mode. Additionally, the competitive fluorescence study with ethidium bromide and also the effect of iodide ion and salt concentration on fluorescence of the complex-DNA system is investigated. Experimental results indicate that the Dy(III) complex strongly binds to DNA, presumably via groove binding mode. Furthermore, the complex shows a potent antibacterial activity and DNA cleavage ability.

  15. Correlation Between Structural, Spectroscopic, and Reactivity Properties Within a Series of Structurally Analogous Metastable Manganese(III)-Alkylperoxo Complexes

    PubMed Central

    Coggins, Michael K.; Martin-Diaconescu, Vlad; DeBeer, Serena; Kovacs, Julie A.

    2013-01-01

    Manganese–peroxos are proposed as key intermediates in a number of important biochemical and synthetic transformations. Our understanding of the structural, spectroscopic, and reactivity properties of these metastable species is limited, however, and correlations between these properties have yet to be established experimentally. Herein we report the crystallographic structures of a series of structurally related metastable Mn(III)–OOR compounds, and examine their spectroscopic and reactivity properties. The four reported Mn(III)–OOR compounds extend the number of known end-on Mn(III)–(η1-peroxos) to six. The ligand backbone is shown to alter the metal–ligand distances and modulate the electronic properties key to bonding and activation of the peroxo. The mechanism of thermal decay of these metastable species is examined via variable-temperature kinetics. Strong correlations between structural (O–O and Mn⋯Npy,quin distances), spectroscopic (E(πv*(O–O) → Mn CT band), νO–O), and kinetic (ΔH‡ and ΔS‡) parameters for these complexes provide compelling evidence for rate-limiting O–O bond cleavage. Products identified in the final reaction mixtures of Mn(III)–OOR decay are consistent with homolytic O–O bond scission. The N-heterocyclic amines and ligand backbone (Et vs Pr) are found to modulate structural and reactivity properties, and O–O bond activation is shown, both experimentally and theoretically, to track with metal ion Lewis acidity. The peroxo O–O bond is shown to gradually become more activated as the N-heterocyclic amines move closer to the metal ion causing a decrease in π-donation from the peroxo πv*(O–O) orbital. The reported work represents one of very few examples of experimentally verified relationships between structure and function. PMID:23432090

  16. Redshift evolution of the dynamical properties of massive galaxies from SDSS-III/BOSS

    SciTech Connect

    Beifiori, Alessandra; Saglia, Roberto P.; Bender, Ralf; Senger, Robert; Thomas, Daniel; Maraston, Claudia; Steele, Oliver; Masters, Karen L.; Pforr, Janine; Tojeiro, Rita; Johansson, Jonas; Nichol, Robert C.; Chen, Yan-Mei; Wake, David; Bolton, Adam; Brownstein, Joel R.; Leauthaud, Alexie; Schneider, Donald P.; Skibba, Ramin; Pan, Kaike; and others

    2014-07-10

    We study the redshift evolution of the dynamical properties of ∼180, 000 massive galaxies from SDSS-III/BOSS combined with a local early-type galaxy sample from SDSS-II in the redshift range 0.1 ≤ z ≤ 0.6. The typical stellar mass of this sample is M{sub *} ∼2 × 10{sup 11} M{sub ☉}. We analyze the evolution of the galaxy parameters effective radius, stellar velocity dispersion, and the dynamical to stellar mass ratio with redshift. As the effective radii of BOSS galaxies at these redshifts are not well resolved in the Sloan Digital Sky Survey (SDSS) imaging we calibrate the SDSS size measurements with Hubble Space Telescope/COSMOS photometry for a sub-sample of galaxies. We further apply a correction for progenitor bias to build a sample which consists of a coeval, passively evolving population. Systematic errors due to size correction and the calculation of dynamical mass are assessed through Monte Carlo simulations. At fixed stellar or dynamical mass, we find moderate evolution in galaxy size and stellar velocity dispersion, in agreement with previous studies. We show that this results in a decrease of the dynamical to stellar mass ratio with redshift at >2σ significance. By combining our sample with high-redshift literature data, we find that this evolution of the dynamical to stellar mass ratio continues beyond z ∼ 0.7 up to z > 2 as M{sub dyn}/M{sub *} ∼(1 + z){sup –0.30±0.12}, further strengthening the evidence for an increase of M{sub dyn}/M{sub *} with cosmic time. This result is in line with recent predictions from galaxy formation simulations based on minor merger driven mass growth, in which the dark matter fraction within the half-light radius increases with cosmic time.

  17. The Leidenfrost Phenomenon

    ERIC Educational Resources Information Center

    Curzon, F. L.

    1978-01-01

    Describes four demonstrations of the Leidenfrost phenomenon; floating of liquid drops on their own vapor above a hot surface, delayed quenching of red-hot brass by water, explosion of vessels containing suspended liquid droplets, and momentary incombustibility of living tissue immersed in boiling oil. (Author/GA)

  18. Synthesis, structural characterization, luminescent properties and theoretical study of three novel lanthanide metal-organic frameworks of Ho(III), Gd(III) and Eu(III) with 2,5-thiophenedicarboxylate anion

    SciTech Connect

    Marques, Lippy F.; Correa, Charlane C.; Ribeiro, Sidney J.L.; Santos, Molíria V. dos; Dutra, José Diogo L.; Freire, Ricardo O.; Machado, Flávia C.

    2015-07-15

    In this paper, the synthesis of three new metal-organic frameworks of lanthanides (LnMOFs) ([Ln{sub 2}(2,5-tdc){sub 3}(dmso){sub 2}]·H{sub 2}O){sub n} (Ln=Ho (1); Gd (2); Eu (3); 2,5-tdc=2,5-thiophenedicarboxylate anion; dmso=dimethylsulfoxide), and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermogravimetric analysis are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. Crystal structure of (1) reveals that each lanthanide ion is seven-coordinated by oxygen atoms in an overall distorted capped trigonal – prismatic geometry. The 2,5-tdc{sup 2−} ligands connect four Ln(III) centers, adopting (κ{sup 1}–κ{sup 1})–(κ{sup 1}–κ{sup 1})–μ{sub 4} coordination mode, generating an 8-connected uninodal 3D network. In addition, theoretical studies for Eu(III) complex were performed using the Sparkle model for lanthanide complexes. - Graphical abstract: Three new metal-organic frameworks of lanthanides (LnMOFs) ([Ln{sub 2}(2,5-tdc){sub 3}(dmso){sub 2}]·H{sub 2}O){sub n} (Ln=Ho (1); Gd (2); Eu (3); 2,5-tdc=2,5-thiophenedicarboxylate anion; dmso=dimethylsulfoxide), were synthesized and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermogravimetric analysis are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. - Highlights: • Three new LnMOFs were synthesized and fully characterized. • Ho{sup 3+}, Gd{sup 3+} and Eu{sup 3+} complexes photoluminescence properties were investigated. • Theoretical approaches for Eu{sup 3+} complex luminescence has been performed. • An energy level diagram is used to establish the ligand-to-metal energy transfer. • These metal−organic frameworks can act as light conversion molecular devices.

  19. Synthesis and luminescence properties of iridium(III) azide- and triazole-bisterpyridine complexes.

    PubMed

    Goldstein, Daniel C; Peterson, Joshua R; Cheng, Yuen Yap; Clady, Raphael G C; Schmidt, Timothy W; Thordarson, Pall

    2013-07-26

    We describe here the synthesis of azide-functionalised iridium(III) bisterpyridines using the "chemistry on the complex" strategy. The resulting azide-complexes are then used in the copper(I)-catalysed azide-alkyne Huisgen 1,3-dipolar cycloaddition "click chemistry" reaction to from the corresponding triazole-functionalised iridium(III) bisterpyridines. The photophysical characteristics, including lifetimes, of these compounds were also investigated. Interestingly, oxygen appears to have very little effect on the lifetime of these complexes in aqueous solutions. Unexpectedly, sodium ascorbate acid appears to quench the luminescence of triazole-functionalised iridium(III) bisterpyridines, but this effect can be reversed by the addition of copper(II) sulfate, which is known to oxidize ascorbate under aerobic conditions. The results demonstrate that iridium(III) bisterpyridines can be functionalized for use in "click chemistry" facilitating the use of these photophysically interesting complexes in the modification of polymers or surfaces, to highlight just two possible applications.

  20. A NdIII enantiomeric pair: Synthesis, crystal structures and near-infrared luminescent properties

    NASA Astrophysics Data System (ADS)

    Li, Feng-Cai; Li, Xi-Li; Hu, Ming; Zhang, Xue-Li; Chen, Conghui; Zhu, Cancan

    2016-08-01

    Based on enantiopure bis-bidentate N-donor ligands (-)/(+)-2,5-bis(4,5-pinene- 2-pyridyl)pyrazine (LR/LS), a new pair of NdIII enantiomers with the formula Nd(dbm)3LR/S·2H2O (R-1 and S-1 being the isomers containing the LR and LS ligands, respectively, and dbm = dibenzoylmethanate) have been isolated and characterized by X-ray crystallography and spectroscopic methods. Notably, unlike our previously reported homodinuclear EuIII and DyIII complexes based on the identical ligands (LR and LS), the dinuclear NdIII congener have not been obtained by controlling the ligand-to-metal ratio as expected, the reason of which was elucidated in this work. The crystal structure analyses of R-1 and S-1 reveal that they are mononuclear NdIII complexes and crystallize in chiral space group P212121 of the orthorhombic system. Circular dichroic (CD) spectra confirmed their chiroptical activities and enantiomeric nature. The photoluminescence investigations showed that they display characteristic near-infrared (NIR) emissions of the NdIII ions with notable emitting lifetime value.

  1. Structural and optical properties of II-VI and III-V compound semiconductors

    NASA Astrophysics Data System (ADS)

    Huang, Jingyi

    This dissertation is on the study of structural and optical properties of some III-V and II-VI compound semiconductors. The first part of this dissertation is a study of the deformation mechanisms associated with nanoindentation and nanoscratching of InP, GaN, and ZnO crystals. The second part is an investigation of some fundamental issues regarding compositional fluctuations and microstructure in GaInNAs and InAlN alloys. In the first part, the microstructure of (001) InP scratched in an atomic force microscope with a small diamond tip has been studied as a function of applied normal force and crystalline direction in order to understand at the nanometer scale the deformation mechanisms in the zinc-blende structure. TEM images show deeper dislocation propagation for scratches along <110> compared to <100>. High strain fields were observed in <100> scratches, indicating hardening due to locking of dislocations gliding on different slip planes. Reverse plastic flow have been observed in <110> scratches in the form of pop-up events that result from recovery of stored elastic strain. In a separate study, nanoindentation-induced plastic deformation has been studied in c-, a-, and m-plane ZnO single crystals and c-plane GaN respectively, to study the deformation mechanism in wurtzite hexagonal structures. TEM results reveal that the prime deformation mechanism is slip on basal planes and in some cases, on pyramidal planes, and strain built up along particular directions. No evidence of phase transformation or cracking was observed in both materials. CL imaging reveals quenching of near band-edge emission by dislocations. In the second part, compositional inhomogeneity in quaternary GaInNAs and ternary InAlN alloys has been studied using TEM. It is shown that exposure to antimony during growth of GaInNAs results in uniform chemical composition in the epilayer, as antimony suppresses the surface mobility of adatoms that otherwise leads to two-dimensional growth and

  2. Raynaud's phenomenon in children.

    PubMed

    Ortega Vicente, Elena; Garrido Redondo, Mercedes

    Raynaud's Phenomenon is caused by spasm of the small arteries and arterioles of the fingers. It is triggered by various stimuli including exposure to cold or a stressful event. It may be symmetrical or wrap one end. The appearance of this entity in children is rare. We report the case of a 4 year old male consultation health center by episodes of coldness, pallor and pain in both feet.

  3. Volatile organic compounds sensing properties of tetrakis(alkylthio)-substituted lutetium(III) bisphthalocyanines thin films.

    PubMed

    Kilinç, Necmettin; Atilla, Devrim; Gürek, Ayşe Gül; Oztürk, Zafer Ziya; Ahsen, Vefa

    2009-11-15

    The effect of volatile organic compounds (VOCs) such as acetone, methanol, ethanol, chloroform, carbon tetrachloride, dichloromethane, and hexane on electrical conductivity of thin films of bis[tetrakis(alkylthio)phthalocyaninato]lutetium(III) double decker complexes [(C(n)H(2n+1)S)(4)Pc](2)Lu(III) was investigated. The [(C(n)H(2n+1)S)(4)Pc](2)Lu(III) molecules substituted with different alkylthia chains (n=6, 8, 10, 12, and 16) were coated on interdigital transducers using a jet spray technique. A change (increase or decrease) in the conductivity of the [(C(n)H(2n+1)S)(4)Pc](2)Lu(III) films was observed depending on the concentration of the VOCs, which was ranging from 500 to 5000 ppm. The decrease in the conductivity of the sensors for the dissolvent of the compounds (chloroform, carbon tetrachloride, dichloromethane and hexane) could be related to swelling of the films. On the other hand, the increase in the conductivity of the sensors for the other VOCs (acetone, methanol and ethanol) could be resulted from that the VOCs act as electron donors and/or acceptors in the films. A linear relationship between the sensor response and concentration of the VOC vapors is obtained. The sensitivities of the [(C(n)H(2n+1)S)(4)Pc](2)Lu(III) films were in the range of 2.10(-4)-3.10(-3)%/ppm.

  4. Expression and functional properties of the Streptococcus intermedius surface protein antigen I/II.

    PubMed

    Petersen, F C; Pasco, S; Ogier, J; Klein, J P; Assev, S; Scheie, A A

    2001-07-01

    Streptococcus intermedius is associated with deep-seated purulent infections. In this study, we investigated expression and functional activities of antigen I/II in S. intermedius. The S. intermedius antigen I/II appeared to be cell surface associated, with a molecular mass of approximately 160 kDa. Northern blotting indicated that the S. intermedius NCTC 11324 antigen I/II gene was transcribed as a monocistronic message. Maximum expression was seen during the early exponential phase. Insertional inactivation of the antigen I/II gene resulted in reduced hydrophobicity during early exponential phase, whereas no effect was detected during mid- and late exponential phases. Binding to human fibronectin and laminin was reduced in the isogenic mutant, whereas binding to human collagen types I and IV and to rat collagen type I was not significant for either the wild type or the mutant. Compared to the wild type, the capacity of the isogenic mutant to induce interleukin 8 (IL-8) release by THP-1 monocytic cells was significantly reduced. The results indicate that the S. intermedius antigen I/II is involved in adhesion to human receptors and in IL-8 induction.

  5. Vacuum phenomenon: Clinical relevance.

    PubMed

    Gohil, Ishan; Vilensky, Joel A; Weber, Edward C

    2014-04-01

    Vacuum phenomenon (VP) is an anatomical entity of potential confusion in the diagnosis and evaluation of joint pathology. Observation of this phenomenon has been demonstrated on basic radiographs, computed tomography, and magnetic resonance imaging. Although VP is most often associated with degenerative joint disease, it is observed with other pathologies. Two problematic scenarios can occur: a false-positive diagnosis of serious pathology instead of benign VP and a false-negative diagnosis of benign VP with a more serious underlying process Despite this potential for confusion, criteria for distinguishing VP from other causes of joint pain and for evaluating a suspected case of VP have not been fully established. We reviewed the literature to determine underlying mechanism, symptomology, associated pathologies, and clinical importance of VP. The formation of VP can be explained by gas solubility, pressure-volume relationships, and human physiology. CT, GRE-MRI, and multipositional views are the best imaging studies to view VP. Although most cases of VP are benign, it can be associated with clinical signs and symptoms. VP outside the spine is an underreported finding on imaging studies. VP should be on the differential diagnosis for joint pain, especially in the elderly. We have proposed criteria for diagnosing VP and generated a basic algorithm for its workup. Underreporting of this phenomenon shows a lack of awareness of VP on the part of physicians. By identifying true anatomic VP, we can prevent harm from suboptimal treatment of patients.

  6. Fibrous materials on polyhydroxybutyrate and ferric iron (III)-based porphyrins basis: physical-chemical and antibacterial properties

    NASA Astrophysics Data System (ADS)

    Olkhov, A.; Lobanov, A.; Staroverova, O.; Tyubaeva, P.; Zykova, A.; Pantyukhov, P.; Popov, A.; Iordanskii, A.

    2017-02-01

    Ferric iron (III)-based complexes with porphyrins are the homogenous catalysts of auto-oxidation of several biogenic substances. The most perspective carrier for functional low-molecular substances is the polymer fibers with nano-dimensional parameters. Application of natural polymers, poly-(3-hydroxybutyrate) or polylactic acid for instance, makes possible to develop fiber and matrice systems to solve ecological problem in biomedicine The aim of the article is to obtain fibrous material on poly-(3-hydroxybutyrate) and ferric iron (III)-based porphyrins basis and to examine its physical-chemical and antibacterial properties. The work is focused on possibility to apply such material to biomedical purposes. Microphotographs of obtained material showed that addition of 1% wt. ferric iron (III)-based porphyrins to PHB led to increased average diameter and disappeared spindly structures in comparison with initial PHB. Biological tests of nonwoven fabrics showed that fibers, containing ferric iron (III)-based tetraphenylporphyrins, were active in relation to bacterial test-cultures. It was found that materials on polymer and metal complexes with porphyrins basis can be applied to production of decontamination equipment in relation to pathogenic and opportunistic microorganisms.

  7. Direct observation of lanthanide(III)-phthalocyanine molecules on Au(111) by using scanning tunneling microscopy and scanning tunneling spectroscopy and thin-film field-effect transistor properties of Tb(III)- and Dy(III)-phthalocyanine molecules.

    PubMed

    Katoh, Keiichi; Yoshida, Yusuke; Yamashita, Masahiro; Miyasaka, Hitoshi; Breedlove, Brian K; Kajiwara, Takashi; Takaishi, Shinya; Ishikawa, Naoto; Isshiki, Hironari; Zhang, Yan Feng; Komeda, Tadahiro; Yamagishi, Masakazu; Takeya, Jun

    2009-07-29

    The crystal structures of double-decker single molecule magnets (SMM) LnPc(2) (Ln = Tb(III) and Dy(III); Pc = phthalocyanine) and non-SMM YPc(2) were determined by using X-ray diffraction analysis. The compounds are isomorphous to each other. The compounds have metal centers (M = Tb(3+), Dy(3+), and Y(3+)) sandwiched by two Pc ligands via eight isoindole-nitrogen atoms in a square-antiprism fashion. The twist angle between the two Pc ligands is 41.4 degrees. Scanning tunneling microscopy was used to investigate the compounds adsorbed on a Au(111) surface, deposited by using the thermal evaporation in ultrahigh vacuum. Both MPc(2) with eight lobes and MPc with four lobes, which has lost one Pc ligand, were observed. In the scanning tunneling spectroscopy images of TbPc molecules at 4.8 K, a Kondo peak with a Kondo temperature (T(K)) of approximately 250 K was observed near the Fermi level (V = 0 V). On the other hand, DyPc, YPc, and MPc(2) exhibited no Kondo peak. To understand the observed Kondo effect, the energy splitting of sublevels in a crystal field should be taken into consideration. As the next step in our studies on the SMM/Kondo effect in Tb-Pc derivatives, we investigated the electronic transport properties of Ln-Pc molecules as the active layer in top- and bottom-contact thin-film organic field effect transistor devices. Tb-Pc molecule devices exhibit p-type semiconducting properties with a hole mobility (mu(H)) of approximately 10(-4) cm(2) V(-1) s(-1). Interestingly, the Dy-Pc based devices exhibited ambipolar semiconducting properties with an electron mobility (mu(e)) of approximately 10(-5) and a mu(H) of approximately 10(-4) cm(2) V(-1) s(-1). This behavior has important implications for the electronic structure of the molecules.

  8. Syntheses, structures, and spectroscopic properties of plutonium and americium phosphites and the redetermination of the ionic radii of Pu(III) and Am(III).

    PubMed

    Cross, Justin N; Villa, Eric M; Wang, Shuao; Diwu, Juan; Polinski, Matthew J; Albrecht-Schmitt, Thomas E

    2012-08-06

    A series of isotypic rare earth phosphites (RE = Ce(III), Pr(III), Nd(III), Pu(III), or Am(III)) with the general formulas RE(2)(HPO(3))(3)(H(2)O) along with a Pu(IV) phosphite, Pu[(HPO(3))(2)(H(2)O)(2)], have been prepared hydrothermally via reactions of RECl(3) with phosphorous acid. The structure of RE(2)(HPO(3))(3)(H(2)O) features a face-sharing interaction of eight- and nine-coordinate rare earth polyhedra. By use of the crystallographic data from the isotypic series along with data from previously reported isotypic series, the ionic radii for higher coordinate Pu(III) and Am(III) were calculated. The (VIII)Pu(III) radius was calculated as 1.112 ± 0.004 Å, and the (IX)Pu(III) radius was calculated to be 1.165 ± 0.002 Å. The (VIII)Am(III) radius was calculated as 1.108 ± 0.004 Å, and the (IX)Am(III) radius was calculated as 1.162 ± 0.002 Å.

  9. Electrochemical and Thermodynamic Properties of Ln(III) (Ln = Eu, Sm, Dy, Nd) in 1-Butyl-3-Methylimidazolium Bromide Ionic Liquid

    PubMed Central

    Yang, Xiao; He, Ling; Qin, Song; Tao, Guo-Hong; Huang, Ming; Lv, Yi

    2014-01-01

    The electrochemical behavior and thermodynamic properties of Ln(III) (Ln = Eu, Sm, Dy, Nd) were studied in 1-butyl-3-methylimidazolium bromide ionic liquid (BmimBr) at a glassy carbon (GC) electrode in the range of 293–338 K. The electrode reaction of Eu(III) was found to be quasi-reversible by the cyclic voltammetry, the reactions of the other three lanthanide ions were regarded as irreversible systems. An increase of the current intensity was obtained with the temperature increase. At 293 K, the cathodic peak potentials of −0.893 V (Eu(III)), −0.596 V (Sm(III)), −0.637 V (Dy(III)) and −0.641 V (Nd(III)) were found, respectively, to be assigned to the reduction of Ln(III) to Ln(II). The diffusion coefficients (Do), the transfer coefficients (α) of Ln(III) (Ln = Eu, Sm, Dy, Nd) and the charge transfer rate constants (ks) of Eu(III) were estimated. The apparent standard potential (E0*) and the thermodynamic properties of the reduction of Eu(III) to Eu(II) were also investigated. PMID:24752584

  10. PARACEST properties of a dinuclear neodymium(III) complex bound to DNA or carbonate.

    PubMed

    Nwe, Kido; Andolina, Christopher M; Huang, Ching-Hui; Morrow, Janet R

    2009-07-01

    A dinuclear Nd(III) macrocyclic complex of 1 (1,4-bis[1-(4,7,10-tris(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane]-p-xylene) and mononuclear complexes of 1,4,7-tris-1,4,7,10-tetraazacyclododecane, 2, and 1,4,7-tris[(N-N-diethyl)carbamoylmethyl]-1,4,7,10-tetraazacyclododecane, 3, are prepared. Complexes of 1 and 2 give rise to a PARACEST (paramagnetic chemical exchange saturation transfer) peak from exchangeable amide protons that resonate approximately 12 ppm downfield from the bulk water proton resonance. The dinuclear Nd(III) complex is promising as a PARACEST contrast agent for MRI applications, because it has an optimal pH of 7.5 and the rate constant for amide proton exchange (2700 s(-1)) is nearly as large as it can be within slow exchange conditions with bulk water. Dinuclear Ln(2)(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethyl phosphate, and DNA. The CEST amide peak of Nd(2)(1) is enhanced by certain DNA sequences that contain hairpin loops, but decreases in the presence of diethyl phosphate or carbonate. Direct excitation luminescence studies of Eu(2)(1) show that double-stranded and hairpin-loop DNA sequences displace one water ligand on each Eu(III) center. DNA displaces carbonate ion despite the low dissociation constant for the Eu(2)(1) carbonate complex (K(d) = 15 microM). Enhancement of the CEST effect of a lanthanide complex by binding to DNA is a promising step toward the preparation of PARACEST agents containing DNA scaffolds.

  11. Evolution of corundum-structured III-oxide semiconductors: Growth, properties, and devices

    NASA Astrophysics Data System (ADS)

    Fujita, Shizuo; Oda, Masaya; Kaneko, Kentaro; Hitora, Toshimi

    2016-12-01

    The recent progress and development of corundum-structured III-oxide semiconductors are reviewed. They allow bandgap engineering from 3.7 to ∼9 eV and function engineering, leading to highly durable electronic devices and deep ultraviolet optical devices as well as multifunctional devices. Mist chemical vapor deposition can be a simple and safe growth technology and is advantageous for reducing energy and cost for the growth. This is favorable for the wide commercial use of devices at low cost. The III-oxide semiconductors are promising candidates for new devices contributing to sustainable social, economic, and technological development for the future.

  12. Group B Streptococcal Type II and III Conjugate Vaccines: Physicochemical Properties That Influence Immunogenicity

    PubMed Central

    Michon, Francis; Uitz, Catherine; Sarkar, Arun; D'Ambra, Anello J.; Laude-Sharp, Maryline; Moore, Samuel; Fusco, Peter C.

    2006-01-01

    Recent efforts toward developing vaccines against group B streptococci (GBS) have focused on increasing the immunogenicity of GBS polysaccharides by conjugation to carrier proteins. However, partial depolymerization of GBS polysaccharides for the production of vaccines is a difficult task because of their acid-labile, antigenically critical sialic acids. Here we report a method for the partial depolymerization of type II and III polysaccharides by mild deaminative cleavage to antigenic fragments with reducing-terminal 2,5-anhydro-d-mannose residues. Through the free aldehydes of their newly formed end groups, the fragments were conjugated to tetanus toxoid by reductive amination. The resulting conjugates stimulated the production in animals of high-titer type II- and III-specific antibodies which induced opsonophagocytic killing of type II and III strains of group B streptococci. For the type II conjugates, immunogenicity increased as oligosaccharide size decreased, whereas for type III conjugates, the size of the oligosaccharides did not significantly influence immunogenicity. When oligosaccharides of defined size were conjugated through sialic acid residues, the resulting cross-linkages were shown to affect immunogenicity. When oligosaccharides were conjugated through terminal aldehyde groups generated by deamination, modification of the exocyclic chain of sialic acid did not influence immunogenicity. PMID:16893995

  13. Structural effects on the photophysical properties of mono-β-diketonate and bis-β-diketonate Eu(III) complexes.

    PubMed

    Zhu, Tianyu; Chen, Peng; Li, Hongfeng; Sun, Wenbin; Gao, Ting; Yan, Pengfei

    2015-06-28

    Two ligands, mono-β-diketone (p-methoxylbenzoyl)trifluoroacetone (MBTF) and bis-β-diketone 1,2-bis(4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl))phenoxyl ethane (BTPE) with similar chemical structures, have been designed and prepared for the purpose of building the relationship between the structures and luminescence properties of Eu(iii) complexes. Structures of the Eu(iii) complexes [Eu(MBTF)3(DMSO)(H2O)] and [Eu2(BTPE)3(DMSO)4] have been defined by single crystal X-ray crystallography. The mono-β-diketone complex [Eu(MBTF)3(DMSO)(H2O)] is a mononuclear structure, the central Eu(iii) ion is coordinated by eight oxygen atoms from three ligands and two solvents, in a distorted trigonal-dodecahedral (8-TDH) geometry. Whereas, the bis-β-diketone complex [Eu2(BTPE)3(DMSO)4] adopts a triple-stranded dinuclear structure in which the two Eu(iii) ions are helically wrapped by three bis-bidentate ligands, and each Eu(iii) ion is eight-coordinated by six oxygen atoms from the ligands and two oxygen atoms from the coordinated DMSO molecules, in a distorted square-antiprismatic (8-SAP) geometry. The photophysical properties related to the electronic transition are characterized by the absorbance spectra, the emission spectra, the emission quantum yields, the emission lifetimes, and the radiative (kr) and nonradiative rate constants (knr). The mono-β-diketone complex [Eu(MBTF)3(DMSO)(H2O)] offers a relatively high emission quantum yield (38%, in solid) compared to that observed in the bis-β-diketone complex [Eu2(BTPE)3(DMSO)4] (25%, in solid). This enhancement of emission quantum yield in the mono-β-diketone complex can be attributed to its lower site symmetry around the Eu(iii) ion, lower non-radiative rate constant and higher energy transfer efficiency from the ligand to the metal ion.

  14. Equatorially connected diruthenium(II,III) units toward paramagnetic supramolecular structures with singular magnetic properties.

    PubMed

    Barral, M Carmen; Gallo, Teresa; Herrero, Santiago; Jiménez-Aparicio, Reyes; Torres, M Rosario; Urbanos, Francisco A

    2006-05-01

    The reaction of Ru2Cl(O2CMe)(DPhF)3 (DPhF = N,N'-diphenylformamidinate) with mono- and polycarboxylic acids gives a clean substitution of the acetate ligand, leading to the formation of complexes Ru2Cl(O2CC6H5)(DPhF)3 (1), Ru2Cl(O2CC6H4-p-CN)(DPhF)3 (2), [Ru2Cl(DPhF)3(H2O)]2(O2C)2 (3), [Ru2Cl(DPhF)3]2[C6H4-p-(CO2)2] (4), and [Ru2Cl(DPhF)3]3[C6H3-1,3,5-(CO2)3] (5). The preparation of [Ru2(NCS)(DPhF)3]3[C6H3-1,3,5-(CO2)3] (6) and {[Ru2(DPhF)3(H2O)]3[C6H3-1,3,5-(CO2)3]}(SO3CF3)3 (7) from 5 is also described. All complexes are characterized by elemental analysis, IR and electronic spectroscopy, mass spectrometry, cyclic voltammetry, and variable-temperature magnetic measurements. The crystal structure determinations of complexes 2.0.5THF and 3.THF.4H2O (THF = tetrahydrofuran) are reported. The reactions carried out demonstrate the high chemical stability of the fragment [Ru2(DPhF)3]2+, which is preserved in all tested experimental conditions. The stability of this fragment is also corroborated by the mass spectra. Electrochemical measurements reveal in all complexes one redox process due to the equilibrium Ru2(5+) <--> Ru2(6+). In the polynuclear complex 7, some additional oxidation processes are also observed that have been ascribed to the presence of two types of dimetallic units rather than two consecutive reversible oxidations. The magnetic behavior toward temperature for complexes 1-7 from 300 to 2 K is analyzed. Complexes 1-7 show low values of antiferromagnetic coupling in accordance with the molecular nature in 1 and 2 and the absence of important antiferromagnetic interaction through the carboxylate bridging ligands in 3-7, respectively. In addition, the magnetic properties of complex 7 do not correspond to any magnetic behavior described for diruthenium(II,III) complexes. The experimental data of compound 7 are simulated considering a physical mixture of S = 1/2 and 3/2 spin states. This magnetic study demonstrates the high sensitivity of the electronic

  15. Chemistry and Artists' Colors: Part III. Preparation and Properties of Artists' Pigments.

    ERIC Educational Resources Information Center

    Orna, Mary Virginia

    1980-01-01

    Describes laboratory methods for synthesizing chrome yellow, prussian blue, and phthalalocyanine blue; reviews chemical properties of artists' pigments including chemical structure and light-scattering properties; and explains how pigments are classified. (CS)

  16. Phosphorescent Iridium(III) Complexes Bearing Fluorinated Aromatic Sulfonyl Group with Nearly Unity Phosphorescent Quantum Yields and Outstanding Electroluminescent Properties.

    PubMed

    Zhao, Jiang; Yu, Yue; Yang, Xiaolong; Yan, Xiaogang; Zhang, Huiming; Xu, Xianbin; Zhou, Guijiang; Wu, Zhaoxin; Ren, Yixia; Wong, Wai-Yeung

    2015-11-11

    A series of heteroleptic functional Ir(III) complexes bearing different fluorinated aromatic sulfonyl groups has been synthesized. Their photophysical features, electrochemical behaviors, and electroluminescent (EL) properties have been characterized in detail. These complexes emit intense yellow phosphorescence with exceptionally high quantum yields (ΦP > 0.9) at room temperature, and the emission maxima of these complexes can be finely tuned depending upon the number of the fluorine substituents on the pendant phenyl ring of the sulfonyl group. Furthermore, the electrochemical properties and electron injection/transporting (EI/ET) abilities of these Ir(III) phosphors can also be effectively tuned by the fluorinated aromatic sulfonyl group to furnish some desired characters for enhancing the EL performance. Hence, the maximum luminance efficiency (ηL) of 81.2 cd A(-1), corresponding to power efficiency (ηP) of 64.5 lm W(-1) and external quantum efficiency (ηext) of 19.3%, has been achieved, indicating the great potential of these novel phosphors in the field of organic light-emitting diodes (OLEDs). Furthermore, a clear picture has been drawn for the relationship between their optoelectronic properties and chemical structures. These results should provide important information for developing highly efficient phosphors.

  17. Novel polymer anchored Cr(III) Schiff base complexes: Synthesis, characterization and antimicrobial properties

    NASA Astrophysics Data System (ADS)

    Selvi, Canan; Nartop, Dilek

    2012-09-01

    New polymer-bound Schiff bases and Cr(III) complexes have been synthesized by the reaction of 4-benzyloxybenzaldehyde, polymer-bound with 2-aminophenol, 2-amino-4-chlorophenol and 2-amino-4-methylphenol. The structure of polymeric-Schiff bases and their Cr(III) complexes have been characterized by elemental analyses, magnetic measurements, IR, UV-Vis, TG-DTA and 1H-NMR. All these compounds have also been investigated for antibacterial activity by the well-diffusion method against Staphylococcus aureus (RSKK-07035), Shigella dysenteria type 10 (RSKK 1036), Listeria monocytogenes 4b(ATCC 19115, Escherichia coli (ATCC 1230), Salmonella typhi H (NCTC 901.8394), Staphylococcus epidermis (ATCC 12228), Brucella abortus (RSKK-03026), Micrococcs luteus (ATCC 93419, Bacillus cereus sp., Pseudomonas putida sp. and for antifungal activity against Candida albicans (Y-1200-NIH).

  18. Synthesis, Structure and Antitumour Properties of a New 1,2-Propylenediaminetetraacetate-Ruthenium(III) Compound

    PubMed Central

    Vilaplana, R.; Romero, M. A.; Quirós, M.; Salas, J. M.

    1995-01-01

    A novel complex formed by ruthenium (III) and the sequestering ligand 1,2-propylenediaminetetraacetic acid (PDTA) has been synthetized and characterized. The structure of the monomeric compound, studied by X-ray diffraction , shows an almost symmetric octahedral geometry around the metal ion, with two chlorine atoms in a cis conformation. The antitumour activity against a variety of murine and human cancers is reported. PMID:18472768

  19. [Synthesis, characterization and luminescence properties of novel beta-diketone and Eu(III) ternary complex].

    PubMed

    Cheng, Guo; Wei, Chang-Ping; Ren, Xiao-Ming; Wang, He; Wei, Wen-Tao

    2011-09-01

    The novel beta-diketone 1-(4-bromophenyl)-3-phenylpropane-1, 3-dione (L) was synthesized at room temperature by classical Claisen condensation reaction. With the beta-diketone L as the first ligand and phen as the secondary ligand, and a new rare-earth Eu (III) ternary complex was prepared. The ligand L and ternary complex were characterized by elemental analysis, IR spectra, UV spectra and fluorescence spectra. IR spectra indicated that: the novel ligand L contained the structure of beta-diketone, where the content of enol was high; the Eu3+ ion in the ternary complex was coordinated with six oxygen atoms of three L ligands and two nitrogen atoms of the second ligand phen. UV spectra showed that the main absorption was from the first ligand L in the Eu (III) ternary complex. The excitation and emission spectra of the ternary complex were measured and investigated. Fluorescence spectra demonstrated that the ternary complex could emit characteristic fluorescence of rare earth Eu3+ ion and the strongest emission band was narrow which was attributed to the 5 D0 --> 7 F2 transitions of the 4f electrons of the central Eu3+ ions. So, the new Eu(III) ternary complex is an excellent red-emitter which would be regarded as a valuable material with bright red fluorescence because it presents good monochromaticity.

  20. Crystal structure, spectral and thermal properties of 1,2-bis[2-(4,4,4-trifluoro-1-hydroxy-3-oxobut-1-enyl)phenoxy]-ethane and luminescent properties of its complexes with Al(III) and Eu(III)

    NASA Astrophysics Data System (ADS)

    Khamidullina, Liliya A.; Obydennov, Konstantin L.; Slepukhin, Pavel A.; Puzyrev, Igor S.

    2016-12-01

    Describing the crystal structure, packing, FT-IR, UV-Vis and NMR spectra and thermal properties of new polydentate O-ligand based on aryl-β-diketone moieties connected by ethylene glycol spacer is the subject of this article. The results of IR, UV-Vis and 1H NMR spectroscopy as well X-ray crystallography of 1,2-bis[2-(4,4,4-trifluoro-1-hydroxy-3-oxobut-1-enyl)phenoxy]-ethane (BTFPE) indicate that the compound exists in solution and in solid as enol. The crystal structure analysis shows that BTFPE has C2/c group of the monoclinic system. Typical S(6) intramolecular hydrogen bond occurs in each 1,3-diketo moiety. This bond is asymmetric and the H atom is closest to the O atom adjacent to the phenyl ring. The packing of the crystal is sustained by numerous Csbnd H⋯O, Osbnd H⋯F, Csbnd H⋯F interactions. In the crystal, supramolecular zig-zag chains are formed along the c-axis. Short contacts interconnect the molecules into a two-dimensional layered structure wherein each molecule is node between chains. According to the thermal investigation this compound is stable up to 200 °C in air atmosphere, above this temperature it decomposes. Photoluminescent properties of aluminum(III) and europium(III) complexes of BTFPE were evaluated in chloroform solution and in the solid state. Aluminum complex of BTFPE shows blue luminescence with maximum at 445 nm. Europium complex exhibits intense red color luminescence at 613 nm from central Eu(III) ion through the excitation of the ligand.

  1. The neutron channeling phenomenon.

    PubMed

    Khanouchi, A; Sabir, A; Boulkheir, M; Ichaoui, R; Ghassoun, J; Jehouani, A

    1997-01-01

    Shields, used for protection against radiation, are often pierced with vacuum channels for passing cables and other instruments for measurements. The neutron transmission through these shields is an unavoidable phenomenon. In this work we study and discuss the effect of channels on neutron transmission through shields. We consider an infinite homogeneous slab, with a fixed thickness (20 lambda, with lambda the mean free path of the neutron in the slab), which contains a vacuum channel. This slab is irradiated with an infinite source of neutrons on the left side and on the other side (right side) many detectors with windows equal to 2 lambda are placed in order to evaluate the neutron transmission probabilities (Khanouchi, A., Aboubekr, A., Ghassoun, J. and Jehouani, A. (1994) Rencontre Nationale des Jeunes Chercheurs en Physique. Casa Blanca Maroc; Khanouchi, A., Sabir, A., Ghassoun, J. and Jehouani, A. (1995) Premier Congré International des Intéractions Rayonnements Matière. Eljadida Maroc). The neutron history within the slab is simulated by the Monte Carlo method (Booth, T. E. and Hendricks, J. S. (1994) Nuclear Technology 5) and using the exponential biasing technique in order to improve the Monte Carlo calculation (Levitt, L. B. (1968) Nuclear Science and Engineering 31, 500-504; Jehouani, A., Ghassoun, J. and Aboubker, A. (1994) In Proceedings of the 6th International Symposium on Radiation Physics, Rabat, Morocco). Then different geometries of the vacuum channel have been studied. For each geometry we have determined the detector response and calculated the neutron transmission probability for different detector positions. This neutron transmission probability presents a peak for the detectors placed in front of the vacuum channel. This study allowed us to clearly identify the neutron channeling phenomenon. One application of our study is to detect vacuum defects in materials.

  2. Optical Properties of Iridium(III) Cyclometalates: Excited State Interaction with Small Molecules and Dynamics of Light-Harvesting Materials

    NASA Astrophysics Data System (ADS)

    Schwartz, Kyle Robert

    phototophysical properties of Ir(III) cyclometalates with pendant terthiophenes as secondary organic chromophores is presented. The interplay of the excited states between each chromophore represents an interesting photoredox active system for energy-to-light or light-to-energy devices. Greater knowledge of the primary photophysical events within these complexes will provide a better understanding of how energy moves in these hybrid systems after light absorption, leading to increased device efficiency.

  3. An alternative splicing event which occurs in mouse pachytene spermatocytes generates a form of DNA ligase III with distinct biochemical properties that may function in meiotic recombination.

    PubMed Central

    Mackey, Z B; Ramos, W; Levin, D S; Walter, C A; McCarrey, J R; Tomkinson, A E

    1997-01-01

    Three mammalian genes encoding DNA ligases have been identified. However, the role of each of these enzymes in mammalian DNA metabolism has not been established. In this study, we show that two forms of mammalian DNA ligase III, alpha and beta, are produced by a conserved tissue-specific alternative splicing mechanism involving exons encoding the C termini of the polypeptides. DNA ligase III-alpha cDNA, which encodes a 103-kDa polypeptide, is expressed in all tissues and cells, whereas DNA ligase III-beta cDNA, which encodes a 96-kDa polypeptide, is expressed only in the testis. During male germ cell differentiation, elevated expression of DNA ligase III-beta mRNA is restricted, beginning only in the latter stages of meiotic prophase and ending in the round spermatid stage. In 96-kDa DNA ligase III-beta, the C-terminal 77 amino acids of DNA ligase III-alpha are replaced by a different 17- to 18-amino acid sequence. As reported previously, the 103-kDa DNA ligase III-alpha interacts with the DNA strand break repair protein encoded by the human XRCC1 gene. In contrast, the 96-kDa DNA ligase III-beta does not interact with XRCC1, indicating that DNA ligase III-beta may play a role in cellular functions distinct from the DNA repair pathways involving the DNA ligase III-alpha x XRCC1 complex. The distinct biochemical properties of DNA ligase III-beta, in combination with the tissue- and cell-type-specific expression of DNA ligase III-beta mRNA, suggest that this form of DNA ligase III is specifically involved in the completion of homologous recombination events that occur during meiotic prophase. PMID:9001252

  4. Are Earthquakes a Critical Phenomenon?

    NASA Astrophysics Data System (ADS)

    Ramos, O.

    2014-12-01

    Earthquakes, granular avalanches, superconducting vortices, solar flares, and even stock markets are known to evolve through power-law distributed events. During decades, the formalism of equilibrium phase transition has coined these phenomena as critical, which implies that they are also unpredictable. This work revises these ideas and uses earthquakes as the paradigm to demonstrate that slowly driven systems evolving through uncorrelated and power-law distributed avalanches (UPLA) are not necessarily critical systems, and therefore not necessarily unpredictable. By linking the correlation length to the pdf of the distribution, and comparing it with the one obtained at a critical point, a condition of criticality is introduced. Simulations in the classical Olami-Feder-Christensen (OFC) earthquake model confirm the findings, showing that earthquakes are not a critical phenomenon. However, one single catastrophic earthquake may show critical properties and, paradoxically, the emergence of this temporal critical behaviour may eventually carry precursory signs of catastrophic events.

  5. Cyano-decorated ligands: a powerful alternative to fluorination for tuning the photochemical properties of cyclometalated Ir(iii) complexes.

    PubMed

    Mills, Isaac N; Kagalwala, Husain N; Bernhard, Stefan

    2016-06-21

    A new cyclometalating ligand, featuring nitrile moieties to enhance the photophysical and consequently photocatalytic properties of bis-cyclometalated Ir(iii) complexes, was synthesized. Nitrile moieties were selected to replace expensive and environmentally problematic fluoride moieties commonly employed for synthetic tuning of chromophores. Two new chromophores bearing the new nitrile-decorated ligand were synthesized with strong electron-donating and electron-withdrawing ancillary ligands to probe extremes of the complexes' tunability. These complexes possessed rich and drastically different electrochemical and photophysical properties. One chromophore possessed a particularly long lifetime of approximately 8 μs; it was also a remarkably efficient triplet emitter with a quantum yield of 63%. The complexes were finally assessed as photosensitizers of water reduction with Pt colloids, where both complexes produced hydrogen with optimized conditions reaching 2000 and 1400 turnovers.

  6. Self-assembly synthesis, structural features, and photophysical properties of dilanthanide complexes derived from a novel amide type ligand: energy transfer from Tb(III) to Eu(III) in a heterodinuclear derivative.

    PubMed

    Gao, Cunji; Kirillov, Alexander M; Dou, Wei; Tang, Xiaoliang; Liu, Liangliang; Yan, Xuhuan; Xie, Yujie; Zang, Peixian; Liu, Weisheng; Tang, Yu

    2014-01-21

    A novel amide type ligand benzyl-N,N-bis[(2'-furfurylaminoformyl)phenoxyl)ethyl]-amine (L) has been designed and applied for the self-assembly generation of homodinuclear lanthanide coordination compounds [Ln2(μ2-L)2(NO3)6(EtOH)2] [Ln = Eu (1), Tb (2), and Gd (3)] and a heterodinuclear derivative [EuTb(μ2-L)2(NO3)6(EtOH)2] (4). All the complexes have been characterized by the X-ray single-crystal diffraction analyses. They are isostructural, crystallize in a monoclinic space group P21/c, and form [2 + 2] rectangular macrocycle structures. Compound 4 is the first example of a [2 + 2] rectangular macrocycle heterodinuclear EuTb complex assembled from an amide type ligand. In 4, the discrete 0D dimeric [EuTb(μ2-L)2(NO3)6(EtOH)2] units are extended, via the multiple N-H···O hydrogen bonds, into a 2D supramolecular network that has been topologically classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology. The triplet state ((3)ππ*) of L studied by the Gd(III) complex 3 demonstrated that the ligand beautifully populates Tb(III) emission (Φ = 52%), whereas the corresponding Eu(III) derivative 1 shows weak luminescence efficiency (Φ = 0.7%) because the triplet state of L has a poor match with (5)D1 energy level of Eu(III). Furthermore, the photoluminescent properties of heterodinuclear complex 4 have been compared with those of the analogous homodinuclear compounds. The quantum yield and lifetime measurements prove that energy transfer from Tb(III) to Eu(III) is being achieved, namely, that the Tb(III) center is also acting to sensitize the Eu(III) and enhancing Eu(III) emission in 4.

  7. Covalent lanthanide(III) macrocyclic complexes: the bonding nature and optical properties of a promising single antenna molecule.

    PubMed

    Rabanal-León, Walter A; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

    2014-12-21

    The present work is focused on the elucidation of the electronic structure, bonding nature and optical properties of a series of low symmetry (C2) coordination compounds of type [Ln(III)HAM](3+), where "Ln(III)" are the trivalent lanthanide ions: La(3+), Ce(3+), Eu(3+) and Lu(3+), while "HAM" is the neutral six-nitrogen donor macrocyclic ligand [C22N6H26]. This systematic study has been performed in the framework of the Relativistic Density Functional Theory (R-DFT) and also using a multi-reference approach via the Complete Active Space (CAS) wavefunction treatment with the aim of analyzing their ground state and excited state electronic structures as well as electronic correlation. Furthermore, the use of the energy decomposition scheme proposed by Morokuma-Ziegler and the electron localization function (ELF) allows us to characterize the bonding between the lanthanide ions and the macrocyclic ligand, obtaining as a result a dative-covalent interaction. Due to a great deal of lanthanide optical properties and their technological applications, the absorption spectra of this set of coordination compounds were calculated using the time-dependent density functional theory (TD-DFT), where the presence of the intense Ligand to Metal Charge Transfer (LMCT) bands in the ultraviolet and visible region and the inherent f-f electronic transitions in the Near-Infra Red (NIR) region for some lanthanide ions allow us to propose these systems as "single antenna molecules" with potential applications in NIR technologies.

  8. Magnetic properties of layered III-VI Diluted Magnetic Semiconductors (DMS)

    NASA Astrophysics Data System (ADS)

    Pekarek, Thomas; Miotkowski, I.; Ramdas, A. K.

    2015-03-01

    The new class of quasi-two-dimensional III-VI Diluted Magnetic Semiconductors (DMS) exhibits a rich collection of magnetic behavior. The Ga1-xMnxS system exhibits a 3-D spin-glass transition, which was unexpected given its four atom thick two dimensional structure. The best scaling fit was found for critical exponents (γ = 4.0, β = 0.8, and δ = 5.5) similar to the three dimensional Zn1-xMnxTe system. Ga1-xFexSe exhibits a prominent magnetic anisotropy over the temperature range from 10 to 400 K. Theoretical models for In1-xMnxSe, In1-xMnxS, and Ga1-xMnxS provide good agreement with experimental results over a wide range of temperatures and fields. The mechanism behind an unusually large thermal hysteresis (ΔT ~ 200 K) in In1-xMnxSe, which extends up to room temperature, is not completely understood at this time. Typically, thermal hysteresis in most materials has a ΔT ~ 20 K occurring well below room temperature. The host III-VI semiconductors themselves are among the best non-linear optical materials. This research was supported by the UNF Terry Presidential Professorship, the Florida Space Grant Consortium, A Purdue U. Academic Reinvestment Program, and by NSF Grant Nos. DMR-07-06593 and DMR-14-29428.

  9. Structural Properties of 2/2 Hemoglobins: The Group III Protein from Helicobacter hepaticus

    PubMed Central

    Nothnagel, Henry J.; Winer, Benjamin Y.; Vuletich, David A.; Pond, Matthew P.; Lecomte, Juliette T.J.

    2011-01-01

    Summary The ε-proteobacterium Helicobacter hepaticus (Hh) contains a gene coding for a hemoglobin (Hb). The protein belongs to the 2/2 Hb lineage and is representative of Group III, a set of Hbs about which little is known. An expression and purification procedure was developed for Hh Hb. Electronic absorption and NMR spectra were used to characterize ligation states of the ferric and ferrous protein. The pKa of the acid/alkaline transition of ferric Hh Hb was 7.3, an unusually low value. NMR analysis of the cyanomet complex showed the orientation of the heme group to be reversed compared to most Group I and II 2/2 Hbs. Ferrous Hh Hb formed a stable cyanide complex that yielded NMR spectra similar to those of the carbonmonoxy complex. All forms of Hh Hb self-associated at NMR concentrations. Comparison was made to the related Campylobacter jejuni 2/2 Hb (Ctb), and the amino acid conservation pattern of Group III was re-inspected to help in the generalization of structure–function relationships. PMID:21445851

  10. Coordination properties of warfarin towards Pr(III) predicted from DFT and FT-IR studies

    NASA Astrophysics Data System (ADS)

    Mihaylov, Tz.; Trendafilova, N.; Georgieva, I.; Kostova, I.

    2010-08-01

    The coordination behavior of warfarin towards Pr(III) in Pr(L) 3·5H 2O complex (L - warfarin) is investigated through molecular modeling at B3LYP/6-31G(d,p) level and consequent exhaustive comparative vibrational analysis of the ligand and the complex. The calculated NPA charges, Fukui functions and MEP values of the anionic ligand in solution pointed out that the oxygen atoms of the deprotonated hydroxyl and the coumarin carbonyl groups are the most probable reactive sites upon coordination. The metal-ligand binding mode of warfarin is predicted through molecular modeling and energy estimation of different Pr(III)-warfarin structures. In the most stable model structure, the ligand-metal binding is realized through the oxygen of the deprotonated OH group and the oxygen of the keto C dbnd O group in pseudo-octahedral polyhedron. The suggested metal-ligand binding mode is confirmed by comparative vibrational analysis of the free ligand and various model structures with different metal-ligand binding modes.

  11. Synthesis and characterization of dopamine substitue tripodal trinuclear [(salen/salophen/salpropen)M] (Mdbnd Cr(III), Mn(III), Fe(III) ions) capped s-triazine complexes: Investigation of their thermal and magnetic properties

    NASA Astrophysics Data System (ADS)

    Uysal, Şaban; Koç, Ziya Erdem

    2016-04-01

    In this work, we aimed to synthesize and characterize a novel tridirectional ligand including three catechol groups and its novel tridirectional-trinuclear triazine core complexes. For this purpose, we used melamine (2,4,6-triamino-1,3,5-triazine) (MA) as starting material. 2,4,6-tris(4-carboxybenzimino)-1,3,5-triazine (II) was synthesized by the reaction of an equivalent melamine (I) and three equivalent 4-carboxybenzaldehyde. 4,4‧,4″-((1E,1‧E,1″E)-((1,3,5-triazine-2,4,6-triyl)tris(azanylylidene))tris(methanylylidene))tris(N-(3,4-dihydroxyphenethyl)benzamide) L (IV) was synthesized by the reaction of one equivalent (II) and three equivalent dopamine (3,4-dihydroxyphenethylamine) (DA) by using two different methods. (II, III, IV) and nine novel trinuclear Cr(III), Mn(III) and Fe(III) complexes of (IV) were characterized by means of elemental analyses, 1H NMR, FT-IR spectrometry, LC-MS (ESI+) and thermal analyses. The metal ratios of the prepared complexes were performed using Atomic Absorption Spectrophotometry (AAS). We also synthesized novel tridirectional-trinuclear systems and investigated their effects on magnetic behaviors of [salen, salophen, salpropen Cr(III)/Mn(III)/Fe(III)] capped complexes. The complexes were determined to be low-spin distorted octahedral Mn(III) and Fe(III), and distorted octahedral Cr(III) all bridged by catechol group.

  12. Cozen's phenomenon: a reminder.

    PubMed

    Dorman, S; Jariwala, A; Campbell, D

    2013-08-01

    A four-year-old child attended Accident and Emergency following a fall from a slide with a displaced and angulated proximal tibial metaphyseal fracture. Treatment included closed manipulation under anaesthesia and an above knee cast for seven weeks. Serial radiographs over the following few months were satisfactory demonstrating good alignment and evidence of healing. However, at four-months review new-onset genu valgum with mechanical axis deviation was noted. No evidence of spontaneous resolution was noted over the following 12 months and hence a corrective hemi-epiphysiodesis was performed. At 12-months post-operatively, there was marked clinical and radiographical improvement in alignment. Classically Cozen's phenomenon is described as the late-onset post-traumatic valgus deformity associated with proximal tibial metaphyseal fractures in children. We want to reemphasise the early recognition of children at risk of this unique complication. In addition, we wish to highlight the progression of the late-onset valgus and its subsequent management.

  13. Synthesis, luminescence properties of Eu(III) and Tb(III) complexes with a novel aromatic carboxylic acid and their interactions with bovine serum albumin

    NASA Astrophysics Data System (ADS)

    Shen, Liqun; Yang, Zhengfa; Tang, Ruiren

    2012-12-01

    A novel aromatic carboxylic acid ligand (L) was synthesized and its corresponding Eu(III) and Tb(III) complexes, Na3EuLCl3·2H2O (EuL) and Na3TbLCl3·3H2O (TbL), were successfully prepared. L and its corresponding complexes were characterized by means of MS, elemental analysis, IR, 1H NMR and TG. The luminescence spectra of Eu(III) and Tb(III) complexes were investigated and the results showed that L was an efficient sensitizer for Eu(III) and Tb(III) luminescence. The interactions of L, EuL and TbL with bovine serum albumin (BSA) have been investigated through fluorescence spectroscopy under physiological conditions. The Stern-Volmer analysis indicated that the fluorescence quenching of BSA by L, EuL and TbL was resulted from static mechanism, and the binding constants (Ka) were 2.22 × 104, 1.33 × 105 and 4.27 × 105 at 300 K, respectively. The binding sites (n) and the corresponding thermodynamic parameters ΔH, ΔS, and ΔG were calculated at different temperatures. According to the theoretical and experimental results, van der Waals interactions and hydrogen bonds were found to play major roles in the binding reaction. Furthermore, UV-Vis absorption spectroscopy and synchronous fluorescence spectra indicated that the conformation of BSA was changed. The results obtained in the work can help understand the action mode between L and its corresponding Eu(III) and Tb(III) complexes with BSA, and they are also expected to provide important information of designs of new inspired drugs based on Eu and Tb.

  14. Evidence of bimodal physical properties of intervening, optically thin C III absorbers at z ˜ 2.5

    NASA Astrophysics Data System (ADS)

    Kim, T.-S.; Carswell, R. F.; Ranquist, D.

    2016-03-01

    We present the Voigt profile analysis of 132 intervening C IV+C III components associated with optically thin H I absorbers at 2.1 < z < 3.4 in the 19 high-quality UVES/VLT and HIRES/Keck QSO spectra. For log N_{C I} in [11.7, 14.1], N_{C III} ∝ N_{C IV}^{1.42± 0.11} and < N_{C III}/N_{C {IV} > = 1.0± 0.3 with a negligible redshift evolution. For 54 C IV components tied (aligned) with H I at log N_{H I} in [12.2, 16.0] and log N_{C IV} in [11.8, 13.8], the gas temperature Tb estimated from absorption line widths is well approximated to a Gaussian peaking at log Tb ˜ 4.4 ± 0.3 for log Tb ∈ [3.5, 5.5], with a negligible non-thermal contribution. For 32 of 54 tied H I+C IV pairs, also tied with C III at log N_{C {III} in [11.7, 13.8], we ran both photoionization equilibrium (PIE) and non-PIE (using a fixed temperature Tb) CLOUDY models for the Haardt-Madau QSOs+galaxies 2012 UV background. We find evidence of bimodality in observed and derived physical properties. High-metallicity branch absorbers have a carbon abundance [C/H]temp ≥ -1.0, a line-of-sight length Ltemp ≤ 20 kpc and a total (neutral and ionized) hydrogen volume density log nH,temp ∈ [-4.5, -3.3] and log Tb ∈ [3.9, 4.5]. Low-metallicity branch absorbers have [C/H]temp ≤ -1.0, Ltemp ∈ [20, 480] kpc and log nH,temp ∈ [-5.2, -4.3] and log Tb ˜ 4.5. High-metallicity branch absorbers seem to be originated from extended discs, inner haloes or outflowing gas of intervening galaxies, while low-metallicity absorbers are produced by galactic haloes or the surrounding intergalactic medium filament.

  15. Internal energy transfer phenomenon and light-emission properties of γ-LiAlO2 phosphor doped with Mn2+

    NASA Astrophysics Data System (ADS)

    Wang, Bai-Bin; Chang, Chi-Fen; Yang, Wein-Duo

    2013-07-01

    γ-LiAlO2:Mn2+ phosphor was synthesized using the cellulose-citric acid sol-gel method, and its light emission and energy transfer properties were investigated. Excitation and emission spectrum analysis revealed a decrease in intensity of the spectrum as the amount of Mn2+ doping increased. Blasse's equation determined the maximum distance for energy transfer between Mn2+ ions as 4.3142 nm. Dexter's theory verifies that the mechanism of energy transfer between Mn2+ ions conforms to an electric dipole and electric quadrupole interaction.

  16. Technical Progress Report for "Optical and Electrical Properties of III-Nitrides and Related Materials"

    SciTech Connect

    Jiang, Hongxing

    2008-10-31

    Investigations have been conducted focused on the fundamental material properties of AIN and high AI-content AIGaN alloys and further developed MOCVD growth technologies for obtaining these materials with improved crystalline quality and conductivities.

  17. The Alternative complex III: properties and possible mechanisms for electron transfer and energy conservation.

    PubMed

    Refojo, Patrícia N; Teixeira, Miguel; Pereira, Manuela M

    2012-10-01

    Alternative complexes III (ACIII) are recently identified membrane-bound enzymes that replace functionally the cytochrome bc(1/)b(6)f complexes. In general, ACIII are composed of four transmembrane proteins and three peripheral subunits that contain iron-sulfur centers and C-type hemes. ACIII are built by a combination of modules present in different enzyme families, namely the complex iron-sulfur molybdenum containing enzymes. In this article a historical perspective on the investigation of ACIII is presented, followed by an overview of the present knowledge on these enzymes. Electron transfer pathways within the protein are discussed taking into account possible different locations (cytoplasmatic or periplasmatic) of the iron-sulfur containing protein and their contribution to energy conservation. In this way several hypotheses for energy conservation modes are raised including linear and bifurcating electron transfer pathways. This article is part of a Special Issue entitled: 17th European Bioenergetics Conference (EBEC 2012).

  18. Synthesis, structure, and spectral and electrochemical properties of chromium(III) tris-(8-hydroxyquinolinate).

    PubMed

    Freitas, Ana R; Silva, Mónica; Ramos, M Luísa; Justino, Licínia L G; Fonseca, Sofia M; Barsan, Madalina M; Brett, Christopher M A; Silva, M Ramos; Burrows, Hugh D

    2015-07-07

    The kinetically inert chromium(III) tris-(8-hydroxyquinolinate), Crq3, has been synthesized, crystallized from 90% methanol-water, and characterized by MALDI-TOF mass spectrometry, thermogravimetry, FTIR, NMR spectroscopy, and X-ray powder diffraction. It is formed as a methanol solvate, but the solvent can be removed by heating. Large paramagnetic shifts and spectral broadening in (1)H NMR spectra indicate electron delocalization between the metal and the ligand. DFT calculations show it is present as the meridional isomer, with the HOMO largely based on one of the metal 3d orbitals and the LUMO essentially localized on the ligands. Cyclic voltammetry (CV) in acetonitrile solutions shows four oxidation peaks and two, less intense reduction waves on the first scan. The HOMO energy determined from the first oxidation peak is fairly close to that obtained by DFT, in agreement with this being mainly metal based. Although the number of peaks decreases on subsequent CV scans, the complex shows markedly enhanced electrochemical stability compared with aluminium(III) tris-(8-hydroxyquinolinate). Solution UV/visible absorption and solid diffuse reflectance spectra have a weak, long wavelength band, assigned to the metal based d-d transition, in addition to the normal, ligand based bands seen in metal quinolates. The energy of the lowest energy band is identical to the HOMO-LUMO separation obtained by cyclic voltammetry, in agreement with the above description. The compound is only weakly luminescent, in contrast to many other metal quinolates, due to the lowest energy transition being metal rather than ligand based. The potential of this compound as an electron transporting/hole blocking layer in optoelectronic devices is indicated.

  19. [Phenomenon of dental fear].

    PubMed

    Moore, R; Birn, H

    1990-01-01

    Odontophobia is a rather unique phobia with special psychosomatic components that impact on the dental health of odontophobic persons. It also has psychosocial components largely as a result of destruction of the teeth and subsequent embarrassment that can affect a person and cause a vicious cycle of dental fear. The phenomenon is facilitated by misunderstandings and myths generated by both patients and dentists. The most common reasons given in the literature for such strong fears of dental treatment are: 1) bad experiences in childhood for 85% of cases, 2) feeling of powerlessness and lack of control over personal emotional reactions and over the social situation in the dental chair, 3) social learning processes in which the image of the dentist is cast in a negative light by the mass media or by the person's relatives or friends and 4) that the person has other psychologic problems (in 20% of cases), such as serious phobias and/or neuroses. A strategy of researching and thus tackling the problem is presented which focuses on three essential targets that require studying and change: 1) the community at large and their image of the dentist, 2) the patient role and 3) the dentist role. Various model projects are presented along with their diagnostic systems. These are seen to focus in varying degrees on different elements of the target groups that effect the dentist-patient relationship but the need to come out into the community and make the social environment right for these patients is an important factor in all strategies.(ABSTRACT TRUNCATED AT 250 WORDS)

  20. Photophysics, photoelectrical properties and photoconductivity relaxation dynamics of quantum-sized bismuth(III) sulfide thin films

    SciTech Connect

    Pejova, Biljana . E-mail: biljana@iunona.pmf.ukim.edu.mk; Tanusevski, Atanas; Grozdanov, Ivan

    2005-06-15

    Electrical and photoelectrical properties (including both the stationary photoresponse and the photocarriers' relaxation dynamics) of nanocrystalline semiconducting bismuth(III) sulfide thin films were investigated. The experimental design of photoelectrical properties was achieved by controlling the chemistry of the deposition process (varying the reagent concentration in the reaction system) and also by physical means (controlling the crystal dimensions by post-deposition annealing). The band gap energy of thin films characterized by most pronounced photoelectrical properties was calculated, on the basis of measured photoconductivity spectral response curves, by several approaches. All of the obtained values are in very good agreement with the corresponding ones obtained from optical spectroscopy data within the framework of parabolic approximation for dispersion relation. On the basis of measured temperature dependence of dark electrical resistivity of nanocrystalline bismuth(III) sulfide films, the thermal band gap energy and the ionization energy of the impurity level (of donor type) were calculated. The corresponding values are 1.50 and 0.42eV. Dynamics of non-equilibrium charge carriers' relaxation processes was studied with the oscilloscopic method. By analysis of the photoconductivity decay kinetics data it is found that recombination of non-equilibrium charge carriers is carried out according to the linear mechanism. The calculated relaxation time of photoexcited charge carriers is 1.58ms, the relaxation processes occurring via local trapping centers. Recombination processes occurring via a single-type trapping center can be described within the framework of the Schockley-Read model. The practically linear regime detected in the measured lux-ampere characteristics of the studied films ({delta}{sigma}{approx}{phi}{sup 0.98}) indicate as well a linear recombination mechanism of the photoexcited charge carriers.

  1. Fabrication and photonics properties of III-V semiconductor nanowire structures

    NASA Astrophysics Data System (ADS)

    Lin, Tzu-ging

    III-V semiconductor nanowires (NWs) have shown great potential to be building blocks for optical, optoelectronic, and electronic devices due to their special transverse confinement of electrons and photons along the nanowire axis. In addition, semiconductor nanowires with subwavelength structures exhibit strong optical Mie resonance, making them ideal platforms for realizing novel optical devices, such as extreme solar energy absorbers and broadband light trapping devices. This special 1D optical Mie resonance can be enhanced by using semiconductor-core dielectric-shell (CS) and metal-core semiconductor-shell dielectric-outer shell (CSS) nanowire heterostructures. Those advantages can be even leveraged up by utilizing nanowire arrays, attributing to the increasing optical inter-wire interaction between incident light and nanostructures. However, to form a very thin, vertical IIIV nanowire array is challenging for both conventional top-down and bottom-up approaches due to the limitation of the resolution of lithographically defined masks and thermodynamic limits of growth direction and diameter of nanowires, respectively. By employing nanoscale self-mask effects, those limitations can be circumvented. In this dissertation, we presented a novel top-down etching method to fabricate very thin, high aspect ratio and vertical III-V nanowire arrays without lithographically defined masks. The mechanism of the formation of nanowire arrays was proposed and verified by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) in this work. Optical characterizations, such as optical reflectance and Raman spectroscopy, were also performed on those nanowire arrays. By employing those nanowire arrays, broadband light trapping can be achieved. Besides, the effects of contact electrodes, such as indium tin oxide (ITO), silver, and copper, on semiconductor nanowire solar cell devices with different bandgaps were also investigated with a focus on optical

  2. Synthesis, properties and applications of 2D layered M(III)X(VI) (M = Ga, In; X = S, Se, Te) materials.

    PubMed

    Xu, Kai; Yin, Lei; Huang, Yun; Shifa, Tofik Ahmed; Chu, Junwei; Wang, Feng; Cheng, Ruiqing; Wang, Zhenxing; He, Jun

    2016-09-29

    Group III-VI compounds M(III)X(VI) (M = Ga, In; X = S, Se, Te) are one class of important 2D layered materials and are currently attracting increasing interest due to their unique electronic and optoelectronic properties and their great potential applications in various other fields. Similar to 2D layered transition metal dichalcogenides (TMDs), M(III)X(VI) also have the significant merits of ultrathin thickness, ultrahigh surface-to-volume ratio, and high compatibility with flexible devices. More impressively, in contrast with TMDCs, M(III)X(VI) demonstrate many superior properties, such as direct band gap electronic structure, high carrier mobility, rare p-type electronic behaviors, high charge density, and so on. These unique characteristics cause high-performance device applications in electronics, optoelectronics, and optics. In this review, we aim to provide a summary of the state-of-the-art of research activities in 2D layered M(III)X(VI) materials. The scope of the review covers the synthesis and properties of 2D layered M(III)X(VI) materials and their van der Waals heterostructures. We especially focus on the applications in electronics and optoelectronics. Moreover, the review concludes with some perspectives on future developments in this field.

  3. Fully first-principles sX-LDA calculations of excited states and optical properties of III-V semiconductors

    NASA Astrophysics Data System (ADS)

    Hyon Rhim, Sung; Kim, Miyoung; Freeman, A. J.

    2004-03-01

    III-V semiconductors are important for their extensive applications as optical devices such as laser diodes and infrared sensors. Optical properties, [ɛ_2(ω), n, k, R, and α], of III-V semiconductors (InAs, InSb, GaSb, and AlSb), are investigated using our highly precise full-potential linearized augmented plane wave(E.Wimmer,H.Krakauer, M.Weinert, A.J.Freeman, PRB,24), 864 (1981)(FLAPW) method with the screened-exchange local density approximation( R.Asahi,W.Mannstadt, A.J.Freeman,PRB,59), 7486 (1999)(sX-LDA) solved self-consistently and with spin-orbit coupling included. The imaginary part of the dielectric constant, ɛ_2(ω) is calculated using the longitudinal expression with full e^iqotr matrix elements, due to the nonlocality of the potential in the sX-LDA method(R.Del Sole, R.Girlanda, PRB 48), 11789 (1993). The structure of the ɛ_2(ω)'s are analyzed with band structures and consideration of interband transitions. The result shows good agreement of the peak positions in ɛ_2(ω) with experiment( D.E.Aspnes,A.A.Studna, PRB 27), 985 (1983) .

  4. Synthesis, photophysical and electroluminescent properties of novel iridium (III) complexes based on 5-methyl-2-phenylbenzo[d]oxazole derivatives

    NASA Astrophysics Data System (ADS)

    Li, Xiao; Chi, Hai-Jun; Dong, Yan; Xiao, Guo-Yong; Lei, Peng; Zhang, Dong-Yu; Cui, Zheng

    2013-12-01

    A new series of phosphorescent iridium (III) complexes based on 5-methyl-2-phenylbenzo[d]oxazole derivatives as main ligands, i.e. bis(5-methyl-2- phenylbenzo[d]oxazole-N,C2‧)iridium(acetylacetonate) [(mpbo)2Ir(acac)], bis(2-(4-fluorophenyl)-5-methylbenzo[d]oxazole-N,C2‧)iridium(acetylacetonate) [(fmbo)2Ir(acac)] and bis(5-methyl-2-p-tolylbenzo[d]oxazole-N,C2‧) iridium(acetylacetonate) [(mtbo)2Ir(acac)], were synthesized for organic light-emitting diodes (OLEDs), and their photophysical, electroluminescent properties were investigated. All complexes have high thermal stability and emit intense phosphorescence from green to yellow at room temperature with high quantum efficiencies and relatively short lifetimes. The OLED based on (fmbo)2Ir(acac) as dopant emitter showed very high luminance of 26,004 cd m-2 and luminance efficiency of 18.5 cd A-1. The evidences indicated that this series of iridium (III) complexes were potential candidates for applications in organic electroluminescent devices.

  5. Blue light emission from cyclometallated iridium (III) cyano complexes: Syntheses, crystal structures, and photophysical properties

    DOE PAGES

    Sanner, Robert D.; Cherepy, Nerine J.; Young, Jr., Victor G.

    2015-11-02

    In this study, we describe the synthesis and crystal structures of four iridium compounds containing the 2-(4,6-difluorophenyl)pyridyl ligand. Cleavage of dichloro-bridged iridium(III) dimers with phosphorus ligands leads to (46dfppy)2Ir(L)(Cl) where L = PPh3 or P(OPh)3. Treatment of the chloro compounds with cyanide forms the cyano complexes (46dfppy)2Ir(L)(CN). All complexes exhibit a trans effect in their molecular structures due to the phosphorus ligands, with the phosphite having a greater effect than the phosphine. With L = PPh3, blue photoluminescence with CIE coordinates (x = 0.16, y = 0.24), quantum yield of 0.66 ± 0.15 and 4.5 ± 0.5 μs decay timemore » is measured. For L = P(OPh)3, blue photoluminescence with CIE coordinates (x = 0.16, y = 0.21), quantum yield of 0.65 ± 0.15 and 2.9 ± 0.3 μs decay time is measured.« less

  6. Blue light emission from cyclometallated iridium (III) cyano complexes: Syntheses, crystal structures, and photophysical properties

    SciTech Connect

    Sanner, Robert D.; Cherepy, Nerine J.; Young, Jr., Victor G.

    2015-11-02

    In this study, we describe the synthesis and crystal structures of four iridium compounds containing the 2-(4,6-difluorophenyl)pyridyl ligand. Cleavage of dichloro-bridged iridium(III) dimers with phosphorus ligands leads to (46dfppy)2Ir(L)(Cl) where L = PPh3 or P(OPh)3. Treatment of the chloro compounds with cyanide forms the cyano complexes (46dfppy)2Ir(L)(CN). All complexes exhibit a trans effect in their molecular structures due to the phosphorus ligands, with the phosphite having a greater effect than the phosphine. With L = PPh3, blue photoluminescence with CIE coordinates (x = 0.16, y = 0.24), quantum yield of 0.66 ± 0.15 and 4.5 ± 0.5 μs decay time is measured. For L = P(OPh)3, blue photoluminescence with CIE coordinates (x = 0.16, y = 0.21), quantum yield of 0.65 ± 0.15 and 2.9 ± 0.3 μs decay time is measured.

  7. Optical properties of layered III-VI semiconductor γ-InSe:M (M=Mn, Fe, Co, Ni)

    NASA Astrophysics Data System (ADS)

    Milutinović, Aleksandra; Lazarević, Zorica Ž.; Jakovljević, Milka; Hadzić, Branka; Petrović, Milica; Gilić, Martina; Dobrowolski, Witold Daniel; Romčević, Nebojša Ž.

    2016-02-01

    Indium selenide belongs to layered III-VI semiconductors with highly anisotropic optical and electronic properties. Energy gap of 1.32 eV makes this material very attractive for solar energy conversion. We investigated the influence of 1% 3-d transition metals M=Mn, Fe, Co, Ni, used as dopants, on energy levels of InSe:M in the range 1.4-6.5 eV and especially in the range of energy gap <1.4 eV by means of ellipsometric measurements. It was concluded that at ambient temperature foregoing dopants, all divalent, with 4s2 valent electrons, in the similar way influenced on blue-shift of energy levels in valent zone, but did not influence on the fundamental energy gap. Photoluminescence measurements confirmed blue-shift of the valent zone energy levels and an existence of deep impurity levels.

  8. Two- and three-dimensional networks of gadolinium(III) with dicarboxylate ligands: synthesis, crystal structure, and magnetic properties.

    PubMed

    Cañadillas-Delgado, Laura; Pasan, Jorge; Fabelo, Oscar; Hernandez-Molina, María; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2006-12-25

    Four gadolinium(III) complexes with dicarboxylate ligands of formulas [Gd2(mal)3(H2O)5]n.2nH2O (1), [Gd2(mal)3(H2O)6]n (2), [NaGd(mal)(ox)(H2O)3]n (3), and [Gd2(ox)3(H2O)6]n.2.5nH2O (4) (mal = malonate; ox = oxalate) have been prepared, and their magnetic properties have been investigated as a function of the temperature. The structures of 1-3 have been determined by X-ray diffraction methods. The crystal structure of 4 was already known, and it is made of hexagonal layers of Gd atoms that are bridged by bis-bidentate oxalate. Compound 1 is isostructural with the europium(III) malonate complex [Eu2(mal)3(H2O)5]n.2nH2O,1 whose structure was reported elsewhere. The Gd atoms in 1 define a two-dimensional network where a terminal bidentate and bridging bidentate/bis-monodentate and tris-bidentate coordination modes of malonate occur. Compound 2 has a three-dimensional structure with a structural phase transition at 226 K, which involves a change of the space group from I2/a to Ia. Although its structure at room temperature was already known, that below 226 K was not. Pairs of Gd atoms with a double oxo-carboxylate bridge occur in both phases, and the main differences between both structures deal with the Gd environment and the H-bond pattern. 3 is also a three-dimensional compound, and it was obtained by reacting Gd(III) ions with malonic acid in a silica gel medium. Oxalic acid results as an oxidized product of the malonic acid, and single crystals of the heteroleptic complex were produced. The Gd atoms in 3 are connected through bis-bidentate oxalate and carboxylate-malonate bridges in the anti-anti and anti-syn coordination modes. Compounds 1 and 2 exhibit weak but significant ferromagnetic couplings between the Gd(III) ions through the single (1) and double (2) oxo-carboxylate bridges, whereas antiferromagnetic interactions across the bis-bidentate oxalate account for the overall antiferromagnetic behavior observed in 3 and 4.

  9. [Raynaud's phenomenon: pathogenesis and prevalence].

    PubMed

    Mikulska, Danuta

    2010-01-01

    Raynaud's phenomenon is defined as occasional ischemia of the distal parts of the extremities. Ischemia may be idiopathic as in primary Raynaud's disease or instigated by a comorbidity as in Raynaud's syndrome. Opinions on the etiopathogenesis of Raynaud's phenomenon have changed during recent years. Research has shown that enhanced vascular reactivity is attributable more to local factors and less to abnormalities in the central nervous system. Local factors are classified as vascular, nervous, and intravascular. Changes in our understanding of the etiopathogenesis of Raynaud's phenomenon have resulted in modified therapeutic guidelines. The present work reviews current opinions on the etiopathogenesis of Raynaud's phenomenon.

  10. Amine templated open-framework vanadium(III) phosphites with catalytic properties.

    PubMed

    Orive, Joseba; Larrea, Edurne S; Fernández de Luis, Roberto; Iglesias, Marta; Mesa, José L; Rojo, Teófilo; Arriortua, María I

    2013-04-07

    Four novel amine templated open-framework vanadium(III) phosphites with the formula (C(5)N(2)H(14))(0.5)[V(H(2)O)(HPO(3))(2)], 1 (C(5)N(2)H(14) = 2-methylpiperazinium), and (L)(4-x)(H(3)O)(x)[V(9)(H(2)O)(6)(HPO(3))(14-y)(HPO(4))(y)(H(2)PO(3))(3-z)(H(2)PO(4))z]·nH(2)O (2, L = cyclopentylammonium, x = 0, y = 3.5, z = 3, n = 0; , L = cyclohexylammonium, x = 1, y = 0, z = 0.6, n = 2.33; , L = cycloheptylammonium, x = 1, y = 0, z = 0, n = 2.33) were synthesized employing solvothermal reactions and characterized by single-crystal X-ray diffraction, ICP-AES and elemental analyses, thermogravimetric and thermodiffractometric analyses, and IR and UV/vis spectroscopy. Single-crystal data indicate that 1 crystallizes in the triclinic system, space group P1, whereas 2, 3 and 4 crystallize in the hexagonal space group P6(3)/m. Compound 1 has a two-dimensional motif with anionic sheets of [V(H(2)O)(HPO(3))(2)](-) formula, whose charge is compensated by the 2-methylpiperazinium cations embedded between the layers. In contrast, 2, 3 and 4 present a pillar-layer network giving rise to a three-dimensional framework containing intersecting 16-ring channels with the primary amine templates and the crystallization water molecules enclosed in them. 1, 2, 3 and 4 behave as heterogeneous catalysts for the selective oxidation of alkyl aryl sulfides, with tert-butylhydroperoxide (TBHP) as the oxidizing agent, being active, selective and recyclable for several successive cycles of reaction.

  11. THE SPATIAL STRUCTURE OF YOUNG STELLAR CLUSTERS. III. PHYSICAL PROPERTIES AND EVOLUTIONARY STATES

    SciTech Connect

    Kuhn, Michael A.; Feigelson, Eric D.; Getman, Konstantin V.; Sills, Alison; Bate, Matthew R.; Borissova, Jordanka

    2015-10-20

    We analyze the physical properties of stellar clusters that are detected in massive star-forming regions in the MYStIX project—a comparative, multiwavelength study of young stellar clusters within 3.6 kpc that contain at least one O-type star. Tabulated properties of subclusters in these regions include physical sizes and shapes, intrinsic numbers of stars, absorptions by the molecular clouds, and median subcluster ages. Physical signs of dynamical evolution are present in the relations of these properties, including statistically significant correlations between subcluster size, central density, and age, which are likely the result of cluster expansion after gas removal. We argue that many of the subclusters identified in Paper I are gravitationally bound because their radii are significantly less than what would be expected from freely expanding clumps of stars with a typical initial stellar velocity dispersion of ∼3 km s{sup −1} for star-forming regions. We explore a model for cluster formation in which structurally simpler clusters are built up hierarchically through the mergers of subclusters—subcluster mergers are indicated by an inverse relation between the numbers of stars in a subcluster and their central densities (also seen as a density versus radius relation that is less steep than would be expected from pure expansion). We discuss implications of these effects for the dynamical relaxation of young stellar clusters.

  12. Detecting effects of filaments on galaxy properties in the Sloan Digital Sky Survey III

    NASA Astrophysics Data System (ADS)

    Chen, Yen-Chi; Ho, Shirley; Mandelbaum, Rachel; Bahcall, Neta A.; Brownstein, Joel R.; Freeman, Peter E.; Genovese, Christopher R.; Schneider, Donald P.; Wasserman, Larry

    2017-04-01

    We study the effects of filaments on galaxy properties in the Sloan Digital Sky Survey (SDSS) Data Release 12 using filaments from the 'Cosmic Web Reconstruction' catalogue, a publicly available filament catalogue for SDSS. Since filaments are tracers of medium- to high-density regions, we expect that galaxy properties associated with the environment are dependent on the distance to the nearest filament. Our analysis demonstrates that a red galaxy or a high-mass galaxy tends to reside closer to filaments than a blue or low-mass galaxy. After adjusting the effect from stellar mass, on average, early-forming galaxies or large galaxies have a shorter distance to filaments than late-forming galaxies or small galaxies. For the main galaxy sample, all signals are very significant (>6σ). For the LOWZ and CMASS sample, the stellar mass and size are significant (>2σ). The filament effects we observe persist until z = 0.7 (the edge of the CMASS sample). Comparing our results to those using the galaxy distances from redMaPPer galaxy clusters as a reference, we find a similar result between filaments and clusters. Moreover, we find that the effect of clusters on the stellar mass of nearby galaxies depends on the galaxy's filamentary environment. Our findings illustrate the strong correlation of galaxy properties with proximity to density ridges, strongly supporting the claim that density ridges are good tracers of filaments.

  13. The Carbon Star Phenomenon

    NASA Astrophysics Data System (ADS)

    Wing, Robert F.

    2000-06-01

    The atmospheres of many stars have chemical compositions that are significantly different from that of the interstellar medium from which they are formed. This symposium considered all kinds of late-type stars showing altered compositions, the carbon stars being simply the best-known of these. All stages of stellar evolution from the main sequence to the ejection of a planetary nebula were considered, with emphasis on the changes that occur on the asymptotic giant branch. The spectroscopic properties of the photospheres and circumstellar envelopes of chemically-peculiar red giant stars, their origins via single-star evolution or mass transfer in binary systems, and the methods currently used to study them were all discussed in detail. This volume includes the full texts of papers given orally at the symposium and abstracts of the posters. Link: http://www.wkap.nl/book.htm/0-7923-6347-7

  14. The Lyman alpha reference sample. III. Properties of the neutral ISM from GBT and VLA observations

    SciTech Connect

    Pardy, Stephen A.; Cannon, John M.; Melinder, Jens E-mail: jcannon@macalester.edu; and others

    2014-10-20

    We present new H I imaging and spectroscopy of the 14 UV-selected star-forming galaxies in the Lyman Alpha Reference Sample (LARS), aimed for a detailed study of the processes governing the production, propagation, and escape of Lyα photons. New H I spectroscopy, obtained with the 100 m Green Bank Telescope (GBT), robustly detects the H I spectral line in 11 of the 14 observed LARS galaxies (although the profiles of two of the galaxies are likely confused by other sources within the GBT beam); the three highest redshift galaxies are not detected at our current sensitivity limits. The GBT profiles are used to derive fundamental H I line properties of the LARS galaxies. We also present new pilot H I spectral line imaging of five of the LARS galaxies obtained with the Karl G. Jansky Very Large Array (VLA). This imaging localizes the H I gas and provides a measurement of the total H I mass in each galaxy. In one system, LARS 03 (UGC 8335 or Arp 238), VLA observations reveal an enormous tidal structure that extends over 160 kpc from the main interacting systems and that contains >10{sup 9} M {sub ☉} of H I. We compare various H I properties with global Lyα quantities derived from Hubble Space Telescope measurements. The measurements of the Lyα escape fraction are coupled with the new direct measurements of H I mass and significantly disturbed H I velocities. Our robustly detected sample reveals tentative correlations between the total H I mass and linewidth, and key Lyα tracers. Further, on global scales, these data support a complex coupling between Lyα propagation and the H I properties of the surrounding medium.

  15. Optical properties of a tetradentate bis(beta-diketonate) europium(III) complex.

    PubMed

    Chen, Biao; Luo, Yanhua; Liang, Hao; Xu, Jie; Guo, Fuquan; Zhang, Yizhong; Lin, Aibin; Liu, Xuan

    2008-10-01

    Eu2(BPOPB)3H2O, an europium complex chelated with bis(beta-diketone), was synthesized. Its properties have been investigated by absorption spectrum, emission spectrum and luminescence lifetime measurement. The complex displays strong red luminescence upon irradiation at the ligand band around 355 nm, which indicates that the bis-beta-diketonate ligand BPOPB is an efficient sensitizer. The Judd-Ofelt parameters obtained from the emission spectrum of Eu2(BPOPB)3H2O have been used to calculate the total spontaneous emission probabilities (A), the radiative lifetime (tau(rad)), the fluorescence branching ratio (beta) and the stimulated emission cross-sections (sigma). The luminescence lifetimes are determined to be 402 and 169 micros for Eu2(BPOPB)3H2O and Eu(DBM)3(H2O)2, respectively. The relationship between the structures of rare-earth complexes and luminescence lifetimes was analyzed. The radiative properties reveal that Eu2(BPOPB)3H2O is potential to be an efficient luminescent material.

  16. Tetrathiafulvalene-Supported Triple-Decker Phthalocyaninato Dysprosium(III) Complex: Synthesis, Properties and Surface Assembly

    PubMed Central

    Gao, Feng; Zhang, Xue-Mei; Cui, Long; Deng, Ke; Zeng, Qing-Dao; Zuo, Jing-Lin

    2014-01-01

    Self-assembly of functional compounds into a prerequisite nanostructure with desirable dimension and morphology by controlling and optimizing intermolecular interaction attracts an extensive research interest for chemists and material scientist. In this work, a new triple-decker sandwich-type lanthanide complex with phthalocyanine and redox-active Schiff base ligand including tetrathiafulvalene (TTF) units has been synthesized, and characterized by single crystal X-ray diffraction analysis, absorption spectra, electrochemical and magnetic measurements. Interestingly, the non-centrosymmetric target complex displays a bias dependent selective adsorption on a solid surface, as observed by scanning tunneling microscopy (STM) at the single molecule level. Density function theory (DFT) calculations are utilized to reveal the formation mechanism of the molecular assemblies, and show that such electrical field dependent selective adsorption is regulated by the interaction between the external electric field and intrinsic molecular properties. Our results suggest that this type of multi-decker complex involving TTF units shows intriguing multifunctional properties from the viewpoint of structure, electric and magnetic behaviors, and fabrication through self-assembly. PMID:25088605

  17. Optical properties of a tetradentate bis(β-diketonate) europium(III) complex

    NASA Astrophysics Data System (ADS)

    Chen, Biao; Luo, Yanhua; Liang, Hao; Xu, Jie; Guo, Fuquan; Zhang, Yizhong; Lin, Aibin; Liu, Xuan

    2008-10-01

    Eu 2(BPOPB) 3H 2O, an europium complex chelated with bis(β-diketone), was synthesized. Its properties have been investigated by absorption spectrum, emission spectrum and luminescence lifetime measurement. The complex displays strong red luminescence upon irradiation at the ligand band around 355 nm, which indicates that the bis-β-diketonate ligand BPOPB is an efficient sensitizer. The Judd-Ofelt parameters obtained from the emission spectrum of Eu 2(BPOPB) 3H 2O have been used to calculate the total spontaneous emission probabilities ( A), the radiative lifetime ( τrad), the fluorescence branching ratio (β) and the stimulated emission cross-sections ( σ). The luminescence lifetimes are determined to be 402 and 169 μs for Eu 2(BPOPB) 3H 2O and Eu(DBM) 3(H 2O) 2, respectively. The relationship between the structures of rare-earth complexes and luminescence lifetimes was analyzed. The radiative properties reveal that Eu 2(BPOPB) 3H 2O is potential to be an efficient luminescent material.

  18. Structures, luminescent and magnetic properties of six lanthanide-organic frameworks: observation of slow magnetic relaxation behavior in the DyIII compound.

    PubMed

    Hou, Yin-Ling; Xiong, Gang; Shen, Bo; Zhao, Bin; Chen, Zhi; Cui, Jian-Zhong

    2013-03-14

    Six novel three-dimensional (3D) lanthanide metal-organic frameworks (LnMOFs), {[Ln(2)(ispc)(3)(H(2)O)(3)]·mH(2)O}(n) (Ln = Pr (1, m = 5); Eu (2, m = 5); Gd (3, m = 4); Tb (4, m = 5); Dy (5, m = 5) and Ho (6, m = 4)), ispc = 3-(4-carboxyphenylsulfonyloxy)-4-methoxybenzoic anion) have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction revealed they are isostructural and crystallize in the triclinic crystal system, space group P1[combining macron]. The investigations on luminescent properties and lifetimes of 2 (Eu(III)), 4 (Tb(III)), and 5 (Dy(III)) exhibit characteristic emissions of Eu(III), Tb(III) and Dy(III) ions and the corresponding luminescent lifetimes are 0.14 ms, 9.93 μs and 1.25 ms, respectively. The different luminescent intensities and lifetimes among them were further discussed. Furthermore, magnetic studies of 1-6 reveal that 3-6 exhibit ferromagnetic coupling, and 5 (Dy(III)) exhibits remarkably slow magnetic relaxation behavior with the energy barrier ΔE/k(B) = 49.2 K.

  19. Electrical properties and band diagram of InSb-InAs nanowire type-III heterojunctions

    NASA Astrophysics Data System (ADS)

    Shik, A.; Chen, C. Y.; Pitanti, A.; Tredicucci, A.; Ercolani, D.; Sorba, L.; Beltram, F.; Ruda, H. E.

    2013-03-01

    The electrical properties of nanowire-based n-InSb-n-InAs heterojunctions were investigated theoretically and experimentally. Analysis of the current-voltage characteristics showed that the current through the heterojunction is caused mostly by generation-recombination processes in the InSb and at the heterointerface. Due to the partially overlapping valence band of InSb and the conduction band of InAs, the second process is fast and activationless. Theoretical analysis showed that, depending on the heterojunction parameters, the flux of non-equilibrium minority carriers may have a different direction, explaining the experimentally observed non-monotonic coordinate dependence of the electron beam induced current.

  20. Optical properties and electrical transport of thin films of terbium(III) bis(phthalocyanine) on cobalt

    PubMed Central

    Robaschik, Peter; Siles, Pablo F; Bülz, Daniel; Richter, Peter; Monecke, Manuel; Fronk, Michael; Klyatskaya, Svetlana; Grimm, Daniel; Schmidt, Oliver G; Ruben, Mario; Zahn, Dietrich R T

    2014-01-01

    Summary The optical and electrical properties of terbium(III) bis(phthalocyanine) (TbPc2) films on cobalt substrates were studied using variable angle spectroscopic ellipsometry (VASE) and current sensing atomic force microscopy (cs-AFM). Thin films of TbPc2 with a thickness between 18 nm and 87 nm were prepared by organic molecular beam deposition onto a cobalt layer grown by electron beam evaporation. The molecular orientation of the molecules on the metallic film was estimated from the analysis of the spectroscopic ellipsometry data. A detailed analysis of the AFM topography shows that the TbPc2 films consist of islands which increase in size with the thickness of the organic film. Furthermore, the cs-AFM technique allows local variations of the organic film topography to be correlated with electrical transport properties. Local current mapping as well as local I–V spectroscopy shows that despite the granular structure of the films, the electrical transport is uniform through the organic films on the microscale. The AFM-based electrical measurements allow the local charge carrier mobility of the TbPc2 thin films to be quantified with nanoscale resolution. PMID:25551034

  1. Synthesis, photoluminescence and biological properties of terbium(III) complexes with hydroxyketone and nitrogen containing heterocyclic ligands.

    PubMed

    Poonam; Kumar, Rajesh; Boora, Priti; Khatkar, Anurag; Khatkar, S P; Taxak, V B

    2016-01-05

    The ternary terbium(III) complexes [Tb(HDAP)3⋅biq], [Tb(HDAP)3⋅dmph] and [Tb(HDAP)3⋅bathophen] were prepared by using methoxy substituted hydroxyketone ligand HDAP (2-hydroxy-4,6-dimethoxyacetophenone) and an ancillary ligand 2,2-biquinoline or 5,6-dimethyl-1,10-phenanthroline or bathophenanthroline respectively. The ligand and synthesized complexes were characterised based on elemental analysis, FT-IR and (1)H NMR. Thermal behaviour of the synthesized complexes illustrates the general decomposition patterns of the complexes by thermogravimetric analysis. Photophysical properties such as excitation spectra, emission spectra and luminescence decay curves of the complexes were investigated in detail. The main green emitting peak at 548nm can be attributed to (5)D4→(7)F5 of Tb(3+) ion. Thus, these complexes might be used to make a bright green light-emitting diode for display purpose. In addition the in vitro antibacterial activities of HDAP and its Tb(III) complexes against Bacillus subtilis, Staphylococcus aureus, Escherichia coli and antifungal activities against Candida albicans and Aspergillus niger are reported. The Tb(3+) complexes were found to be more potent antimicrobial agent as compared to the ligand. Among all these complexes, [Tb(HDAP)3⋅bathophen] exhibited excellent antimicrobial activity which proves its potential usefulness as an antimicrobial agent. Furthermore, in vitro antioxidant activity tests were carried out by using DPPH method which indicates that the complexes have considerable antioxidant activity when compared with the standard ascorbic acid.

  2. Synthesis, photoluminescence and biological properties of terbium(III) complexes with hydroxyketone and nitrogen containing heterocyclic ligands

    NASA Astrophysics Data System (ADS)

    Poonam; Kumar, Rajesh; Boora, Priti; Khatkar, Anurag; Khatkar, S. P.; Taxak, V. B.

    2016-01-01

    The ternary terbium(III) complexes [Tb(HDAP)3ṡbiq], [Tb(HDAP)3ṡdmph] and [Tb(HDAP)3ṡbathophen] were prepared by using methoxy substituted hydroxyketone ligand HDAP (2-hydroxy-4,6-dimethoxyacetophenone) and an ancillary ligand 2,2-biquinoline or 5,6-dimethyl-1,10-phenanthroline or bathophenanthroline respectively. The ligand and synthesized complexes were characterised based on elemental analysis, FT-IR and 1H NMR. Thermal behaviour of the synthesized complexes illustrates the general decomposition patterns of the complexes by thermogravimetric analysis. Photophysical properties such as excitation spectra, emission spectra and luminescence decay curves of the complexes were investigated in detail. The main green emitting peak at 548 nm can be attributed to 5D4 → 7F5 of Tb3+ ion. Thus, these complexes might be used to make a bright green light-emitting diode for display purpose. In addition the in vitro antibacterial activities of HDAP and its Tb(III) complexes against Bacillus subtilis, Staphylococcus aureus, Escherichia coli and antifungal activities against Candida albicans and Aspergillus niger are reported. The Tb3+ complexes were found to be more potent antimicrobial agent as compared to the ligand. Among all these complexes, [Tb(HDAP)3ṡbathophen] exhibited excellent antimicrobial activity which proves its potential usefulness as an antimicrobial agent. Furthermore, in vitro antioxidant activity tests were carried out by using DPPH method which indicates that the complexes have considerable antioxidant activity when compared with the standard ascorbic acid.

  3. 1,2-Hydroxypyridonate/Terephthalamide Complexes of Gadolinium(III): Synthesis, Stability, Relaxivity, and Water Exchange Properties

    PubMed Central

    Werner, Eric J.; Kozhukh, Julia; Botta, Mauro; Moore, Evan G.; Avedano, Stefano; Aime, Silvio; Raymond, Kenneth N.

    2009-01-01

    Four new Gd(III) complexes based on the 1,2-hydroxypyridinone chelator have been synthesized and evaluated as potential MRI contrast agents. Previously reported work examining Gd-TREN-1,2-HOPO (3) suggests that the 1,2-HOPO unit binds strongly and selectively to Gd(III), encouraging further study of the stability and relaxivity properties of this class of compounds. Among the new complexes presented in this paper are the homopodal Gd-Ser-TREN-1,2-HOPO (Gd-5) and three heteropodal bis-1,2-HOPO-TAM complexes (Gd-6, Gd-7, and Gd-8). Conditional stability constants were determined and all pGd values are in the range of 18.5 − 19.7, comparable to other analogous HOPO complexes and currently used commercial contrast agents. Relaxivities for all complexes are about twice those of commercial agents, ranging from 7.8 − 10.5 mM−1s−1 (20 MHz; 25 °C), and suggest two inner-sphere water molecules in fast exchange. Luminescent measurements were used to verify the number of coordinated waters for Gd-5, and VT 17O NMR experiments were employed for the highly soluble Gd-TREN-bis-1,2-HOPO-TAM-N3 (Gd-8) complex to measure a fast water exchange rate, 298kex = 1/τM, of 5.1(±0.4) × 108 s−1 (298τM ∼ 2 ns). PMID:19032045

  4. Syntheses, crystal structures and properties of new lead(II) or bismuth(III) selenites and tellurite.

    PubMed

    Zhang, Su-Yun; Hu, Chun-Li; Li, Pei-Xin; Jiang, Hai-Long; Mao, Jiang-Gao

    2012-08-21

    Four new lead(II) or bismuth(III) selenites and a tellurite, namely, Pb(3)(TeO(3))Cl(4), Pb(3)(SeO(3))(2)Br(2), Pb(2)Cd(3)(SeO(3))(4)I(2)(H(2)O), Pb(2)Ge(SeO(3))(4) and BiFe(SeO(3))(3), have been prepared and structurally characterized by single crystal X-ray diffraction (XRD) analyses. These compounds exhibit five different types of structures. The structure of Pb(3)(TeO(3))Cl(4) features a three-dimensional (3D) lead(II) chloride network with tellurite anions filling in the 1D tunnels of Pb(4) 4-member rings (MRs) along the c-axis. Pb(3)(SeO(3))(2)Br(2) contains a 3D network composed of lead(II) selenite layers interconnected by bromide anions. Pb(2)Cd(3)(SeO(3))(4)I(2)(H(2)O) is a 3D structure based on 2D cadmium(II) selenite layers which are further connected by 1D lead(II) iodide ladder chains with lattice water molecules located at the 1D tunnels of the structure. Pb(2)Ge(SeO(3))(4) features a 3D framework constructed by the alternate arrangement of lead(II) selenite layers and germanium(iv) selenite layers in the [100] direction. The structure of BiFe(SeO(3))(3) is built on the 3D anionic framework of ion(III) selenite with the bismuth(III) ions located at its Fe(6)Se(6) 12-MR tunnels. Pb(3)(TeO(3))Cl(4) (Pna2(1)) is polar and BiFe(SeO(3))(3) (P2(1)2(1)2(1)) is noncentrosymmetric. Powder second-harmonic generation (SHG) measurements using 1064 nm radiation indicate that BiFe(SeO(3))(3) exhibits a weak SHG efficiency of about 0.2 × KH(2)PO(4) (KDP). Magnetic property measurements for BiFe(SeO(3))(3) show a dominant antiferromagnetic interaction with weak spin-canting at low temperatures. IR, UV-vis and thermogravimetric, as well as electronic structure calculations were also performed.

  5. A multiwavelength study of the IRAS Deep Survey galaxy sample. III. Spectral classification and dynamical properties

    NASA Astrophysics Data System (ADS)

    Bettoni, D.; Mazzei, P.; Della Valle, A.

    2012-02-01

    FIR properties of the whole sample well. Moreover, their optical properties are typical of the sample itself since 62% of these belong to the 60 μm selected complete sample.

  6. Synthesis, characterization, photophysical and oxygen-sensing properties of a novel europium(III) complex

    NASA Astrophysics Data System (ADS)

    Feng, Nan; Xie, Jing; Zhang, Dawei

    2010-09-01

    In this paper, we report the synthesis, characterization, crystal structure, and photophysical properties of a novel Eu 3+ complex of Eu(DBM) 3IPD, where DBM = 1,3-diphenyl-propane-1,3-dione and IPD = 4-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)-N,N-diphenylaniline. Its elementary application for oxygen-sensing application is also investigated by doping it into a silica matrix of MCM-41. Experimental data suggest that the 20 mg/g doped Eu(DBM) 3IPD/MCM-41 system exhibits a high sensitivity of 3.6 towards molecular oxygen with a good linear relationship of R2 = 0.9987. In addition, the 20 mg/g doped Eu(DBM) 3IPD/MCM-41 system owns a quick response of 8 s towards oxygen, along with its excellent atmosphere insensitivity and photobleaching resistance. All these results suggest that both Eu(DBM) 3IPD and Eu(DBM) 3IPD/MCM-41 systems are promising candidates for oxygen-sensing optical sensors.

  7. Terrestrial kilometric radiation. III - Average spectral properties. [observations by IMP-6 and RAE-2 satellites

    NASA Technical Reports Server (NTRS)

    Kaiser, M. L.; Alexander, J. K.

    1977-01-01

    The spectral properties of terrestrial kilometric radiation (TKR) derived from observations made during radio-astronomy experiments on board the Imp 6 and Radio Astronomy Explorer 2 spacecraft are studied. As viewed from near the equatorial plane, TKR is most intense and most often observed in the 2100-2400 LT zone and is rarely seen in the 0900-1200 LT zone. The absolute flux levels in the 100- to 600-kHz TKR band increase significantly with increasing substorm activity as inferred from the auroral electrojet index (AE). In the late-evening sector the median power increases by about 3 orders of magnitude between quiet periods (AE less than 75 gammas) and disturbed periods (AE above 200 gammas). The peak flux density usually occurs near 250 kHz, although the frequency of the peak in the flux spectrum appears to vary inversely with AE from a maximum near 300 kHz during very quiet times to a minimum below 200 kHz during very disturbed times. The half-power bandwidth is typically 100% of the peak frequency. The variation of TKR flux density with apparent source altitude indicates that source strength decreases more rapidly than the inverse square of distance.

  8. Addressing the electronic properties of III-V nanowires by photoluminescence excitation spectroscopy

    NASA Astrophysics Data System (ADS)

    De Luca, M.

    2017-02-01

    Semiconductor nanowires (NWs) have been attracting an increasing interest in the scientific community. This is due to their peculiar filamentary shape and nanoscale diameter, which renders them versatile and cost-effective components of novel technological devices and also makes them an ideal platform for the investigation of a variety of fascinating physical effects. Absorption spectroscopy is a powerful and non-destructive technique able to provide information on the physical properties of the NWs. However, standard absorption spectroscopy is hard to perform in NWs, because of their small volume and the presence of opaque substrates. Here, we demonstrate that absorption can be successfully replaced by photoluminescence excitation (PLE). First, the use of polarization-resolved PLE to address the complex and highly-debated electronic band structure of wurtzite GaAs and InP NWs is shown. Then, PLE is used as a statistically-relevant method to localize the presence of separate wurtzite and zincblende NWs in the same InP sample. Finally, a variety of resonant exotic effects in the density of states of In x Ga1-x As/GaAs core/shell NWs are highlighted by high-resolution PLE. , which features invited work from the best early-career researchers working within the scope of J. Phys. D. This project is part of the Journal of Physics’ series 50th anniversary celebrations in 2017. Marta De Luca was selected by the Editorial Board of J. Phys. D as a Leader.

  9. Structural and Optical Properties of Group III Doped Hydrothermal ZnO Thin Films

    NASA Astrophysics Data System (ADS)

    Mughal, Asad J.; Carberry, Benjamin; Speck, James S.; Nakamura, Shuji; DenBaars, Steven P.

    2017-01-01

    In this work, we employ a simple two-step growth technique to deposit impurity doped heteroepitaxial thin films of (0001) ZnO onto (111) MgAl2O4 spinel substrates through a combination of atomic layer deposition (ALD) and hydrothermal growth. The hydrothermal layer is doped with Al, Ga, and In through the addition of their respective nitrate salts. We evaluated the effect that varying the concentrations of these dopants has on both the structural and optical properties of these films. It was found that the epitaxial ALD layer created a < 111rangle_{{{{MgAl}}2 {{O}}4 }} | {< 0001rangle_{{ZnO}} } out-of-plane orientation and a < bar{1}bar{1}2rangle_{{{{MgAl}}2 {{O}}4 }} | {< 01bar{1}0rangle_{{ZnO}} } in-plane orientation between the film and substrate. The rocking curve line widths ranged between 0.75° and 1.80° depending on dopant concentration. The optical bandgap determined through the Tauc method was between 3.28 eV and 3.39 eV and showed a Burstein-Moss shift with increasing dopant concentration.

  10. Synthesis, crystal structure, spectroscopic, thermal and dielectric properties of a novel semi-organic pentachloroantimonate (III)

    NASA Astrophysics Data System (ADS)

    Lahbib, Ikram; Rzaigui, Mohamed; Smirani, Wajda

    2016-09-01

    A new organic-inorganic hybrid material of formula (C10H15N2F)5(SbCl5)5.2H2O was synthesized and characterized by X-Ray diffraction analysis. It crystallizes in the monoclinic space group P21/c with the following unit cell parameters a = 15.819(4) Å, b = 17.685(3) Å, c = 30.529(4) Å, Z = 4 and V = 8540(3) Å3. The examination of the structure shows that the three-dimensional frameworks are produced by Nsbnd H⋯Cl, Nsbnd H⋯O, Csbnd H⋯Cl and Nsbnd H⋯F, Csbnd H⋯F hydrogen bonding and Cl⋯Cl interactions. IR, Raman and UV-Visible spectroscopies were also used to characterize this compound. In addition, the fluorescent properties of this compound have been investigated in the liquid state at room temperature. Differential scanning calorimetry (DSC) has revealed a structural phase transition of the order-disorder type around 370 K. Dielectric investigations revealed a step-wise change of the electric permittivity at Ttr characteristic of the crystal in the high-temperature phase. The evolution of dielectric constant as a function of temperature of the sample has been investigated in order to determine some related parameters. Measurements of AC conductivity as a function of frequency at different temperatures indicated a hopping conduction mechanism and/or reorientational motion.

  11. Structural and Optical Properties of Group III Doped Hydrothermal ZnO Thin Films

    NASA Astrophysics Data System (ADS)

    Mughal, Asad J.; Carberry, Benjamin; Speck, James S.; Nakamura, Shuji; DenBaars, Steven P.

    2017-03-01

    In this work, we employ a simple two-step growth technique to deposit impurity doped heteroepitaxial thin films of (0001) ZnO onto (111) MgAl2O4 spinel substrates through a combination of atomic layer deposition (ALD) and hydrothermal growth. The hydrothermal layer is doped with Al, Ga, and In through the addition of their respective nitrate salts. We evaluated the effect that varying the concentrations of these dopants has on both the structural and optical properties of these films. It was found that the epitaxial ALD layer created a < 111rangle_{{{{MgAl}}2 {{O}}4 }} | {< 0001rangle_{{ZnO}} } . out-of-plane orientation and a < bar{1}bar{1}2rangle_{{{{MgAl}}2 {{O}}4 }} | {< 01bar{1}0rangle_{{ZnO}} } . in-plane orientation between the film and substrate. The rocking curve line widths ranged between 0.75° and 1.80° depending on dopant concentration. The optical bandgap determined through the Tauc method was between 3.28 eV and 3.39 eV and showed a Burstein-Moss shift with increasing dopant concentration.

  12. Structural and magnetic properties of nanoclusters formed in III-V semiconductors

    NASA Astrophysics Data System (ADS)

    Lawniczak-Jablonska, Krystyna; Wolska, Anna; Klepka, Marcin T.

    2016-05-01

    Studies of X-ray magnetic circular dichroism (XMCD) were performed for a set of GaMnAs films with different Mn concentrations priory and after high temperature annealing (500 and 600 oC). After thermal treatment, GaMnAs samples with zinc blende structure and MnAs hexagonal nano-clusters were formed. In most of the samples, both types of clusters were detected by EXAFS studies. Dependence of the orbital and the spin moments on magnetic field were calculated from XMCD data by applying the sum rule. It was shown that both moments were much larger for MnAs nano-clusters. When these inclusions are formed even in a small amount, they dominate the XMCD signal. Interestingly, in some of samples the zinc blende GaMnAs nano-clusters were observed at a surface while in the bulk of hexagonal MnAs. Therefore, the location of magnetic ions in the host matrix is crucial for their magnetic properties. This unique information can be provided by XAS and XMCD.

  13. Theory of the shimmy phenomenon

    NASA Astrophysics Data System (ADS)

    Zhuravlev, V. Ph.; Klimov, D. M.

    2010-06-01

    The shimmy phenomenon is the appearance of angular self-excited vibrations of the carriage wheels. Such self-excited vibrations provide a serious safety hazard for motion, which explains the great interest of scientists in this phenomenon [1-6]. This problem is most serious for the aircraft fore wheels. It is commonly agreed that themain cause of the shimmyphenomenon is the tyre deformation [2]. We do not doubt this thesis, but still we note that this cause is not unique. The shimmy phenomenon can be observed in everyday life in the case of various hand trucks with rigid wheels, where the reference to the elastic tyre is out of place. In what follows, we show that the theory of polycomponent dry friction can completely explain the shimmy phenomenon for absolutely rigid wheels, and hence can be at least one of the causes of this phenomenon in the general case. Dry friction has been ignored by the scientists in their explanations of the shimmy phenomenon, because this friction has not been fully investigated until now, and it has been impossible to explain the shimmy phenomenon in the framework of the former representations.

  14. CCD photometry of distant comets. III. Ensemble properties of Jupiter-family comets

    NASA Astrophysics Data System (ADS)

    Lowry, S. C.; Fitzsimmons, A.; Collander-Brown, S.

    2003-01-01

    We describe the results of a ground-based observational ``snapshot'' study of Jupiter-family comets in the heliocentric range 2.29 AU <= Rh <= 5.72 AU. Results are presented based on observations from the 1m JKT on the island of La Palma. A total of 25 comets were targeted with 15 being positively detected. Broad-band VRI photometry was performed to determine dimensions, colour indices, and dust production rates in terms of the ``Afrho '' formalism. The results for selected comets are compared with previous investigations. Ensemble properties of the Jupiter-family population have been investigated by combining the results presented here with those of Lowry et al. (\\cite{Lowry1999}), and Lowry & Fitzsimmons (\\cite{Lowry2001}). We find that the cumulative size distribution of the Jupiter-family comets can be described by a power law of the form; Sigma (> r)~ r-1.6 +/- 0.1. This size distribution is considerably shallower than that found for the observed Edgeworth-Kuiper belt objects, which may reflect either an intrinsic difference at small km-sizes in the belt, or the various processes affecting the nuclei of comets as their orbits evolve from the Edgeworth-Kuiper belt to the inner Solar system. Also, there would appear to be no correlation between nuclear absolute magnitude and perihelion distance. Finally, for the sample of active comets, there is a distinct correlation between absolute R band magnitude and perihelion distance, which can be explained by either a discovery bias towards brighter comets or in terms of ``rubble'' mantle formation.

  15. Numerical Simulation of Hot Accretion Flows. III. Revisiting Wind Properties Using the Trajectory Approach

    NASA Astrophysics Data System (ADS)

    Yuan, Feng; Gan, Zhaoming; Narayan, Ramesh; Sadowski, Aleksander; Bu, Defu; Bai, Xue-Ning

    2015-05-01

    Previous MHD simulations have shown that wind must exist in black hole hot accretion flows. In this paper, we continue our study by investigating the detailed properties of wind and the mechanism of wind production. For this aim, we make use of a 3D general relativistic MHD simulation of hot accretion flows around a Schwarzschild black hole. To distinguish real wind from turbulent outflows, we track the trajectories of the virtual Lagrangian particles from simulation data. We find two types of real outflows, i.e., a jet and a wind. The mass flux of wind is very significant, and its radial profile can be described by {{\\dot{M}}wind}≈ {{\\dot{M}}BH}≤ft( r/20 {{r}s} \\right), with {{\\dot{M}}BH} being the mass accretion rate at the black hole horizon and rs being the Schwarzschild radius. The poloidal wind speed almost remains constant once they are produced, but the flux-weighted wind speed roughly follows {{v}p,wind}(r)≈ 0.25{{v}k}(r), with vk(r) being the Keplerian speed at radius r. The mass flux of the jet is much lower, but the speed is much higher, {{v}p,jet} ˜ (0.3-0.4)c. Consequently, both the energy and momentum fluxes of the wind are much larger than those of the jet. The wind is produced and accelerated primarily by the combination of centrifugal force and magnetic pressure gradient, while the jet is mainly accelerated by the magnetic pressure gradient. Finally, we find that the wind production efficiency {{ɛ }wind}\\equiv {{\\dot{E}}wind}/{{\\dot{M}}BH}{{c}2}˜ 1/1000 is in good agreement with the value required from large-scale galaxy simulations with active galactic nucleus feedback.

  16. Visible-light-driven photocatalytic properties of simply synthesized α-Iron(III)oxide nanourchins.

    PubMed

    Jiao, Yang; Liu, Yang; Qu, Fengyu; Umar, Ahmad; Wu, Xiang

    2015-08-01

    Well-crystalline α-Fe2O3 nanourchins were successfully prepared via a facile hydrothermal method using dimethylsulfoxide (DMSO) as the growth template and characterized in detail in terms of their morphological, structural, compositional and photocatalytic properties. To understand the growth process for the formation of α-Fe2O3 nanourchins, several reaction time and DMSO amount dependant experiments were performed and it was found that reaction time and the amount of DMSO are critical parameters to obtain urchin-shaped morphologies. A plausible growth mechanism for the formation of α-Fe2O3 nanourchins was presented. The prepared α-Fe2O3 nanourchins were used as efficient photocatalyst for the photocatalytic degradation of three harmful organic dyes, i.e. Congo red (CR), Eosin red (ER) and methylene blue (MB) under visible light illumination. The order of degradation rate for all used dyes are MB (80%)

  17. Characterization of the Photophysical, Thermodynamic, and Structural Properties of the Terbium(III)-DREAM Complex.

    PubMed

    Gonzalez, Walter G; Ramos, Victoria; Diaz, Maurizio; Garabedian, Alyssa; Molano-Arevalo, Juan Camilo; Fernandez-Lima, Francisco; Miksovska, Jaroslava

    2016-03-29

    properties of DREAM using lanthanides as well as the study of DREAM-protein complexes by lanthanide resonance energy transfer or nuclear magnetic resonance.

  18. [Raynaud's phenomenon, disease or syndrome?].

    PubMed

    Fiessinger, Jean-Noël

    2011-09-01

    Raynaud's phenomenon is a common symptom. More often it is usually an idiopathic and benign condition. But it can be an early manifestation of a connective tissue disease especially scleroderma and primary Sjogren's syndrom. Thus it is necessary to develop reasonable screening model. If the vasomotor symptoms are localized, a diagnosis of secondary Raynaud's phenomenon is highly probable and the main etiology is an arterial disease. Occupational arterial lesions are a particularly aspect of secondary Raynaud's phenomenon. Calcium channel blockers are the reference for the symptomatic treatment of Raynaud's phenomenon. In severe secondary forms, intravenous iloprost infusion is effective. New drugs as endothelin antagonist and phospodiesterase type 5 inhibitors are still to be evaluated.

  19. [Methylphenidate and secondary Raynaud's phenomenon].

    PubMed

    Iglesias Otero, M; Portela Romero, M; Bugarín González, R; Ventura Victoria, M A

    2013-09-01

    Raynaud's phenomenon is a clinical disease characterized by episodic attacks of vasoconstriction of the arteries and arterioles of the extremities such as fingers and toes, sometimes the ears and nose, in response to cold or emotional stimuli. A classic attack is the pallor of the distal extremity, followed by cyanosis and redness, accompanied by paresthesia, usually as heat. When it occurs without apparent cause is called primary Raynaud's phenomenon. When associated with other disease, is called secondary Raynaud's phenomenon. The secondary table is associated with increased frequency of rheumatic diseases of collagen. They can also present certain drugs that cause vasoconstriction, such as ergotamine, beta-adrenergic antagonists, contraception and sympathomimetic drugs. Regarding the latter, we present a case of Raynaud's phenomenon secondary to methylphenidate in a 14 years.

  20. The Mechanical Properties of III-V Compound Semiconductors Used in High Efficiency Multijunction Photovoltaic Cells

    NASA Astrophysics Data System (ADS)

    Zakaria, Abdallah

    Lattice-mismatched heteroepitaxy enables the fabrication of metamorphic solar cells that have reached record light conversion efficiencies in the last five years. These devices are accelerating the commercialization of concentrator photovoltaics that can compete with fossil fuels for terrestrial energy production. A critical part of metamorphic structures is the graded buffer layer (GBL) needed to progressively change the lattice constant of the substrate to that the epilayer of interest. The effectiveness of the graded buffer layer in relieving misfit strain affects the quality of the device grown and depends on a variety of parameters. This study focuses on the mechanical properties of semiconductor compounds used in graded buffer layers. First, the effect of compound semiconductor spontaneous atomic ordering on hardness is assessed. In1--xGaxP was deposited on Ge wafers in two structures. A surfactant was used in experiment A to induce a lower degree of order. High resolution x-ray diffraction (HRXRD) estimated a theoretical band gap energy Eg corrected for strain effects. Photoluminescence measured the actual Eg. By comparing the two, the degree of order eta was determined to be 0.12-0.15 for samples A and 0.43-0.44 for samples B. Atomic force microscopy (AFM) demonstrated that all wafers had an equivalent surface roughness of 6.1-7.4 A. Nanoindentation measurements determined that the degree of order has no effect on the hardness of InGaP. Using 1/2 (115) superlattice reflection scans, the InGaP ordered domains size was estimated to be 28.5 nm for sample B1. No superlattice peak was detected in sample A1. The large ordered domain size in B1 explains why no order-hardening behavior was observed in InGaP. Second, a correlation between the composition of a ternary compound semiconductor and hardness is established and the effect of oxidation is determined. A structure consisting of three different AlxGa1--xAs layers separated by In0.01Ga0.99As etch stops was

  1. Further characterization of the metabolic properties of triglyceride-rich lipoproteins from human and mouse apoC-III transgenic mice.

    PubMed

    Aalto-Setälä, K; Weinstock, P H; Bisgaier, C L; Wu, L; Smith, J D; Breslow, J L

    1996-08-01

    We previously showed that human apoC-III expression in transgenic mice causes hypertriglyceridemia due to the accumulation of enlarged very low density lipoprotein (VLDL)-like particles, with increased triglycerides and apoC-III and decreased apoE. In vivo turnover studies indicated the metabolic basis was decreased particle fractional catabolic rate. The presence of enlarged triglyceride-rich particles with prolonged residence time in plasma implied defective lipolysis, but in vitro these particles were good substrates for purified lipoprotein lipase (LPL). In the current study we further characterize the metabolic properties of these particles. We show that expression of a mouse apoC-III transgene can also cause hypertriglyceridemia with a similar accumulation of a VLDL-like particle with increased apoC-III and decreased apoE. A vitamin A fat tolerance test was used to show that MoCIIITg and HuCIIITg mice had similarly delayed clearance of triglyceride-rich postprandial particles. Thus, the previously observed hypertriglyceridemia caused by human apoC-III transgene expression was not due interspecies incompatibility but a property of apoC-III. In further experiments we showed VLDL from apoC-III transgenic mice interacted poorly with fibroblast lipoprotein receptors and this could be corrected by adding exogenous apoE. In addition, control VLDL interaction could be decreased by exogenous apoC-III. Moreover, the hypertriglyceridemia of HuCIIITg mice could be normalized by crossbreeding with HuETg mice. Thus, a functionally significant reciprocal relationship of apoC-III and apoE exists, presumably due to competition for space on the surface of triglyceride-rich lipoproteins. Finally, VLDL from HuCIITg and MoCIIITg mice showed decreased binding to heparin-Sepharose. This suggests and additional locus of the defect in these mice could potentially be in the binding of triglyceride-rich lipoproteins to heparan sulfate proteoglycan matrix on the surface of endothelial

  2. Third-Order Nonlinear Optic and Optical Limiting Properties of a Mn(iii) Transition Metal Complex

    NASA Astrophysics Data System (ADS)

    Karakas, Asli; Elmali, Ayhan; Yahsi, Yasemin; Kara, Hulya

    N,N‧-bis(5-bromosalicylidene)propane-1,2-diamine-O,O‧,N,N‧)-manganese(III) chloride transition metal complex has been synthesized and characterized by elemental analysis and UV-vis spectroscopy. Its crystal structure has been determined using X-ray diffraction analysis. To provide an insight into the optical limiting (OL) behavior of the title compound, the third-order nonlinear optical (NLO) properties, one-photon absorption (OPA) and two-photon absorption (TPA) characterizations have been theoretically investigated by means of the time-dependent Hartree-Fock (TDHF), AM1 and configuration interaction (CI) methods, respectively. According to ab initio calculation results, the examined molecule exhibits second hyperpolarizabilities (γ) with non-zero values at the positions of TPA peaks, implying microscopic third-order optical nonlinearity. The maximum OPA wavelengths recorded by linear optical experiment and quantum mechanical computations are estimated in the UV region to be shorter than 400 nm, showing good optical transparency to the visible light. The TPA cross-sections (δ(ω)) at λ max(2) values indicate that the synthesized compound might possess OL phenomena, which are in accord with the experimental observations on the manganese complexes in the literature.

  3. Synthesis and luminescent properties of complexes of Eu(III) with 2-thienyltrifluoroacetonate, terephthalic acid and phenanthroline

    NASA Astrophysics Data System (ADS)

    Zhao, X. H.; Huang, K. L.; Jiao, F. P.; Liu, S. Q.; Liu, Z. G.; Hu, S. Q.

    2007-09-01

    This work reports the synthesis and luminescent properties of complexes of europium(III) with 2-thienyltrifluoroacetonate (HTTA), terephthalic acid (TPA) and phenanthroline (Phen), in the solid state. The new complexes were characterized by elemental analysis, infrared (IR) spectroscopy, scanning electronic microscopy (SEM) and thermal stability analysis. Both binuclear complex Eu2(TPA)(TTA)4Phen2 and polynuclear complex Eu(TPA)(TTA)Phen present better thermal stability than the mononuclear complex Eu(TTA)3Phen does. The formation of the binuclear/polynuclear structure of the complexes appears to be responsible for the enhancement of the thermal stability. The emission spectra show narrow emission bands that arise from the 5D0→7FJ (J=0 4) transition of the Eu3+ ion. The spectral data of the complexes Eu(TPA)(TTA)Phen and Eu2(TPA)(TTA)4Phen2 present only one sharp peak in the region of the 5D0→7F0 transition indicating that only one Eu3+ ion species is present in each sample. In addition, the luminescence decay curves of the complexes Eu(TPA)(TTA)Phen and Eu2(TPA)(TTA)4Phen2 fit a single-exponential decay law. The values of quantum efficiencies of the emitting 5D0 level for the complexes Eu(TPA)(TTA)Phen and Eu2(TPA)(TTA)4Phen2 are 29% and 28%, respectively.

  4. Magnetic properties of the layered III-VI diluted magnetic semiconductor Ga1-xFexTe

    NASA Astrophysics Data System (ADS)

    Pekarek, T. M.; Edwards, P. S.; Olejniczak, T. L.; Lampropoulos, C.; Miotkowski, I.; Ramdas, A. K.

    2016-05-01

    Magnetic properties of single crystalline Ga1-xFexTe (x = 0.05) have been measured. GaTe and related layered III-VI semiconductors exhibit a rich collection of important properties for THz generation and detection. The magnetization versus field for an x = 0.05 sample deviates from the linear response seen previously in Ga1-xMnxSe and Ga1-xMnxS and reaches a maximum of 0.68 emu/g at 2 K in 7 T. The magnetization of Ga1-xFexTe saturates rapidly even at room temperature where the magnetization reaches 50% of saturation in a field of only 0.2 T. In 0.1 T at temperatures between 50 and 400 K, the magnetization drops to a roughly constant 0.22 emu/g. In 0 T, the magnetization drops to zero with no hysteresis present. The data is consistent with Van-Vleck paramagnetism combined with a pronounced crystalline anisotropy, which is similar to that observed for Ga1-xFexSe. Neither the broad thermal hysteresis observed from 100-300 K in In1-xMnxSe nor the spin-glass behavior observed around 10.9 K in Ga1-xMnxS are observed in Ga1-xFexTe. Single crystal x-ray diffraction data yield a rhombohedral space group bearing hexagonal axes, namely R3c. The unit cell dimensions were a = 5.01 Å, b = 5.01 Å, and c = 17.02 Å, with α = 90°, β = 90°, and γ = 120° giving a unit cell volume of 369 Å3.

  5. Syntheses, structures, and magnetic properties of acetato- and diphenolato-bridged 3d-4f binuclear complexes [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (M = Zn(II), Cu(II), Ni(II), Co(II); Ln = La(III), Gd(III), Tb(III), Dy(III); 3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato; ac = acetato; hfac = hexafluoroacetylacetonato; x = 0 or 1).

    PubMed

    Towatari, Masaaki; Nishi, Koshiro; Fujinami, Takeshi; Matsumoto, Naohide; Sunatsuki, Yukinari; Kojima, Masaaki; Mochida, Naotaka; Ishida, Takayuki; Re, Nazzareno; Mrozinski, Jerzy

    2013-05-20

    A series of 3d-4f binuclear complexes, [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (x = 0 for M = Cu(II), Zn(II); x = 1 for M = Co(II), Ni(II); Ln = Gd(III), Tb(III), Dy(III), La(III)), have been synthesized and characterized, where 3-MeOsaltn, ac, and hfac denote N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, acetato, and hexafluoroacetylacetonato, respectively. The X-ray analyses demonstrated that all the complexes have an acetato- and diphenolato-bridged M(II)-Ln(III) binuclear structure. The Cu(II)-Ln(III) and Zn(II)-Ln(III) complexes are crystallized in an isomorphous triclinic space group P1, where the Cu(II) or Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of 3-MeOsaltn at the equatorial coordination sites and one oxygen atom of the bridging acetato ion at the axial site. The Co(II)-Ln(III) and Ni(II)-Ln(III) complexes are crystallized in an isomorphous monoclinic space group P2(1)/c, where the Co(II) or Ni(II) ion at the high-spin state has an octahedral coordination environment with N2O2 donor atoms of 3-MeOsaltn at the equatorial sites, and one oxygen atom of the bridged acetato and a methanol oxygen atom at the two axial sites. Each Ln(III) ion for all the complexes is coordinated by four oxygen atoms of two phenolato and two methoxy oxygen atoms of "ligand-complex" M(3-MeOsaltn), four oxygen atoms of two hfac(-), and one oxygen atom of the bridging acetato ion; thus, the coordination number is nine. The temperature dependent magnetic susceptibilities from 1.9 to 300 K and the field-dependent magnetization up to 5 T at 1.9 K were measured. Due to the important orbital contributions of the Ln(III) (Tb(III), Dy(III)) and to a lesser extent the M(II) (Ni(II), Co(II)) components, the magnetic interaction between M(II) and Ln(III) ions were investigated by an empirical approach based on a comparison of the magnetic properties of the M(II)-Ln(III), Zn(II)-Ln(III), and M(II)-La(III) complexes. The differences of χ(M)T and M

  6. Color Change of Sudan III against Concentrated Sulfuric Acid in Acetonitrile and Quantification for a Small Amount of Concentrated Sulfuric Acid.

    PubMed

    Sakurai, Takao; Kurata, Shoji; Ogino, Kenji

    2016-01-01

    The color-changing phenomenon of hydrophobic bisazo dye, Sudan III in an acetonitrile solution against the addition of concentrated sulfuric acid has been discovered and the chromic properties investigated. Based on observations, a novel quantification method of concentrated sulfuric acid has been developed. Sudan III changes its color from orange to blue against a small volume of sulfuric acid, and the acetonitrile solution of Sudan III is the most suitable for observing the color-change phenomenon. (1)H-NMR and UV-Vis spectroscopic studies showed that the color-change mechanism of Sudan III against sulfuric acid is due to the protonation of the dye by sulfuric acid. This phenomenon is applicable to the quantification of concentrated sulfuric acid by introducing the Hammett acidity function. The proposed method requires only a small amount of the sample, 0.04 mL, and enables rapid quantification.

  7. Diffusion phenomenon in Hilbert spaces and applications

    NASA Astrophysics Data System (ADS)

    Radu, Petronela; Todorova, Grozdena; Yordanov, Borislav

    2011-06-01

    We prove an abstract version of the striking diffusion phenomenon that offers a strong connection between the asymptotic behavior of abstract parabolic and dissipative hyperbolic equations. An important aspect of our approach is that we use in a natural way spectral analysis without involving complicated resolvent estimates. Our proof of the diffusion phenomenon does not use the individual behavior of solutions; instead we show that only their difference matters. We estimate the Hilbert norm of the difference in terms of the Hilbert norm of solutions to the parabolic problems, which allows us to transfer the decay from the parabolic to the hyperbolic problem. The application of these estimates to operators with Markov property combined with a weighted Nash inequality yields explicit and sharp decay rates for hyperbolic problems with variable (x-dependent) coefficients in exterior domains. Our method provides new insight in this area of extensive research which was not well understood until now.

  8. Nutcracker phenomenon and nutcracker syndrome.

    PubMed

    Kurklinsky, Andrew K; Rooke, Thom W

    2010-06-01

    Nutcracker phenomenon refers to compression of the left renal vein, most commonly between the aorta and the superior mesenteric artery, with impaired blood outflow often accompanied by distention of the distal portion of the vein. The nutcracker syndrome (NCS) is the clinical equivalent of nutcracker phenomenon characterized by a complex of symptoms with substantial variations. Depending on specific manifestations, NCS may be encountered by different medical specialists. Although it may be associated with substantial morbidity, the diagnosis of NCS is often difficult and is commonly delayed. Diagnostic and treatment criteria are not well established, and the natural history of NCS is not well understood. We performed an initial review of the literature through MEDLINE, searching from 1950 to date and using the keywords nutcracker syndrome, nutcracker phenomenon, and renal vein entrapment. We performed additional reviews based on the literature citations of the identified articles. We attempted to elucidate clinical relevance of these conditions and their prominent features and to summarize professional experience.

  9. Terbium(III) and yttrium(III) complexes with pyridine-substituted nitronyl nitroxide radical and different β-diketonate ligands. Crystal structures and magnetic and luminescence properties.

    PubMed

    Lannes, Anthony; Intissar, Mourad; Suffren, Yan; Reber, Christian; Luneau, Dominique

    2014-09-15

    A terbium(III) complex of nitronyl nitroxide free radical 2-(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro1H-imidazolyl-1-oxy-3-oxide (NIT2Py), [Tb(acac)3NIT2Py]·0.5H2O (3) (acac = acetylacetonate), was synthesized for comparison with the previously reported [Tb(hfac)3NIT2Py]·0.5C7H16 (1) (hfac = hexafluoroacetylacetonate), together with their yttrium analogues [Y(hfac)3NIT2Py]·0.5C7H16 (2) and [Y(acac)3NIT2Py]·0.5H2O (4). The crystal structures show that in all complexes the nitronyl nitroxide radical acts as a chelating ligand. Magnetic studies show that 3 like 1 exhibits slow relaxation of magnetization at low temperature, suggesting single-molecule magnet behavior. The luminescence spectra show resolved vibronic structure with the main interval decreasing from 1600 cm(-1) to 1400 cm(-1) between 80 and 300 K. This effect is analyzed quantitatively using experimental Raman frequencies.

  10. Structural and electronic properties of group III Rich In 0.53Ga 0.47As(001)

    NASA Astrophysics Data System (ADS)

    Shen, Jian; Clemens, Jonathon B.; Chagarov, Evgueni A.; Feldwinn, Darby L.; Melitz, Wilhelm; Song, Tao; Bishop, Sarah R.; Kummel, Andrew C.; Droopad, Ravi

    2010-09-01

    The structural and electronic properties of group III rich In 0.53Ga 0.47As(001) have been studied using scanning tunneling microscopy/spectroscopy (STM/STS). At room temperature (300 K), STM images show that the In 0.53Ga 0.47As(001)-(4 × 2) reconstruction is comprised of undimerized In/Ga atoms in the top layer. Quantitative comparison of the In 0.53Ga 0.47As(001)-(4 × 2) and InAs(001)-(4 × 2) shows the reconstructions are almost identical, but In 0.53Ga 0.47As(001)-(4 × 2) has at least a 4× higher surface defect density even on the best samples. At low temperature (77 K), STM images show that the most probable In 0.53Ga 0.47As(001) reconstruction is comprised of one In/Ga dimer and two undimerized In/Ga atoms in the top layer in a double (4 × 2) unit cell. Density functional theory (DFT) simulations at elevated temperature are consistent with the experimentally observed 300 K structure being a thermal superposition of three structures. DFT molecular dynamics (MD) show the row dimer formation and breaking is facilitated by the very large motions of tricoodinated row edge As atoms and z motion of In/Ga row atoms induced changes in As-In/Ga-As bond angles at elevated temperature. STS results show there is a surface dipole or the pinning states near the valence band (VB) for 300 K In 0.53Ga 0.47As(001)-(4 × 2) surface consistent with DFT calculations. DFT calculations of the band-decomposed charge density indicate that the strained unbuckled trough dimers being responsible for the surface pinning.

  11. Properties of radiolabeled type I, II, and III collagens related to their use as substrates in collagenase assays

    SciTech Connect

    Mookhtiar, K.A.; Mallya, S.K.; Van Wart, H.E.

    1986-11-01

    Calf skin and rat tendon type I, bovine cartilage type II, and human amnion type III collagens have been radiolabeled by reaction with (/sup 3/H)acetic anhydride, (/sup 3/H)formaldehyde, and succinimidyl 2,3-(3H)propionate. All three reactions produce collagens with high specific activities that are suitable for use as substrates in collagenase assays. The identity of the radiolabel and the labeling indices do not alter the molecular weights or thermal stabilities of the collagens or the solubilities of the collagens or gelatins in dioxane-water mixtures at 4 degrees C. However, in contrast to native or sparsely labeled collagens, those with 40 or more lysine + hydroxylysine residues labeled per molecule do not undergo fibrillogenesis in the presence of 0.2-0.4 M NaCl in the 4-35 degree C temperature range. Thus, the modification reactions not only serve to introduce the radiolabel, but also to keep the collagens soluble over a wide range of temperatures and concentrations. The TCA, TCB fragments produced on partial reaction of each collagen type with tissue collagenases can be selectively denatured by a 10-minute incubation under specific conditions and the intact collagens selectively precipitated by addition of 50% v/v dioxane. This serves as the basis for soluble collagenase assays. The effect of labeling index on the properties of the collagens has been investigated and the results establish the range of conditions over which these collagens can be used as substrates for soluble versus fibrillar collagenase assays.

  12. A family of acetato-diphenoxo triply bridged dimetallic Zn(II)Ln(III) complexes: SMM behavior and luminescent properties.

    PubMed

    Oyarzabal, Itziar; Artetxe, Beñat; Rodríguez-Diéguez, Antonio; García, JoséÁngel; Seco, José Manuel; Colacio, Enrique

    2016-06-21

    Eleven dimetallic Zn(II)-Ln(III) complexes of the general formula [Zn(µ-L)(µ-OAc)Ln(NO3)2]·CH3CN (Ln(III) = Pr (1), Nd (2), Sm (3), Eu (4), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11)) have been prepared in a one-pot reaction from the compartmental ligand N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromo-benzyl)ethylenediamine (H2L). In all these complexes, the Zn(II) ions occupy the internal N2O2 site whereas the Ln(III) ions show preference for the O4 external site. Both metallic ions are bridged by an acetate bridge, giving rise to triple mixed diphenoxido/acetate bridged Zn(II)Ln(III) compounds. The Nd, Dy, Er and Yb complexes exhibit field induced single-ion magnet (SIM) behaviour, with Ueff values ranging from 14.12 to 41.55 K. The Er complex shows two relaxation processes, but only the second relaxation process with an energy barrier of 21.0 K has been characterized. The chromophoric L(2-) ligand is able to act as an "antenna" group, sensitizing the near-infrared (NIR) Nd(III) and Yb(III)-based luminescence in complexes 2 and 11 and therefore, both compounds can be considered as magneto-luminescent materials. In addition, the Sm(III), Eu(III) and Tb(III) derivatives exhibit characteristic emissions in the visible region.

  13. Applying the Fe(III) binding property of a chemical transferrin mimetic to Ti(IV) anticancer drug design.

    PubMed

    Parks, Timothy B; Cruz, Yahaira M; Tinoco, Arthur D

    2014-02-03

    As an endogenous serum protein binder of Ti(IV), transferrin (Tf) serves as an excellent vehicle to stabilize the hydrolysis prone metal ion and successfully transport it into cells. This transporting role is thought to be central to Ti(IV)'s anticancer function, but efforts to synthesize Ti(IV) compounds targeting transferrin have not produced a drug. Nonetheless, the Ti(IV) transferrin complex (Ti2Tf) greatly informs on a new Ti(IV)-based anticancer drug design strategy. Ti2Tf interferes with cellular uptake of Fe(III), which is particularly detrimental to cancer cells because of their higher requirement for iron. Ti(IV) compounds of chemical transferrin mimetic (cTfm) ligands were designed to facilitate Ti(IV) activity by attenuating Fe(III) intracellular levels. In having a higher affinity for Fe(III) than Ti(IV), these ligands feature the appropriate balance between stability and lability to effectively transport Ti(IV) into cancer cells, release Ti(IV) via displacement by Fe(III), and deplete the intracellular Fe(III) levels. The cTfm ligand N,N'-di(o-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED) was selected to explore the feasibility of the design strategy. Kinetic studies on the Fe(III) displacement process revealed that Ti(IV) can be transported and released into cells by HBED on a physiologically relevant time scale. Cell viability studies using A549 cancerous and MRC5 normal human lung cells and testing the cytotoxicity of HBED and its Ti(IV), Fe(III), and Ga(III) compounds demonstrate the importance of Fe(III) depletion in the proposed drug design strategy and the specificity of the strategy for Ti(IV) activity. The readily derivatized cTfm ligands demonstrate great promise for improved Ti(IV) anticancer drugs.

  14. Opioid antagonists and the sexual satiation phenomenon.

    PubMed

    Rodríguez-Manzo, G; Fernández-Guasti, A

    1995-11-01

    This study evaluates the effects of the IP injection of naloxone (0.3, 3 and 30 mg/kg) and naltrexone (0.2, 2 and 20 mg/kg) on the sexual satiation phenomenon. It was found that both antagonists exert a dose-based biphasic effect on the proportion of sexually exhausted rats displaying copulation. The intermediate doses of both opioid antagonists were more effective than the low and high doses in increasing the percentage of animals engaged in copulation. The analysis of the specific sexual behaviour parameters revealed that naloxone produces a slight inhibitory effect at the lowest dose, evidenced as an increase in the intromission number. The higher doses of this compound facilitated copulation reflected as a shortening of the ejaculation latency and the interintromission interval (III) and an increase in the copulatory rate. Naltrexone treatment had only facilitatory effects at the lower doses by reducing the III. The higher doses of naloxone (3 and 30 mg/kg) and the intermediate dose of naltrexone (2 mg/kg) decreased the spontaneous ambulatory behaviour of sexually satiated rats without impairing sexual behaviour execution. Data suggest a participation of the endogenous opioid systems in the sexual inhibition resulting from sexual exhaustion.

  15. Lanthanum(III)-Catalyzed Three-Component Reaction of Coumarin-3-carboxylates for the Synthesis of Indolylmalonamides and Analysis of Their Photophysical Properties.

    PubMed

    Jennings, Julia J; Bhatt, Chinmay P; Franz, Annaliese K

    2016-08-05

    New methodology has been developed for the Lewis acid catalyzed synthesis of malonamides. First, the scandium(III)-catalyzed addition of diverse nucleophiles (e.g., indoles, N,N-dimethyl-m-anisidine, 2-ethylpyrrole, and 2-methylallylsilane) to coumarin-3-carboxylates has been developed to afford chromanone-3-carboxylates in high yields as a single diastereomer. Upon investigating a subsequent lanthanum(III)-catalyzed amidation reaction, a new multicomponent reaction was designed by bringing together coumarin-3-carboxylates with indoles and amines to afford indolylmalonamides, which were identified to exhibit fluorescent properties. The photophysical properties for selected compounds have been analyzed, including quantum yield, molar absorptivity, and Stokes shift. Synthetic studies of several reaction byproducts involved in the network of reaction equilibria for the three-component reaction provide mechanistic insight for the development of this methodology.

  16. Translation as a Psycholinguistic Phenomenon

    ERIC Educational Resources Information Center

    Zasyekin, Serhiy

    2010-01-01

    The article sketches the outlines of a theoretical framework for the analysis of translation of literary texts, viewed as psycho-semiotic phenomenon and based on evaluation of earlier attempts in this direction, and on the results of a psycholinguistic empirical study of translations. Central to this framework is the recent insight that the human…

  17. Comprehensive evaluation of the physicochemical properties of Ln(III) complexes of aminoethyl-DO3A as pH-responsive T(1) -MRI contrast agents.

    PubMed

    Baranyai, Zsolt; Rolla, Gabriele A; Negri, Roberto; Forgács, Attila; Giovenzana, Giovanni B; Tei, Lorenzo

    2014-03-03

    N-Substituted aminoethyl groups were attached to 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) with the aim to design pH-responsive Ln(III) complexes based on the pH-dependent on/off ligation of the amine nitrogen to the metal ion. The following ligands were synthesized: AE-DO3A (aminoethyl-DO3A), MAE-DO3A (N-methylaminoethyl-DO3A), DMAE-DO3A (N,N-dimethylaminoethyl-DO3A) and MEM-AE-DO3A (N-methoxyethyl-N-methylaminoethyl-DO3A). The physicochemical properties of the Ln(III) complexes were investigated for the evaluation of their potential applicability as magnetic resonance imaging (MRI) contrast agents. In particular, a (1) H and (17) O NMR relaxometric study was carried out for these Gd(III) complexes at two different pH values: at basic pH (pendant amino group coordinated to the metal centre) and at acidic pH (protonated amine, not interacting with the metal ion). Eu(III) complexes allow one to estimate the number of inner-sphere water molecules through luminescence lifetime measurements and obtain some structural information through variable-temperature (VT) high-resolution (1) H NMR studies. Equilibria between differently hydrated species were found for most of the complexes at both acidic and basic pH. The thermodynamic stability of Ca(II) , Zn(II) , Cu(II) and Ln(III) complexes and kinetics of formation and dissociation reactions of Ln(III) complexes of AE-DO3A and DMAE-DO3A were investigated showing stabilities comparable to currently approved Gd(III) -based CAs. In detail, higher total basicity (Σlog Ki (H) ) and higher stability constants of Ln(III) complexes were found for AE-DO3A with respect to DMAE-DO3A (i.e., log KGd-AE-DO3A =22.40 and log KGd-DMAE-DO3A =20.56). The transmetallation reactions of Gd(III) complexes are very slow (Gd-AE-DO3A: t1/2 =2.7×10(4)  h; Gd-DMAE-DO3A: 1.1×10(5)  h at pH 7.4 and 298 K) and occur through proton-assisted dissociation.

  18. New routes to polymetallic clusters: fluoride-based tri-, deca-, and hexaicosametallic MnIII clusters and their magnetic properties.

    PubMed

    Jones, Leigh F; Rajaraman, Gopalan; Brockman, Jonathon; Murugesu, Muralee; Sanudo, E Carolina; Raftery, Jim; Teat, Simon J; Wernsdorfer, Wolfgang; Christou, George; Brechin, Euan K; Collison, David

    2004-10-11

    The syntheses, structures and magnetic properties of three new MnIII clusters, [Mn26O17(OH)8(OMe)4F10(bta)22(MeOH)14(H2O)2] (1), [Mn(0O6(OH)2(bta)8(py)8F8] (2) and [NHEt3]2[Mn3O(bta)6F3] (3), are reported (bta=anion of benzotriazole), thereby demonstrating the utility of MnF3 as a new synthon in Mn cluster chemistry. The "melt" reaction (100 degrees C) between MnF(3) and benzotriazole (btaH, C6H5N3) under an inert atmosphere, followed by dissolution in MeOH produces the cluster [Mn26O17(OH)8(OMe)4F10(bta)22(MeOH)14(H2O)2] (1) after two weeks. Complex 1 crystallizes in the triclinic space group P1, and consists of a complicated array of metal tetrahedra linked by mu3-O2- ions, mu3- and mu2-OH- ions, mu2-MeO- ions and mu2-bta- ligands. The "simpler" reaction between MnF3 and btaH in boiling MeOH (50 degrees C) also produces complex 1. If this reaction is repeated in the presence of pyridine, the decametallic complex [Mn10O6(OH)2(bta)8(py)8F8] (2) is produced. Complex 2 crystallizes in the triclinic space group P1 and consists of a "supertetrahedral" [Mn(III)10] core bridged by six mu3-O2- ions, two mu3-OH- ions, four mu2-F- ions and eight mu2-bta- ions. The replacement of pyridine by triethylamine in the same reaction scheme produces the trimetallic species [NHEt3]2[Mn3O(bta)6F3] (3). Complex 3 crystallises in the monoclinic space group P2(1)/c and has a structure analogous to that of the basic metal carboxylates of general formula [M3O(RCO2)6L3]0/+, which consists of an oxo-centred metal triangle with mu2-bta- ligands bridging each edge of the triangle and the fluoride ions acting as the terminal ligands. DC magnetic susceptibility measurements in the 300-1.8 K and 0.1-7 T ranges were investigated for all three complexes. For each, the value of chi(M)T decreases with decreasing temperatures; this indicates the presence of dominant antiferromagnetic exchange interactions in 1-3. For complex 1, the low-temperature value of chi(M)T is 10 cm(3) K mol(-1) and fitting of

  19. Synthesis, structure, catalytic and calculated non-linear optical properties of cis- and trans-, mer-chlorobis(triphenyl phosphine/triphenyl arsine)-dipicolinato ruthenium III complexes

    NASA Astrophysics Data System (ADS)

    Trivedi, Manoj; Nagarajan, R.; Kumar, Abhinav; Singh, Narendra K.; Rath, Nigam P.

    2011-05-01

    The new mononuclear Ru III complexes cis-, mer-[Ru( k3-dipic)(EPh 3) 2Cl]·2H 2O (E = P ( 1), As ( 2)), (L = 2,6-pyridyldicarboxylate; dipic) have been synthesized and characterized. The X-ray crystal structure of 1 reveals that the coordination geometry around the Ru III center is distorted octahedral in which three sites are occupied by tridentate dipic ligand and remaining three sites are occupied by two mutually cis triphenyl phosphine ligands and one chloride ions. In chloroform solvent, cis-, mer-[Ru( k3-dipic)(EPh 3) 2Cl]·2H 2O (E = P ( 1), As ( 2)) complexes undergoes thermal rearrangement to more stable trans-, mer-[Ru( k3-dipic)(EPh 3) 2Cl] (E = P( 3), As( 4)) complexes. Complexes 1 and 2 show rhombic EPR spectral features, while complex 3 and 4 show tetragonal distortion. The new Ru III complexes 1 and 2 display both Ru III-Ru II reduction and Ru III-Ru IV oxidation processes. These geometric isomers exhibit textbook differences both in spectroscopic as well as structural properties in the solid state. The new complexes 1 and 2 were found to catalyze the oxidation of alcohols to carbonyl derivatives using N-methyl morpholine- N-oxide as co-oxidant. The first static hyperpolarizability ( β) for all of the complexes have been investigated by density functional theory (DFT) which suggests β value increases from trans to cis form. Also, the solvent-induced effects on the non-linear optical properties (NLO) were studied by using self-consistent reaction field (SCRF) method. As the solvent polarity increases, the β value increases monotonically. The electronic absorption bands of 1 have been assigned by time dependent density functional theory (TD-DFT).

  20. Ba 3M IIITiM VO 9 (M III = Fe, Ga, Y, Lu; M V = Nb, Ta, Sb) perovskite oxides: Synthesis, structure and dielectric properties

    NASA Astrophysics Data System (ADS)

    Joy, Joby E.; Atamanik, Eric; Mani, Rohini; Nag, Abanti; Tiwari, R. M.; Thangadurai, V.; Gopalakrishnan, J.

    2010-12-01

    We describe the synthesis, structures and dielectric properties of new perovskite oxides of the formula, Ba 3M IIITiM VO 9, for M III = Fe, Ga, Y, Lu and M V = Nb, Ta, Sb. While M V = Nb and Ta oxides adopt disordered/partially ordered 3C perovskite structures where M III/Ti/M V metal-oxygen octahedra are corner-connected, the M V = Sb oxides show a distinct preference for the 6H structure, where Sb V/Ti IV metal-oxygen octahedra share a common face forming (Sb,Ti)O 9 dimers that are corner-connected to the M IIIO 6 octahedra. The preference of antimony oxides (Sb V:4d 10) for the 6H structure - which arises from a special Sb V-O chemical bonding that tends to avoid linear Sb-O-Sb linkages unlike Nb V/Ta V:d 0 atoms which prefer ˜180° Nb/Ta-O-Nb/Ta linkages - is consistent with the crystal chemistry of M V-O oxides in general. The dielectric properties reveal a significant difference among M III members. All the oxides with the 3C structure excepting those with M III = Fe show a normal low loss dielectric behaviour with ɛ = 20-60 in the temperature range 50-400 °C; the M III = Fe members with this structure (M V = Nb, Ta) display a relaxor-like ferroelectric behaviour with large ɛ values at frequencies ≤1 MHz (50-500 °C).

  1. The Dependence of Electrical Properties on Miscut Orientation in Direct Bonded III-V Solar Cell Layers

    NASA Astrophysics Data System (ADS)

    Seal, Mark

    Direct bonding is a materials integration process in which wafer substrates are directly bonded without any intermediate layers. This technique has been used to fabricate direct bonded n-GaAs//n-GaAs, n-GaAs//n-InP, and n-InP//n-InP structures comprised of combinations of on-axis substrates and substrates with (001) faces misoriented 4° toward in order to study the effect of relative surface misorientation on the electrical properties of the bonded interface. Simulation and measurement of interface electrical conductivity were used to identify properties including height and shape of the potential barrier. Across all substrate combinations, as the relative surface misorientation was increased, the interface resistance and height of the interfacial potential barrier also increased. Current density -- voltage measurements of GaAs//InP bonded structures revealed no band structure asymmetry at low ( +/- 50 mV) bias. Transmission electron microscopy was used to observe the morphology of the interface between InP//InP and GaAs//InP structures. Consistent with previous reports, results of electrical measurements indicate that the potential barrier height at interfaces containing at least one side InP are less sensitive to increased interface resistance with increasing misorientation. Low temperature (≤ 600 °C) and kPa applied pressure to initiate bonding between (NH4S)2 pretreated GaAs and InP wafers was used to fabricate direct bonded structures. Wafers were bonded face-to-face on-axis, with relative misorientation of 4° or 8°, or a by bonding a combination of 4° miscut substrates bonded such that relative misorientation was zero. The samples were annealed at 400 °C for 2 hours to strengthen the bond, and then subjected to rapid thermal processing at 600 °C for 2 minutes to improve the electrical conductivity. When compared to on-axis structures, the interface resistance at room temperature for 4° misoriented bonded pairs increased from 0.011 O˙cm2 to 2.8 O

  2. Property Accounting for Local and State School Systems. State Educational Records and Reports Series--Handbook III.

    ERIC Educational Resources Information Center

    Reason, Paul L.; Tankard, George G., Jr.

    This handbook serves as a basic guide to property accounting for local and state school systems in the U.S. Information and guidelines are presented regarding--(1) classification of property accounts, (2) definitions of property accounts, (3) measures of school property, (4) supplies and equipment, (5) individual property records, and (6) summary…

  3. Assembly and properties of heterobimetallic Co(II/III)/Ca(II) complexes with aquo and hydroxo ligands.

    PubMed

    Lacy, David C; Park, Young Jun; Ziller, Joseph W; Yano, Junko; Borovik, A S

    2012-10-24

    The use of water as a reagent in redox-driven reactions is advantageous because it is abundant and environmentally compatible. The conversion of water to dioxygen in photosynthesis illustrates one example, in which a redox-inactive Ca(II) ion and four manganese ions are required for function. In this report we describe the stepwise formation of two new heterobimetallic complexes containing Co(II/III) and Ca(II) ions and either hydroxo or aquo ligands. The preparation of a four-coordinate Co(II) synthon was achieved with the tripodal ligand, N,N',N"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzenesulfonamido, [MST](3-). Water binds to [Co(II)MST](-) to form the five-coordinate [Co(II)MST(OH(2))](-) complex that was used to prepare the Co(II)/Ca(II) complex [Co(II)MST(μ-OH(2))Ca(II)⊂15-crown-5(OH(2))](+) ([Co(II)(μ-OH(2))Ca(II)OH(2)](+)). [Co(II)(μ-OH(2))CaOH(2)](+) contained two aquo ligands, one bonded to the Ca(II) ion and one bridging between the two metal ions, and thus represents an unusual example of a heterobimetallic complex containing two aquo ligands spanning different metal ions. Both aquo ligands formed intramolecular hydrogen bonds with the [MST](3-) ligand. [Co(II)MST(OH(2))](-) was oxidized to form [Co(III)MST(OH(2))] that was further converted to [Co(III)MST(μ-OH)Ca(II)⊂15-crown-5](+) ([Co(III)(μ-OH)Ca(II)](+)) in the presence of base and Ca(II)OTf(2)/15-crown-5. [Co(III)(μ-OH)Ca(II)](+) was also synthesized from the oxidation of [Co(II)MST](-) with iodosylbenzene (PhIO) in the presence of Ca(II)OTf(2)/15-crown-5. Allowing [Co(III)(μ-OH)Ca(II)](+) to react with diphenylhydrazine afforded [Co(II)(μ-OH(2))Ca(II)OH(2)](+) and azobenzene. Additionally, the characterization of [Co(III)(μ-OH)Ca(II)](+) provides another formulation for the previously reported Co(IV)-oxo complex, [(TMG(3)tren)Co(IV)(μ-O)Sc(III)(OTf)(3)](2+) to one that instead could contain a Co(III)-OH unit.

  4. Synthesis of activated carbon-based amino phosphonic acid chelating resin and its adsorption properties for Ce(III) removal.

    PubMed

    Chen, Tao; Yan, Chunjie; Wang, Yixia; Tang, Conghai; Zhou, Sen; Zhao, Yuan; Ma, Rui; Duan, Ping

    2015-01-01

    This work aims to investigate the adsorption of Ce(III) onto chelating resin based on activated carbon (CRAC). The CRAC adsorbent was prepared from activated carbon (AC) followed by oxidation, silane coupling, ammoniation and phosphorylation, and characterized by Fourier transform-infrared spectrometry, nitrogen adsorption measurements and scanning electron microscopy. The effects of solution pH, adsorbent dosage and contact time were studied by batch technique. Langmuir and Freundlich isotherms were used to describe the adsorption behaviour of Ce(III) by CRAC, and the results showed that the adsorption behaviour well fitted the Langmuir model. The maximum uptake capacity (qmax) calculated by using the Langmuir equation for cerium ions was found to be 94.34 mg/g. A comparison of the kinetic models and the overall experimental data was best fitted with the type 1 pseudo second-order kinetic model. The calculated thermodynamic parameters (ΔG°, ΔH° and ΔS°) showed that the adsorption for Ce(III) was feasible, spontaneous and exothermic at 25-45 °C. The CRAC showed an excellent adsorptive selectivity towards Ce(III). Moreover, more than 82% of Ce(III) adsorbed onto CRAC could be desorbed with HCl and could be used several times.

  5. Investigations into the synthesis and fluorescence properties of Tb(III) complexes of a novel bis-β-diketone-type ligand and a novel bispyrazole ligand

    NASA Astrophysics Data System (ADS)

    Xiao, Lin-Xiang; Luo, Yi-Ming; Chen, Zhe; Li, Jun; Tang, Rui-Ren

    2008-11-01

    A novel bis-β-diketone organic ligand, 1,1'-(2,6-bispyridyl)bis-3-( p-methoxyphenyl)-1,3-propanedione (L 1) and its derivatives, a novel bispyrazole ligand, 2,6-bis(5-(4-methoxyphenyl)-1H-pyrazol-3-yl)pyridine (L 2) were designed and synthesized and their complexes with Tb(III) ion were successfully prepared. The ligands and the corresponding metal complexes were characterized by elemental analysis, infrared, proton nuclear magnetic resonance spectroscopy and TG-DTA. Analysis of the IR spectra suggested that the lanthanide metal ion Tb(III) coordinated to the ligands via the nitrogen atom of the pyridine ring and the carbonyl oxygen atoms for ligand L 1 and the nitrogen atom of the pyrazole ring for ligand L 2. The fluorescence properties of the two complexes in solid state were investigated and it was discovered that the Tb(III) ions could be sensitized by both the ligand (L 1) and ligand (L 2) to some extent. In particular, the complex of ligand (L 2) is a better green luminescent material that could be used as a candidate material in organic light-emitting devices (OLEDs) since it could be much better sensitized by the ligand (L 2), and the fluorescence intensity of Tb(III) complex of L 2 are almost as twice strong as L 1's.

  6. Investigations into the synthesis and fluorescence properties of Tb(III) complexes of a novel bis-beta-diketone-type ligand and a novel bispyrazole ligand.

    PubMed

    Xiao, Lin-Xiang; Luo, Yi-Ming; Chen, Zhe; Li, Jun; Tang, Rui-Ren

    2008-11-15

    A novel bis-beta-diketone organic ligand, 1,1'-(2,6-bispyridyl)bis-3-(p-methoxyphenyl)-1,3-propanedione (L1) and its derivatives, a novel bispyrazole ligand, 2,6-bis(5-(4-methoxyphenyl)-1H-pyrazol-3-yl)pyridine (L2) were designed and synthesized and their complexes with Tb(III) ion were successfully prepared. The ligands and the corresponding metal complexes were characterized by elemental analysis, infrared, proton nuclear magnetic resonance spectroscopy and TG-DTA. Analysis of the IR spectra suggested that the lanthanide metal ion Tb(III) coordinated to the ligands via the nitrogen atom of the pyridine ring and the carbonyl oxygen atoms for ligand L1 and the nitrogen atom of the pyrazole ring for ligand L2. The fluorescence properties of the two complexes in solid state were investigated and it was discovered that the Tb(III) ions could be sensitized by both the ligand (L1) and ligand (L2) to some extent. In particular, the complex of ligand (L2) is a better green luminescent material that could be used as a candidate material in organic light-emitting devices (OLEDs) since it could be much better sensitized by the ligand (L2), and the fluorescence intensity of Tb(III) complex of L2 are almost as twice strong as L1's.

  7. An unexpected cobalt(III) complex containing a Schiff base ligand: Synthesis, crystal structure, spectroscopic behavior, electrochemical property and SOD-like activity.

    PubMed

    Chai, Lan-Qin; Huang, Jiao-Jiao; Zhang, Hong-Song; Zhang, Yu-Li; Zhang, Jian-Yu; Li, Yao-Xin

    2014-10-15

    An unexpected mononuclear Co(III) complex, [Co(L2)2·(CH3COO)]·CH3OH (HL2=1-(2-{[(E)-3,5-dichloro-2-hydroxybenzylidene]amino}phenyl)ethanone oxime), has been synthesized via complexation of Co(II) acetate tetrahydrate with HL1 originally. The plausible reaction mechanism for the formation of quinazoline-type ligand was proposed. HL1 and its corresponding Co(III) complex were characterized by IR, as well as by elemental analysis and UV-vis spectroscopy. The crystal structure of the complex has been determined by single-crystal X-ray diffraction. Each complex links two other molecules into an infinite 1-D chain via intermolecular hydrogen bonding interactions. Moreover, the electrochemical properties of the cobalt(III) complex were studied by cyclic voltammetry and X-ray photoelectron spectrum (XPS). In addition, superoxide dismutase-like activities of HL1 and Co(III) complex were also investigated.

  8. Synthesis, structure and properties of a tetranuclear europium(III) complex based on 9,9-dimethylfluorene-2,7-diphosphonic acid

    NASA Astrophysics Data System (ADS)

    Li, Liang; Li, Ao; Song, Lin; Wang, Zi-Hao; Zhou, Xin-Hui; Yang, Tao; Huang, Wei

    2014-06-01

    One tetranuclear europium(III) phosphonate complex [Eu2(H4MFDP)(H3MFDP)4(H2MFDP)(H2O)4]·13.5H2O (EuMFDP), has been prepared by reactions of the new ligand 9,9-dimethylfluorene-2,7-diphosphonic acid (H4MFDP) with europium(III) nitrates. The crystal structure of complex EuMFDP has been determined using single-crystal X-ray diffraction. It features a strip-like tetranuclear structure, in which four ligands and four Eu(III) ions constitute the core. Interestingly, the four ligands in the core possess paddle-like arrangement. Although the free ligand H4MFDP exhibits the emission centered at 333 nm and 438 nm upon excitation at 310 nm, complex EuMFDP shows only very weak characteristic emission of Eu(III) ions, probably due to the strong quenching effect of OH vibration. The thermal property of EuMFDP has also been studied.

  9. Microcalorimetric and spectroscopic investigation of the antibacterial properties of cationic ytterbium(III)-porphyrin complexes lacking charged peripheral groups.

    PubMed

    Hou, An-Xin; Xue, Zhi; Liu, Yi; Qu, Song-Sheng; Wong, Wai-Kwok

    2007-12-01

    The antibacterial activities towards Escherichia coli of two cationic Yb(III)-monoporphyrin complexes, [Yb(III)(TMP)(H2O)3]Cl (1) and [Yb(III)(TTP)(H2O)3]Cl (2), were investigated at the cellular and sub-cellular levels. The biological effects of the complexes on the growth of E. coli were evaluated by microcalorimetry and by analysis of the resulting metabolic thermogenic curves, from which IC50 values and metabolic parameters such as growth rate and generation time were derived. At the subcellular level, DNA-binding experiments were performed by means of UV/VIS- and fluorescence-titration experiments, as well as by near-infrared (NIR) emission, which revealed that 1 and 2 strongly bind to herring-sperm DNA (HS-DNA), though by different binding modes.

  10. Primary structure, expression in Escherichia coli, and properties of S-adenosyl-L-methionine:uroporphyrinogen III methyltransferase from Bacillus megaterium.

    PubMed Central

    Robin, C; Blanche, F; Cauchois, L; Cameron, B; Couder, M; Crouzet, J

    1991-01-01

    A Bacillus megaterium DNA fragment encoding S-adenosyl-L-methionine:uroporphyrinogen III methyltransferase (SUMT) activity was subcloned and sequenced. The encoded polypeptide showed more than 43.5% strict homology to Pseudomonas denitrificans SUMT (F. Blanche, L. Debussche, D. Thibaut, J. Crouzet, and B. Cameron, J. Bacteriol. 171:4222-4231, 1989). The B. megaterium polypeptide was overexpressed in Escherichia coli, partially purified, and shown to exhibit, like P. denitrificans SUMT, substrate inhibition at uroporphyrinogen III concentrations above 0.5 microM, suggesting a common regulation for aerobic cobalamin-producing organisms. Images PMID:1906874

  11. Lattice Dynamical Properties of Group-III Nitrides AN (A = B, Al, Ga and In) in Zinc-Blende Phase

    NASA Astrophysics Data System (ADS)

    Kushwaha, A. K.

    2016-03-01

    In the present paper, we have calculated the phonon dispersion relations, phonon density of states, Debye characteristic temperature and the zone boundary phonons for group-III nitrides AN (A = B, Al, Ga and In) using eleven-parameter three-body shell model with both the ions being polarizable. Our calculated results are in good agreement with experimental results available in the literature.

  12. Studying the sorption properties of a clinoptilolite-containing tuff with respect to europium(III) ions

    NASA Astrophysics Data System (ADS)

    Kozhevnikova, N. M.

    2014-03-01

    The kinetic laws of sorption of europium(III) ions from sulfate solutions by a clinoptilolite-containing tuff are studied. The kinetic parameters of sorption process are determined and absorption isotherms are constructed for europium ions. It is found that both external and internal diffusion are rate-limiting steps, and europium is completely extracted from dilute solutions (<0.0025 m).

  13. An extended Hückel study of the electronic properties of III-V compounds and their alloys

    NASA Astrophysics Data System (ADS)

    Ribeiro, Ingrid A.; Ribeiro, Fabio J.; Martins, A. S.

    2014-05-01

    In this work, we performed tight binding calculations of the electronic structure of III-V semiconductors compounds and their alloys based on the Extended Hückel Theory (EHT). In particular, this paper is focused on the dependency between band gap and the applied pressure and also the alloy composition.

  14. Electronic Structures and Spectroscopic Properties of a Novel Iridium (III) Complex with an Ancillary Ligand 2-(4-Trifluoromethyl -2-Hydroxylphenyl) Benzothiazole

    NASA Astrophysics Data System (ADS)

    Lei, Li-Ping; Hao, Yu-Ying; Fan, Wen-Hao; Xu, Bing-She

    2011-06-01

    Iridium (III) complexes with 2-phenylpyridine (ppy) have been demonstrated as a type of promising phosphorescence dopant in emitting layers of organic light emitting diodes (OLEDs). In most iridium (III) complexes, there exist the strong spin-orbit coupling between π-orbitals of cyclometalated ligands and 5d orbitals of the centric iridium. We study a novel iridium (III) complex (ppy)2Ir(4-TfmBTZ) with ppy as cyclometalated ligands and 2-(4-trifluoromethyl-2-hydroxylphenyl)benzothiazole (4-TfmBTZ) as an ancillary ligand using the Gaussian 03 program. The geometries, electronic structures and spectroscopic properties of this iridium (III) complex are investigated by density functional theory (DFT) and time-dependent density functional theory (TD-DFT). The results show that the spin-orbit coupling occurs not only between ppy and iridium atom but also between 4-TfmBTZ and iridium atom in this complex. The highest occupied molecular orbital is dominantly localized on the Ir atom and 4-TfmBTZ ligand, while the lowest unoccupied molecular orbital on 4-TfmBTZ ligand. The triplet lowest-lying transition is attributed to the Ir-to-4-TfmBTZ charge-transfer (3MLCT) transition while the sub-low-lying transitions are assigned to the 3MLCT transitions of Ir(ppy)2. The nature of the lowest unoccupied orbital changes from ppy-localized to 4-TfmBTZ-localized and reveals that phosphorescent color of Ir(III) complex can be controlled by the ancillary ligand and substituent.

  15. Synthesis and fluorescence properties of Tb(III) complex with a novel β-diketone ligand as well as spectroscopic studies on the interaction between Tb(III) complex and bovine serum albumin

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenfeng; Tang, Ruiren

    2012-02-01

    A novel aromatic β-diketone ligand, 4-isopropyl-2,6-bisbenzoylactyl pyridine (L), and its corresponding Tb(III) complex Tb2(L)3·5H2O were synthesised in this paper. The ligand was characterized by FT-IR and 1H NMR. The complex was characterized with elemental analysis and FT-IR. The investigation of fluorescence property of the complex showed that the Tb(III) ion could be sensitized efficiently by the ligand. Furthermore, the interaction of Tb2(L)3·5H2O with bovine serum albumin (BSA) has been investigated by fluorescence quenching spectra, UV-vis absorbance and synchronous fluorescence spectra. The fluorescence quenching mechanism of BSA by Tb2(L)3·5H2O was analyzed. The binding constants, binding site number and the corresponding thermodynamic parameters at different temperatures were calculated. The results indicated that the Van der Waals and hydrogen bond interactions were the predominant intermolecular forces in stabilizing the complex. Moreover, the effect of Tb2(L)3·5H2O on the conformation of BSA was analyzed according to synchronous fluorescence.

  16. Religion as a Natural Phenomenon

    ScienceCinema

    Dennett, Daniel [Tufts University, Boston, Massachusetts, United States

    2016-07-12

    Religion is a costly human activity that has evolved over the millennia. Why does it exist and how does it foster such powerful allegiances? To undertake a serious scientific study of religious practices and attitudes we must set aside a traditional exemption from scrutiny which religions have enjoyed. Religious adherents may not welcome this attention, but we should press ahead with it, since if we don't come to understand religion as a natural phenomenon, our attempts to deal with the problems that loom in the twenty-first century will likely be counterproductive.

  17. Religion as a Natural Phenomenon

    SciTech Connect

    Dennett, Daniel

    2006-02-15

    Religion is a costly human activity that has evolved over the millennia. Why does it exist and how does it foster such powerful allegiances? To undertake a serious scientific study of religious practices and attitudes we must set aside a traditional exemption from scrutiny which religions have enjoyed. Religious adherents may not welcome this attention, but we should press ahead with it, since if we don't come to understand religion as a natural phenomenon, our attempts to deal with the problems that loom in the twenty-first century will likely be counterproductive.

  18. Cell phenomenology: The first phenomenon.

    PubMed

    Pattee, H H

    2015-12-01

    As a broad academic discipline phenomenology may be summarized as the study from a first person point of view of what appears to subjective human conscious experience. As a historical philosophical movement phenomenology was often motivated by the belief that subjective human experience is the proper foundation of all philosophy. I explore phenomena from a broader evolutionary and physical point of view. I consider a phenomenon as the subjective consequence of a physical interaction with an individual organism. In physical terms, a phenomenon requires some form of detection or measurement. What is detected is determined by the organism, and is potentially functional for the organism as a self or subject. The concept of function has meaning only for living organisms. The classical human mind-body problem is an ill-defined complicated case of the more general epistemic subject-object problem, which at the origin of life I reduce to the primitive symbol-matter problem. I argue that the first memory-based self-replicating unit, like a cell, is the most primitive case of a necessary symbol-matter distinction. The first phenomena, which include all forms or sensing, detection, and measurement, require a subject-object distinction, called the epistemic cut. It is only because of such a subject-object distinction that populations of individual subjects can selectively adapt to their environment by heritable variations. This basic evolutionary process requires distinguishing the individual's subjective phenomena from the objective events of inexorable physical laws.

  19. Water condensation: a multiscale phenomenon.

    PubMed

    Jensen, Kasper Risgaard; Fojan, Peter; Jensen, Rasmus Lund; Gurevich, Leonid

    2014-02-01

    The condensation of water is a phenomenon occurring in multiple situations in everyday life, e.g., when fog is formed or when dew forms on the grass or on windows. This means that this phenomenon plays an important role within the different fields of science including meteorology, building physics, and chemistry. In this review we address condensation models and simulations with the main focus on heterogeneous condensation of water. The condensation process is, at first, described from a thermodynamic viewpoint where the nucleation step is described by the classical nucleation theory. Further, we address the shortcomings of the thermodynamic theory in describing the nucleation and emphasize the importance of nanoscale effects. This leads to the description of condensation from a molecular viewpoint. Also presented is how the nucleation can be simulated by use of molecular models, and how the condensation process is simulated on the macroscale using computational fluid dynamics. Finally, examples of hybrid models combining molecular and macroscale models for the simulation of condensation on a surface are presented.

  20. Dependence of electrical property on the applied magnetic fields in spin coated Fe(III)-Phorphyrin films

    NASA Astrophysics Data System (ADS)

    Utari; Kusumandari; Purnama, B.; Mudasir; Abraha, K.

    2016-11-01

    We report here on the experimental results of the effect of external magnetic field on the current flow in plane surface of Fe(III)-porphyrin thin layer. The deposition of the Fe(III)- porphyrin thin layer was done by spin coating method. The I-V characteristics of film were measured by means of two point probes. The sample of layer number N = 4 was used to evaluate the magnetic effect on the electrical currents. The ohmic characteristics of the I-V film measurement were obtained. The current decreases when magnetic field is applied to the system and saturated current is obtained at a given magnetic field. Here, the decrease in the current can be attributed to the recombination of carrier charge under the magnetic field. In addition, the magnitude of the saturated current is found to increase with the increase in the voltage used.

  1. A trinuclear oxo-chromium(III) complex containing the natural flavonoid primuletin: Synthesis, characterization, and antiradical properties

    DOE PAGES

    Rocha, Reginaldo C.; Alexiou, Anamaria D.P.; Decandio, Carla C.; ...

    2015-04-10

    A new trinuclear oxo-centered chromium(III) complex with formula [Cr₃O(CH₃CO₂)₆(L)(H₂O)₂] (L = 5-hydroxyflavone, known as primuletin) was synthetized and characterized by ESI mass spectrometry, thermogravimetry, and ¹H-NMR, UV-Vis, and FTIR spectroscopies. In agreement with the experimental results, DFT calculations indicated that the flavonoid ligand is coordinated to one of the three Cr(III) centers in an O,O-bidentate mode through the 5-hydroxy/4-keto groups. In a comparative study involving the uncoordinated primuletin and its corresponding complex, systematic reactions with the free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) showed that antiradical activity increases upon complexation.

  2. Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

    SciTech Connect

    Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; Bae, Seong Hee; Hong, Seungwoo; Cho, Kyung-Bin; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2015-06-19

    Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn2+ ion in (TMC)FeIII-(O2)-Zn(CF3SO3)2 (1-Zn2+) decreases the Lewis acidity of the Zn2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn2+. This further changes the reactivities of 1-Zn2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn2+, whereas 1-Zn2+ coordinating two water molecules, (TMC)FeIII-(O2)-Zn(CF3SO3)2-(OH2)2 [1-Zn2+-(OH2)2], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1-Zn2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn2+-(OH2)2. Finally, the present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.

  3. Tuning the Redox Properties of a Nonheme Iron(III)-Peroxo Complex Binding Redox-Inactive Zinc Ions by Water Molecules

    DOE PAGES

    Lee, Yong-Min; Bang, Suhee; Yoon, Heejung; ...

    2015-06-19

    Here we report redox-inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. We describe the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox-inactive metal ions. The coordination of two water molecules to a Zn2+ ion in (TMC)FeIII-(O2)-Zn(CF3SO3)2 (1-Zn2+) decreases the Lewis acidity of the Zn2+ ion, resulting in the decrease of the one-electron oxidation and reduction potentials of 1-Zn2+. This further changes the reactivities of 1-Zn2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1-Zn2+, whereas 1-Zn2+ coordinatingmore » two water molecules, (TMC)FeIII-(O2)-Zn(CF3SO3)2-(OH2)2 [1-Zn2+-(OH2)2], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1-Zn2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1-Zn2+-(OH2)2. Finally, the present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates.« less

  4. Analytical and preparative enantioseparation and main chiroptical properties of Iridium(III) bis(4,6-difluorophenylpyridinato)picolinato.

    PubMed

    Citti, Cinzia; Battisti, Umberto M; Ciccarella, Giuseppe; Maiorano, Vincenzo; Gigli, Giuseppe; Abbate, Sergio; Mazzeo, Giuseppe; Castiglioni, Ettore; Longhi, Giovanna; Cannazza, Giuseppe

    2016-10-07

    Almost all Iridium(III) complexes employed both as dopants in PhOLEDs and as pharmaceuticals and fluorescence bioprobes are racemic mixtures. In this study the single enantiomers of the most stable diastereomeric form fac-trans-N-N, bis[2-(4,6-difluorophenyl)pyridinato-C(2),N](picolinato)iridium(III) (FIrpic) were separated and analysed. The data obtained showed that the complex can be separated into stable optically active Λ and Δ isomers employing cellulose based chiral stationary phase both in normal and polar phase mode. Their chirality was confirmed and their absolute configuration assigned employing several methods (DFT and TDDFT calculations, CD and VCD). The CPL spectroscopy of the isolated enantiomers of FIrpic was also recorded due to its possible value in the OLEDs field. The chromatographic method was applied for a semipreparative purpose demonstrating that polar organic solvent chromatography (POSC) could be used to avoid the low-solubility issues associated with these Iridium(III) complexes. Finally, the chemical and stereochemical stability of the single isomers was evaluated under thermal stress by liquid chromatography coupled to high-resolution mass spectrometry (LC-QTOF) on both chiral and achiral columns. No racemization and/or isomerization was observed; however, the dissociation of the ancillary ligand was demonstrated employing LC-QTOF.

  5. The dependence of C IV broad absorption line properties on accompanying Si IV and Al III absorption: relating quasar-wind ionization levels, kinematics, and column densities

    SciTech Connect

    Filiz Ak, N.; Brandt, W. N.; Schneider, D. P.; Trump, J. R.; Hall, P. B.; Anderson, S. F.; Hamann, F.; Myers, Adam D.; Pâris, I.; Petitjean, P.; Ross, Nicholas P.; Shen, Yue; York, Don

    2014-08-20

    We consider how the profile and multi-year variability properties of a large sample of C IV Broad Absorption Line (BAL) troughs change when BALs from Si IV and/or Al III are present at corresponding velocities, indicating that the line of sight intercepts at least some lower ionization gas. We derive a number of observational results for C IV BALs separated according to the presence or absence of accompanying lower ionization transitions, including measurements of composite profile shapes, equivalent width (EW), characteristic velocities, composite variation profiles, and EW variability. We also measure the correlations between EW and fractional-EW variability for C IV, Si IV, and Al III. Our measurements reveal the basic correlated changes between ionization level, kinematics, and column density expected in accretion-disk wind models; e.g., lines of sight including lower ionization material generally show deeper and broader C IV troughs that have smaller minimum velocities and that are less variable. Many C IV BALs with no accompanying Si IV or Al III BALs may have only mild or no saturation.

  6. Acoustical phenomenon in ancient Totonac's monument

    NASA Astrophysics Data System (ADS)

    Sánchez-Dehesa, José; Ha˚Kansson, Andreas; Cervera, Francisco; Meseguer, Francisco; Manzanares-Martínez, Betsabé; Ramos-Mendieta, Felipe

    2004-05-01

    The circle of gladiators is a monument built by Totonac Indians in the ceremonial site of Cempoala, which is located near Veracruz (Mexico). The city is believed to date to around 1200 A.D. The monument is a round structure with crenellated wall tops, and it has a diameter of 13.4 m. Though the deterioration of this monument is noticeable, it presents a singular acoustical phenomenon whose strength had to be probably extraordinary on the date of its construction. In brief, along any diameter in the circle, one can find two focal points such that if one person speaks on one focus, another person located on the other hears the sound reinforced. In other words, this circular place acoustically behaves as if it were elliptical. Here, we report the experimental characterization of the phenomenon and present a theoretical explanation. Also, the intentionality of the Totonacs is speculated since these people are associated with the Mayan culture, which is known by its realizations of environments with astonishing sonic properties. [Work supported by CEAL-UAM of Spain.

  7. Translation as a psycholinguistic phenomenon.

    PubMed

    Zasyekin, Serhiy

    2010-06-01

    The article sketches the outlines of a theoretical framework for the analysis of translation of literary texts, viewed as psycho-semiotic phenomenon and based on evaluation of earlier attempts in this direction, and on the results of a psycholinguistic empirical study of translations. Central to this framework is the recent insight that the human cerebral hemisphere functional asymmetry somehow plays a role in structuring the fictional text by its author and in its processing by the interpreter. It is argued that the texts of modernism and post-modernism contain information blocks describing a character's perception of events in altered states of consciousness. This model helps to explain how a translator's inappropriate linguistic choice may influence the target language reader's aesthetic reaction.

  8. Properties of Square-Pyramidal Alkyl-Thiolate FeIII-Complexes, Including an Analogue of the Unmodified Form of Nitrile Hydratase

    PubMed Central

    Lugo-Mas, Priscilla; Taylor, Wendy; Schweitzer, Dirk; Theisen, Roslyn M.; Xu, Liang; Shearer, Jason; Swartz, Rodney D.; Gleaves, Morgan C.; DiPasquale, Antonio; Kaminsky, Werner; Kovacs, Julie A.

    2009-01-01

    The syntheses and structures of three new coordinatively unsaturated, monomeric, square pyramidal thiolate-ligated Fe(III) complexes are described, [FeIII((tame—N3)S2Me2)]+ (1), [FeIII(Et—N2S2Me2)(py)]1- (3), and [FeIII((tame—N2S)S2Me2)]2- (15). The anionic bis-carboxamide, tris-thiolate N2S3 coordination sphere of 15 is potentially similar to that of the yet-to-be characterized unmodified form of NHase. Comparison of the magnetic and reactivity properties of these reveals how anionic charge build-up (from cationic 1 to anionic 3 and dianionic 15) and spin-state influence apical ligand affinity. For all of the ligand-field combinations examined, an intermediate S= 3/2 spin-state was shown to be favored by a strong N2S2 basal plane ligand-field, and this was found to reduce the affinity for apical ligands, even when they are built-in. This is in contrast to the post-translationaly modified NHase active site, which is low-spin, and displays a higher affinity for apical ligands. Cationic 1 and its reduced FeII precursor are shown to bind NO and CO, respectively, to afford [FeIII((tame-N3)S2Me(NO)]+ (18, νNO= 1865 cm-1), an analogue of NO-inactivated NHase, and [FeII((tame-N3)S2Me)(CO)] (16; νCO stretch (1895 cm-1). Anions (N3-, CN-) are shown to be unreactive towards 1, 3 and 15, and neutral ligands unreactive towards 3 and 15, even when present in 100-fold excess, and at low—temperatures. The curtailed reactivity of 15, an analogue of the unmodified form of NHase, and its apical-oxygenated S= 3/2 derivative [FeIII((tame—N2SO2)S2Me2)]2- (20) suggests that regioselective post—translational oxygenation of the basal plane NHase cysteinate sulfurs plays an important role in promoting substrate binding. This is supported by previously reported theoretical (DFT) calculations.1 PMID:18989922

  9. Synthesis, characterization and investigation of the photophysical and photochemical properties of highly soluble novel metal-free, zinc(II), and indium(III) phthalocyanines substituted with 2,3,6-trimethylphenoxy moieties.

    PubMed

    Gürel, Ekrem; Pişkin, Mehmet; Altun, Selçuk; Odabaş, Zafer; Durmuş, Mahmut

    2015-04-07

    This work presents the synthesis and characterization of metal-free, zinc(II), and indium(III)acetate phthalocyanines substituted with 2,3,6-trimethylphenoxy groups at the peripheral and non-peripheral positions. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation under light irradiation) properties of these novel phthalocyanines and unsubstituted zinc(II) and indium(III)acetate phthalocyanines were investigated in dimethylformamide solution. The effects of the types of substituents and their positions and the variety of central metal ions on the phthalocyanine core on their spectroscopic, photophysical and photochemical properties were also determined. The studied 2,3,6-trimethylphenoxy substituted metal-free, zinc(II) and indium(III)acetate phthalocyanines especially indium(III)acetate derivatives exhibited appropriate photophysical and photochemical properties such as high singlet oxygen generation and these phthalocyanines can be potential Type II photosensitizers for photodynamic therapy in cancer applications.

  10. Highly efficient luminescent hybrid materials covalently linking with europium(III) complexes via a novel fluorinated beta-diketonate ligand: synthesis, characterization and photophysical properties.

    PubMed

    Francis, Biju; Ambili Raj, D B; Reddy, M L P

    2010-09-14

    A novel highly fluorinated beta-diketonate ligand, 1-(3,5-bis(benzyloxy)phenyl)-4,4,5,5,5-pentafluoropentane-1,3-dione (HBBPPF) and its corresponding europium(III) ternary complex, Eu(BBPPF)(3)(DDXPO) [DDXPO = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene oxide] were synthesized via a dexterously designed routine, characterized and its photophysical properties (PL) investigated. PL measurement results indicated that the europium(III) ternary complex exhibits intense red emission under UV light excitation with a solid-state quantum yield of 39%. An organic-inorganic mesoporous luminescent hybrid material was also constructed by linking the ternary europium(III) complex to the functionalized hexagonal mesoporous MCM-41 through the modified beta-diketonate ligand (SiBBPPF-Na). Beta-diketonate grafted to the coupling agent 3-(triethoxysilyl)propyl isocyanate was used as the precursor for the preparation of mesoporous materials. A modified MCM-41 mesoporous material containing ternary europium(iii) complex covalently bonded to the silica-based network, designated as Eu(BBPPF-Si)(3)(DDXPO)/MCM-41, was obtained by interacting SiBBPPF-Na with europium nitrate, DDXPO and MCM-41 via a ligand-exchange reaction. The new mesoporous hybrid material was characterized by powder X-ray diffraction, nitrogen adsorption-desorption, thermogravimetry, transmission electron microscopy, dynamic light scattering, FT-IR, (29)Si CP MAS NMR and (13)C NMR solid-state techniques, and photoluminescence spectroscopy. Eu(BBPPF-Si)(3)(DDXPO)/MCM-41 exhibits an efficient intramolecular energy transfer process from the silylated beta-diketonate to the central Eu(3+), namely, the "antenna effect", which favours a strong luminescent intensity (quantum yield = 43%). Thermogravimetric analysis on Eu(BBPPF-Si)(3)(DDXPO)/MCM-41 demonstrated that the thermal stability of the lanthanide complex was evidently improved as it was covalently bonded to the mesoporous MCM-41 matrix.

  11. A cationic iridium(III) complex showing aggregation-induced phosphorescent emission (AIPE) in the solid state: synthesis, characterization and properties.

    PubMed

    Shan, Guo-Gang; Zhang, Ling-Yu; Li, Hai-Bin; Wang, Shuang; Zhu, Dong-Xia; Li, Peng; Wang, Chun-Gang; Su, Zhong-Min; Liao, Yi

    2012-01-14

    We report the synthesis and characterization of two cationic iridium(III) complexes with dendritic carbazole ligands as ancillary ligands, namely, [Ir(ppy)(2)L3]PF(6) (1) and [Ir(ppy)(2)L4]PF(6) (2), where L3 and L4 represent 3,8-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-1,10-phenanthroline and 3,8-bis(3',6'-di-tert-butyl-6-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,9'-bi(9H-carbazol)-9-yl)-1,10-phenanthroline, respectively. Their photophysical properties have been investigated and compared. The results have shown that complex 2 is aggregation-induced phosphorescent emission (AIPE) active and exhibits the highest photoluminescent quantum yield (PLQY) of 16.2% in neat film among the reported cationic Ir(III) complexes with AIPE activity. In addition, it also enjoys redox reversibility, good film-forming ability, excellent thermal stability as well as off/on luminescence switching properties, revealing its potential application as a candidate for light-emitting electrochemical cells and organic vapor sensing. To explore applications in biology, 2 was used to image cells.

  12. Theoretical study on the effect of N-substitution on the electronic structures and photophysical properties of phosphorescent Ir(III) complexes.

    PubMed

    Si, Yanling; Liu, Yuqi; Qu, Xiaochun; Wang, Ying; Wu, Zhijian

    2013-10-21

    DFT/TDDFT calculations were carried out to investigate the electronic structures, absorption and emission spectra, and phosphorescence efficiency of recent synthesized Ir(III) complexes [Ir(tfmppy)2(tpip)] (1), [Ir(dfppy)2(tpip)] (2) (tfmppy = 4-trifluoromethylphenylpyridine; dfppy = 4,6-difluorophenylpyridine; tpip = tetraphenylimidodiphosphinate). The calculated absorption and emission wavelengths are in agreement with experimental data. The electron transition properties have been analyzed. Compared with 2, the higher quantum yield of experimental observation for 1 was explained by its larger separation between 3MLCT/π→π* and 3MC d–d states. Based on these experimental structures, a series of cyclometalated Ir(III) complexes have been designed by substituting “CH” groups with the N atom at 1-, 2-, 3-, and 4-positions on the pyridine moiety in C^N ligands of 1 and 2, respectively. The calculated results reveal that the N substitution not only tunes the emitting color of 1 and 2 but also enhances photoluminescence quantum efficiency. It is hoped that the designed 1a, 2a and 2c could be potential candidates as blue-emitting materials with high quantum efficiency. Moreover, the effects of different functionals on emission properties were also investigated.

  13. Injection, transport, absorption and phosphorescence properties of a series of blue-emitting Ir(III) emitters in OLEDs: a DFT and time-dependent DFT study.

    PubMed

    Li, Xiao-Na; Wu, Zhi-Jian; Si, Zhen-Jun; Zhang, Hong-Jie; Zhou, Liang; Liu, Xiao-Juan

    2009-08-17

    Quantum-chemistry methods were explored to investigate the electronic structures, injection and transport properties, absorption and phosphorescence mechanism of a series of blue-emitting Ir(III) complexes {[(F(2)-ppy)(2)Ir(pta -X/pyN4)], where F(2)-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = phenyl(1); p-tolyl (2); 2,6-difluororophenyl (3); -CF(3) (4), and pyN4 = pyridine-1,2,4-tetrazolate (5)}, which are used as emitters in organic light-emitting diodes (OLEDs). The mobility of hole and electron were studied computationally based on the Marcus theory. Calculations of Ionization potentials (IPs) and electron affinities (EAs) were used to evaluate the injection abilities of holes and electrons into these complexes. The reasons for the lower EL efficiency and phosphorescence quantum yields in 3-5 than in 1and 2 have been investigated. These new structure-property relationships can guide an improved design and optimization of OLED devices based on blue-emitting phosphorescent Ir(III) complexes.

  14. Dynamics of rat entorhinal cortex layer II and III cells: characteristics of membrane potential resonance at rest predict oscillation properties near threshold

    PubMed Central

    Erchova, I; Kreck, G; Heinemann, U; Herz, A V M

    2004-01-01

    Neurones generate intrinsic subthreshold membrane potential oscillations (MPOs) under various physiological and behavioural conditions. These oscillations influence neural responses and coding properties on many levels. On the single-cell level, MPOs modulate the temporal precision of action potentials; they also have a pronounced impact on large-scale cortical activity. Recent studies have described a close association between the MPOs of a given neurone and its electrical resonance properties. Using intracellular sharp microelectrode recordings we examine both dynamical characteristics in layers II and III of the entorhinal cortex (EC). Our data from EC layer II stellate cells show strong membrane potential resonances and oscillations, both in the range of 5–15 Hz. At the resonance maximum, the membrane impedance can be more than twice as large as the input resistance. In EC layer III cells, MPOs could not be elicited, and frequency-resolved impedances decay monotonically with increasing frequency or has only a small peak followed by a subsequent decay. To quantify and compare the resonance and oscillation properties, we use a simple mathematical model that includes stochastic components to capture channel noise. Based on this model we demonstrate that electrical resonance is closely related though not equivalent to the occurrence of sag-potentials and MPOs. MPO frequencies can be predicted from the membrane impedance curve for stellate cells. The model also explains the broad-band nature of the observed MPOs. This underscores the importance of intrinsic noise sources for subthreshold phenomena and rules out a deterministic description of MPOs. In addition, our results show that the two identified cell classes in the superficial EC layers, which are known to target different areas in the hippocampus, also have different preferred frequency ranges and dynamic characteristics. Intrinsic cell properties may thus play a major role for the frequency

  15. Synthesis of a novel heptacoordinated Fe(III) dinuclear complex: experimental and theoretical study of the magnetic properties.

    PubMed

    Craig, Gavin A; Barrios, Leoní A; Sánchez Costa, José; Roubeau, Olivier; Ruiz, Eliseo; Teat, Simon J; Wilson, Chick C; Thomas, Lynne; Aromí, Guillem

    2010-05-28

    A new functionalized bis-pyrazol-pyridine ligand has been prepared by reaction with hydrazine of the corresponding bis-β-diketone precursor, also unprecedented. The aerobic reaction of this ligand with ferrous thiocyanate in the presence of ascorbic or oxalic acid affords the dinuclear complex of seven-coordinate Fe(III), [Fe₂(H₄L2)₂(ox)(NCS)₄] (1), as revealed by single crystal X-ray diffraction. This may represent an entry into a new family of [Fe₂] compounds with heptacoordinate metal centres. The capacity of this unusual chromophore to undergo magnetic super-exchange was investigated by means of bulk magnetization and DFT calculations. Both approaches confirmed the presence of antiferromagnetic interactions within the molecule. The theoretical investigation has served to describe the magnetic orbitals of Fe(III) in this unusual coordination geometry, as well as the exchange mechanism. A brief review of the scarce number of iron heptacoordinate complexes reported in the literature is also included and discussed.

  16. Enantiopure tetranuclear iron(III) complexes using chiral reduced Schiff base ligands: synthesis, structure, spectroscopy, magnetic properties, and DFT studies.

    PubMed

    Singh, Reena; Banerjee, Atanu; Colacio, Enrique; Rajak, Kajal Krishna

    2009-06-01

    Four new tetranuclear iron(III) complexes of formula [{Fe(L)(2)}(3)Fe], 1-4, have been prepared by reacting [Fe(ClO(4))(3)].6H(2)O with H(2)L in methanol. Here, L(2-) is the deprotonated form of N-(2-hyrdoxybenzyl)-l-valinol (H(2)L(1)), N-(2-hyrdoxybenzyl)-l-leucinol (H(2)L(2)), N-(5-chloro-2-hyrdoxybenzyl)-l-leucinol (H(2)L(3)), and N-(2-hyrdoxybenzyl)-l-phenylalaninol (H(2)L(4)). The complexes are prepared in an enantiomeric pure form. The complexes have been characterized with the help of IR, UV-vis, circular dichroism (CD), (1)H, and elemental analyses. The complex [{Fe(L(2))(2)}(3)Fe].CH(3)OH.2H(2)O, 2.CH(3)OH.2H(2)O, crystallizes in enantiomeric pure form containing a propeller-like Fe(4)O(6) core. (1)H and CD spectral studies of the four species are consistent with the structural similarities of the complexes in solution. Variable-temperature magnetic susceptibility of one case shows an intramolecular antiferromagnetic coupling between the Fe(III) ions. Magnetic measurements are in accord with the S = 5 ground state and suggest single molecular magnet behavior. The magnetic exchange coupling constant between the iron centers within the molecule is interpreted using broken-symmetry density functional theory calculation.

  17. Myofibroblast differentiation and its functional properties are inhibited by nicotine and e-cigarette via mitochondrial OXPHOS complex III

    PubMed Central

    Lei, Wei; Lerner, Chad; Sundar, Isaac K.; Rahman, Irfan

    2017-01-01

    Nicotine is the major stimulant in tobacco products including e-cigarettes. Fibroblast to myofibroblast differentiation is a key process during wound healing and is dysregulated in lung diseases. The role of nicotine and e-cigarette derived nicotine on cellular functions including profibrotic response and other functional aspects is not known. We hypothesized that nicotine and e-cigarettes affect myofibroblast differentiation, gel contraction, and wound healing via mitochondria stress through nicotinic receptor-dependent mechanisms. To test the hypothesis, we exposed human lung fibroblasts with various doses of nicotine and e-cigarette condensate and determined myofibroblast differentiation, mitochondrial oxidative phosphorylation (OXPHOS), wound healing, and gel contraction at different time points. We found that both nicotine and e-cigarette inhibit myofibroblast differentiation as shown by smooth muscle actin and collagen type I, alpha 1 abundance. Nicotine and e-cigarette inhibited OXPHOS complex III accompanied by increased MitoROS, and this effect was augmented by complex III inhibitor antimycin A. These mitochondrial associated effects by nicotine resulted in inhibition of myofibroblast differentiation. These effects were associated with inhibition of wound healing and gel contraction suggesting that nicotine is responsible for dysregulated repair during injurious responses. Thus, our data suggest that nicotine causes dysregulated repair by inhibition of myofibroblast differentiation via OXPHOS pathway. PMID:28256533

  18. The phenomenon of Soviet science.

    PubMed

    Kojevnikov, Alexei

    2008-01-01

    The grand "Soviet experiment" constituted an attempt to greatly accelerate and even shortcut the gradual course of historical development on the assumption of presumed knowledge of the general laws of history. This paper discusses the parts of that experiment that directly concerned scientific research and, in fact, anticipated or helped define important global changes in the functioning of science as a profession and an institution during the twentieth century. The phenomenon of Soviet, or socialist, science is analyzed here from the comparative international perspective, with attention to similarities and reciprocal influences, rather than to the contrasts and dichotomies that have traditionally interested cold war-type historiography. The problem is considered at several levels: philosophical (Soviet thought on the relationship between science and society and the social construction of scientific knowledge); institutional (the state recognition of research as a separate profession, the rise of big science and scientific research institutes); demographic (science becoming a mass profession, with ethnic and gender diversity among scientists); and political (Soviet-inspired influences on the practice of science in Europe and the United States through the social relations of science movement of the 1930s and the Sputnik shock of the 1950s).

  19. Mucocutaneous Splendore-Hoeppli phenomenon.

    PubMed

    Hussein, Mahmoud R

    2008-11-01

    Splendore-Hoeppli phenomenon (asteroid bodies) is the in vivo formation of intensely eosinophilic material (radiate, star-like, asteroid or club-shaped configurations) around microorganisms (fungi, bacteria and parasites) or biologically inert substances. This study presents a literature review concerning Splendore-Hoeppli reaction in the mucocutaneous diseases. It examines the histopathological features, nature and differential diagnosis of this reaction. It also discusses the mucocutaneous infections and the non-infective diseases associated with it. Available studies indicate that several mucocutaneous infections can generate Splendore-Hoeppli reaction. The fungal infections include sporotrichosis, pityrosporum folliculitis, zygomycosis, candidiasis, aspergillosis and blastomycosis. The bacterial infections include botryomycosis, nocardiosis and actinomycosis. The parasitic conditions include orbital pythiosis, strongyloidiasis, schistosomiasis and cutaneous larva migrans. In addition, Splendore-Hoeppli reaction may be seen with non-infective pathology such as hypereosinophilic syndrome and allergic conjunctival granulomas. The Splendore-Hoeppli reaction material comprises antigen-antibody complex, tissue debris and fibrin. Although the exact nature of this reaction is unknown, it is thought to be a localized immunological response to an antigen-antibody precipitate related to fungi, parasites, bacteria or inert materials. The characteristic formation of the peribacterial or perifungal Splendore-Hoeppli reaction probably prevents phagocytosis and intracellular killing of the insulting agent leading to chronicity of infection. To conclude, Splendore-Hoeppli reaction is a tell tale of a spectrum of infections and reactive conditions. The molecular pathways involved in the development of this reaction are open for future investigations.

  20. Preparation and application of low molecular weight poly(vinyl chloride). III mechanical properties of blended poly(vinyl chloride)

    SciTech Connect

    Yamamoto, Kikuo; Maehala, Takashi; Mitani, Katsuo; Mizutani, Yukio )

    1993-11-05

    The blending effect of poly(vinyl chloride) with relatively higher molecular weight (HMW-PVC) and relatively lower molecular weight (LMW-PVC) has been investigated by measuring various mechanical properties: melt properties, tensile strength, tensile modulus, and impact strength. The blended PVC has slightly improved melt properties in comparison with the HMW-PVC used. The tensile strength of the blended PVC is related to the weight-average polymerization degree (Pw) of LMW-PVC and the LMW-PVC content. At the LMW-PVC content of 20%, the tensile strength of blended PVC is a maximum: approximately 58 MPa.

  1. Investigating the growth, structural and electrical properties of III-V semiconductor nanopillars for the next-generation electronic and optoelectronic devices

    NASA Astrophysics Data System (ADS)

    Lin, Andrew

    Extensive research efforts have been devoted to the study and development of III-V compound semiconductor nanowires (NWs) and nanopillars (NPs) because of their unique physical properties and ability to form high quality, highly lattice-mismatched axial and radial heterostructures. These advantages lead to precise nano-bandgap engineering to achieve new device functionalities. One unique and powerful approach to realize these NPs is by catalyst-free, selective-area epitaxy (SAE) via metal-organic chemical vapor deposition, in which the NP location and diameter can be precisely controlled lithographically. Early demonstrations of electronic and optoelectronic devices based on these NPs, however, are often inferior compared to their planar counterparts due to a few factors: (1) interface/surface states, (2) inaccurate doping calibration, and (3) increased carrier scattering and trapping from stacking fault formation in the NPs. In this study, the detailed growth mechanisms of different III-As, III-Sb and III-P NPs and their heterostructures are investigated. These NPs are then fabricated into single-NP field-effect transistors (FETs) to probe their electrical properties. It is shown that these devices are highly diameter-dependent, mainly because of the effects of surface states. By growing a high band-gap shell around the NP cores to passivate the surface, the device performance can be significantly improved. Further fabrication and characterization of vertical surround-gate FETs using a high-mobility InAs/InP NP channel is also discussed. Aside from the radial NP heterostructures, different approaches to achieve purely axial heterostructures in InAs/In(As)P materials are also presented with excellent interface quality. Both single barrier and double barrier structures are realized and fabricated into devices that show carrier transport characteristics over a barrier and even resonant tunneling behavior. Antimonide-based NPs are also studied for their immense

  2. Synthesis, one- and two-photon photophysical and excited-state properties, and sensing application of a new phosphorescent dinuclear cationic iridium(III) complex.

    PubMed

    Xu, Wen-Juan; Liu, Shu-Juan; Zhao, Xin; Zhao, Ning; Liu, Zhi-Qiang; Xu, Hang; Liang, Hua; Zhao, Qiang; Yu, Xiao-Qiang; Huang, Wei

    2013-01-07

    A new phosphorescent dinuclear cationic iridium(III) complex (Ir1) with a donor-acceptor-π-bridge-acceptor-donor (D-A-π-A-D)-conjugated oligomer (L1) as a N^N ligand and a triarylboron compound as a C^N ligand has been synthesized. The photophysical and excited-state properties of Ir1 and L1 were investigated by UV/Vis absorption spectroscopy, photoluminescence spectroscopy, and molecular-orbital calculations, and they were compared with those of the mononuclear iridium(III) complex [Ir(Bpq)(2)(bpy)](+)PF(6)(-) (Ir0). Compared with Ir0, complex Ir1 shows a more-intense optical-absorption capability, especially in the visible-light region. For example, complex Ir1 shows an intense absorption band that is centered at λ=448 nm with a molar extinction coefficient (ε) of about 10(4) , which is rarely observed for iridium(III) complexes. Complex Ir1 displays highly efficient orange-red phosphorescent emission with an emission wavelength of 606 nm and a quantum efficiency of 0.13 at room temperature. We also investigated the two-photon-absorption properties of complexes Ir0, Ir1, and L1. The free ligand (L1) has a relatively small two-photon absorption cross-section (δ(max) =195 GM), but, when complexed with iridium(III) to afford dinuclear complex Ir1, it exhibits a higher two-photon-absorption cross-section than ligand L1 in the near-infrared region and an intense two-photon-excited phosphorescent emission. The maximum two-photon-absorption cross-section of Ir1 is 481 GM, which is also significantly larger than that of Ir0. In addition, because the strong B-F interaction between the dimesitylboryl groups and F(-) ions interrupts the extended π-conjugation, complex Ir1 can be used as an excellent one- and two-photon-excited "ON-OFF" phosphorescent probe for F(-) ions.

  3. Experimental investigation of the physical properties of medium and heavy oils, their vaporization and use in explosion engines. Part III

    NASA Technical Reports Server (NTRS)

    Heinlein, Fritz

    1926-01-01

    The test equipment for studying the vaporization of heavy and medium oils is described as well as some of the experimental properties explored such as vaporization speed and diffusion coefficient. The experiemtal arrangement is also discussed.

  4. Lung tissue mechanics as an emergent phenomenon.

    PubMed

    Suki, Béla; Bates, Jason H T

    2011-04-01

    The mechanical properties of lung parenchymal tissue are both elastic and dissipative, as well as being highly nonlinear. These properties cannot be fully understood, however, in terms of the individual constituents of the tissue. Rather, the mechanical behavior of lung tissue emerges as a macroscopic phenomenon from the interactions of its microscopic components in a way that is neither intuitive nor easily understood. In this review, we first consider the quasi-static mechanical behavior of lung tissue and discuss computational models that show how smooth nonlinear stress-strain behavior can arise through a percolation-like process in which the sequential recruitment of collagen fibers with increasing strain causes them to progressively take over the load-bearing role from elastin. We also show how the concept of percolation can be used to link the pathologic progression of parenchymal disease at the micro scale to physiological symptoms at the macro scale. We then examine the dynamic mechanical behavior of lung tissue, which invokes the notion of tissue resistance. Although usually modeled phenomenologically in terms of collections of springs and dashpots, lung tissue viscoelasticity again can be seen to reflect various types of complex dynamic interactions at the molecular level. Finally, we discuss the inevitability of why lung tissue mechanics need to be complex.

  5. Property Accounting. A Handbook of Standard Terminology and a Guide for Classifying Information about Education Property. State Educational Records and Reports Series: Handbook III, Revised 1977.

    ERIC Educational Resources Information Center

    Seibert, Ivan N.

    This handbook is offered as a resource for local, intermediate, state, and federal education officials to assist in the identification, organization, and definition of data and information about education property. An introduction and directions are followed by a discussion of concepts associated with property accounting and some general…

  6. Model Compounds for Iron Proteins. Structures and Magnetic, Spectroscopic, and Redox Properties of Fe(III)M(II) and [Co(III)Fe(III)](2)O Complexes with (&mgr;-Carboxylato)bis(&mgr;-phenoxo)dimetalate and (&mgr;-Oxo)diiron(III) Cores.

    PubMed

    Dutta, Sujit K.; Werner, Rüdiger; Flörke, Ulrich; Mohanta, Sasankasekhar; Nanda, Kausik K.; Haase, Wolfgang; Nag, Kamalaksha

    1996-04-10

    A series of heterobimetallic complexes of the type [Fe(III)M(II)L(&mgr;-OAc)(OAc)(H(2)O)](ClO(4)).nH(2)O (2-5) and [{Fe(III)Co(III)L(&mgr;-OAc)(OAc)}(2)(&mgr;-O)](ClO(4))(2).3H(2)O (6) where H(2)L is a tetraaminodiphenol macrocyclic ligand and M(II) = Zn(2), Ni(3), Co(4), and Mn(5) have been synthesized and characterized. The (1)H NMR spectrum of 6 exhibits all the resonances between 1 and 12 ppm. The IR and UV-vis spectra of 2-5 indicate that in all the cases the metal ions have similar coordination environments. A disordered crystal structure determined for 3 reveals the presence of a (&mgr;-acetate)bis(&mgr;-phenoxide)-Ni(II)Fe(III) core, in which the two metal ions have 6-fold coordination geometry and each have two amino nitrogens and two phenolate oxygens as the in-plane donors; aside from the axial bridging acetate, the sixth coordination site of nickel(II) is occupied by the unidentate acetate and that of iron(III) by a water molecule. The crystal structure determination of 6 shows that the two heterobinuclear Co(III)Fe(III) units are bound by an Fe-O-Fe linkage. 6 crystallizes in the orthorhombic space group Ibca with a = 17.577(4) Å, b = 27.282(7) Å, c = 28.647(6) Å, and Z = 8. The two iron(III) centers in 6 are strongly antiferromagnetically coupled, J = -100 cm(-1) (H = -2JS(1).S(2)), whereas the other two S(1) = S(2) = (5)/(2) systems, viz. [Fe(2)(III)(HL)(2)(&mgr;-OH)(2)](ClO(4))(2) (1) and the Fe(III)Mn(II) complex (5), exhibit weak antiferromagnetic exchange coupling with J = -4.5 cm(-1) (1) and -1.8 cm(-1) (5). The Fe(III)Ni(II) (3) and Fe(III)Co(II) (4) systems, however, exhibit weak ferromagnetic behavior with J = 1.7 cm(-1) (3) and 4.2 cm(-1) (4). The iron(III) center in 2-5 exhibits quasi-reversible redox behavior between -0.44 and -0.48 V vs Ag/AgCl associated with reduction to iron(II). The oxidation of cobalt(II) in 4 occurs quasi-reversibly at 0.74 V, while both nickel(II) and manganese(II) in 3 and 5 undergo irreversible oxidation at 0

  7. Synthesis and photophysical properties of Ir(iii)/Re(i) dyads: control of Ir→Re photoinduced energy transfer.

    PubMed

    Saad, Suad T; Metherell, Alexander J; Baggaley, Elizabeth; Ward, Michael D

    2016-07-28

    A series of dinuclear Ir(iii)/Re(i) complexes has been prepared based on a family of symmetrical bridging ligands containing two bidentate N,N'-chelating pyrazolyl-pyridine termini, connected by a central aromatic or aliphatic spacer. The Ir(iii) termini are based on {Ir(F2ppy)2}(+) units (where F2ppy is the cyclometallating anion of a fluorinated phenylpyridine) and the Re(i) termini are based on {Re(CO)3Cl} units. Both types of terminus are luminescent, with the Ir-based unit showing characteristic strong, structured phosphorescence in the blue region (maximum 452 nm) with a triplet excited state energy of 22 200 cm(-1) and the Re-based unit showing much weaker and lower-energy phosphorescence (maximum 530 nm) with a triplet excited state energy of 21 300 cm(-1). The energy gradient between the two excited states allows for partial Ir→Re photoinduced energy-transfer, with substantial (but incomplete) quenching of the higher-energy Ir-based emission component and sensitised emission - evidenced by an obvious grow-in component - on the lower-energy Re-based emission. The Ir→Re energy-transfer rate constants vary over the range 1-8 × 10(7) s(-1) depending on the bridging ligand: there is no simple correlation between bridging ligand structure and energy-transfer rate, possibly because this will depend substantially on the conformation of these flexible molecules in solution. To test the role of ligand conformation further, we investigated a complex in which the bridging chain is a (CH2CH2O)6 unit whose conformation is known to be solvent-polarity dependent, with such chains adopting an open, elongated conformation in water and more compact, folded conformations in organic solvents. There was a clear link between the rate and extent of Ir→Re energy-transfer which reduced in polar solvents as the chain became elongated and the Ir/Re separation was larger; and increased in less polar solvents as the chain adopted a more compact conformation and the Ir

  8. Structure and dynamics of Type III periplasmic proteins VcFhuD and VcHutB reveal molecular basis of their distinctive ligand binding properties

    NASA Astrophysics Data System (ADS)

    Agarwal, Shubhangi; Dey, Sanjay; Ghosh, Biplab; Biswas, Maitree; Dasgupta, Jhimli

    2017-02-01

    Molecular mechanisms of xenosiderophore and heme acquisitions using periplasmic binding protein (PBP) dependent ATP-binding cassette transporters to scavenge the essential nutrient iron are elusive yet in Vibrio cholerae. Our current study delineates the structures, dynamics and ligand binding properties of two Type III PBPs of V. cholerae, VcFhuD and VcHutB. Through crystal structures and fluorescence quenching studies we demonstrate unique features of VcFhuD to bind both hydroxamate and catecholate type xenosiderophores. Like E. coli FhuD, VcFhuD binds ferrichrome and ferri-desferal using conserved Tryptophans and R102. However, unlike EcFhuD, slightly basic ligand binding pocket of VcFhuD could favour ferri-enterobactin binding with plausible participation of R203, along with R102, like it happens in catecholate binding PBPs. Structural studies coupled with spectrophotometric and native PAGE analysis indicated parallel binding of two heme molecules to VcHutB in a pH dependent manner, while mutational analysis established the relative importance of Y65 and H164 in heme binding. MD simulation studies exhibited an unforeseen inter-lobe swinging motion in Type III PBPs, magnitude of which is inversely related to the packing of the linker helix with its neighboring helices. Small inter-lobe movement in VcFhuD or dramatic twisting in VcHutB is found to influence ligand binding.

  9. Deep-red phosphorescent iridium(III) complexes containing 1-(benzo[b] thiophen-2-yl) isoquinoline ligand: synthesis, photophysical and electrochemical properties and DFT calculations.

    PubMed

    Li, Gao-Nan; Zou, Ying; Yang, Yi-Ding; Liang, Jiao; Cui, Feng; Zheng, Tao; Xie, Hui; Niu, Zhi-Gang

    2014-09-01

    Four new bis-cyclometalated iridium(III) complexes, [Ir(btq) 2phen] [PF6] (3a), [Ir(btq) 2bpy] [PF6] (3b), [Ir(btq) 2dtbipy] [PF6] (3c) and [Ir(btq) 2pic] (3d) (btq = 1-(benzo[b] thiophen-2-yl) isoquinoline, phen = 1,10-phenanthroline, bpy = 2,2'-bipyridine, dtbipy = 4,4'-di-tert-butyl-2,2'-bipyridine, pic = picolinic acid) have been synthesized and fully characterized. The crystal structure of 3a has been determined by X-ray analysis. The photophysical and electrochemical properties of these new complexes 3a - 3d have been studied. The photoluminescence spectra of all Ir(III) complexes exhibit deep-red emission maxima at 682, 682, 683 and 698 nm, respectively. The most representative molecular orbital energy-level diagrams and the lowest energy electronic transitions of 3a - 3d have been calculated with density functional theory (DFT) and time-dependent DFT (TD - DFT). The results show that the pic ancillary ligand of complex 3d influences the absorption and emission energies with a further red-shift relative to other three complexes 3a - 3c.

  10. Ruthenium(III) Complexes of Heterocyclic Tridentate (ONN) Schiff Base: Synthesis, Characterization and its Biological Properties as an Antiradical and Antiproliferative Agent

    PubMed Central

    Ejidike, Ikechukwu P.; Ajibade, Peter A.

    2016-01-01

    The current work reports the synthesis, spectroscopic studies, antiradical and antiproliferative properties of four ruthenium(III) complexes of heterocyclic tridentate Schiff base bearing a simple 2′,4′-dihydroxyacetophenone functionality and ethylenediamine as the bridging ligand with RCHO moiety. The reaction of the tridentate ligands with RuCl3·3H2O lead to the formation of neutral complexes of the type [Ru(L)Cl2(H2O)] (where L = tridentate NNO ligands). The compounds were characterized by elemental analysis, UV-vis, conductivity measurements, FTIR spectroscopy and confirmed the proposed octahedral geometry around the Ru ion. The Ru(III) compounds showed antiradical potentials against 2,2-Diphenyl-1-Picrylhydrazyl (DPPH) and 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radicals, with DPPH scavenging capability in the order: [(PAEBOD)RuCl2] > [(BZEBOD)RuCl2] > [(MOABOD)RuCl2] > [Vit. C] > [rutin] > [(METBOD)RuCl2], and ABTS radical in the order: [(PAEBOD)RuCl2] < [(MOABOD)RuCl2] < [(BZEBOD)RuCl2] < [(METBOD)RuCl2]. Furthermore, in vitro anti-proliferative activity was investigated against three human cancer cell lines: renal cancer cell (TK-10), melanoma cancer cell (UACC-62) and breast cancer cell (MCF-7) by SRB assay. PMID:26742030

  11. Structure and dynamics of Type III periplasmic proteins VcFhuD and VcHutB reveal molecular basis of their distinctive ligand binding properties

    PubMed Central

    Agarwal, Shubhangi; Dey, Sanjay; Ghosh, Biplab; Biswas, Maitree; Dasgupta, Jhimli

    2017-01-01

    Molecular mechanisms of xenosiderophore and heme acquisitions using periplasmic binding protein (PBP) dependent ATP-binding cassette transporters to scavenge the essential nutrient iron are elusive yet in Vibrio cholerae. Our current study delineates the structures, dynamics and ligand binding properties of two Type III PBPs of V. cholerae, VcFhuD and VcHutB. Through crystal structures and fluorescence quenching studies we demonstrate unique features of VcFhuD to bind both hydroxamate and catecholate type xenosiderophores. Like E. coli FhuD, VcFhuD binds ferrichrome and ferri-desferal using conserved Tryptophans and R102. However, unlike EcFhuD, slightly basic ligand binding pocket of VcFhuD could favour ferri-enterobactin binding with plausible participation of R203, along with R102, like it happens in catecholate binding PBPs. Structural studies coupled with spectrophotometric and native PAGE analysis indicated parallel binding of two heme molecules to VcHutB in a pH dependent manner, while mutational analysis established the relative importance of Y65 and H164 in heme binding. MD simulation studies exhibited an unforeseen inter-lobe swinging motion in Type III PBPs, magnitude of which is inversely related to the packing of the linker helix with its neighboring helices. Small inter-lobe movement in VcFhuD or dramatic twisting in VcHutB is found to influence ligand binding. PMID:28216648

  12. A novel europium (III) nitridoborate Eu3[B3N6]: Synthesis, crystal structure, magnetic properties, and Raman spectra

    NASA Astrophysics Data System (ADS)

    Aydemir, Umut; Kokal, Ilkin; Prots, Yurii; Förster, Tobias; Sichelschmidt, Jörg; Schappacher, Falko M.; Pöttgen, Rainer; Ormeci, Alim; Somer, Mehmet

    2016-07-01

    A novel europium (III) nitridoborate, Eu3[B3N6], was successfully synthesized by oxidation of Eu3II[BN2]2 with Br2 at 1073 K. The compound crystallizes in the trigonal space group R 3 barc (No:167) with a=11.9370(4) Å, c=6.8073(4) Å, and Z=6. The crystal structure of Eu3[B3N6] consists of isolated, planar cyclic [B3N6]9- units which are charge-balanced by Eu3+ cations. The oxidation state of Eu was investigated by Mössbauer spectroscopy, electron spin resonance (ESR) spectroscopy, and quantum chemical calculations. The 151Eu Mössbauer spectroscopic measurement at 77 K reveals that the main signal at δ=0.93(7) mm/s is originating from trivalent Europium. Eu3[B3N6] showed no ESR signal in accordance with a non-magnetic (J=0) 7F0 ground state of the 4f6 configuration. Quantum chemical calculations find six electrons in the 4f subshell (4f6) of Eu indicating an oxidation state of +3. We present for the first time the vibrational spectra of a compound with cyclic trimer [B3N6]9- moieties. The Raman spectrum of Eu3[B3N6] is in good agreement with the predicted number of modes for the spectroscopically relevant cyclic [B3N6]9- group with D3h symmetry.

  13. Synthesis, structure, spectroscopic properties, and antiproliferative activity in vitro of novel osmium(III) complexes with azole heterocycles.

    PubMed

    Stepanenko, Iryna N; Krokhin, Artem A; John, Roland O; Roller, Alexander; Arion, Vladimir B; Jakupec, Michael A; Keppler, Bernhard K

    2008-08-18

    Reactions of (H 2azole) 2[OsCl 6], where Hazole = pyrazole, Hpz, ( 1), indazole, Hind, ( 2), imidazole, Him, ( 3) and benzimidazole, Hbzim, ( 4) with the corresponding azole heterocycle in 1:4 molar ratio in boiling isoamyl alcohol or hexanol-1 afforded novel water-soluble osmium(III) complexes of the type trans-[OsCl 2(Hazole) 4]Cl, where Hazole = Hpz ( 5a), Hind ( 6a), Him ( 7a), and Hbzim ( 9a) in 50-70% ( 5a, 7a, 9a) and 5% ( 6a) yields. The synthesis of 7a was accompanied by a concurrent reaction which led to minor formation (<4%) of cis-[OsCl 2(Him) 4]Cl ( 8). The complexes were characterized by elemental analysis, IR spectroscopy, UV-vis spectroscopy, ESI mass spectrometry, cyclic voltammetry, and X-ray crystallography. 5a, 7a, and 9a were found to possess remarkable antiproliferative activity in vitro against A549 (non-small cell lung carcinoma), CH1 (ovarian carcinoma), and SW480 (colon carcinoma) cells, which was compared with that of related ruthenium compounds trans-[RuCl 2(Hazole) 4]Cl, where Hazole = Hpz (5b), Hind (6b), Him (7b), and Hbzim (9b).

  14. Hydrothermal synthesis, structure, heterogeneous catalytic activity and photoluminescent properties of a novel homoleptic Sm(III)-organic framework

    NASA Astrophysics Data System (ADS)

    Ay, Burak; Yildiz, Emel; Felts, Ashley C.; Abboud, Khalil A.

    2016-12-01

    A novel metal-organic framework, (H2pip)n[Sm2(pydc)4(H2O)2]n (1) (H2pydc=2,6-pyridinedicarboxylic acid, H2pip=piperazine) has been synthesized under hydrothermal conditions and characterized by the elemental analysis, inductively coupled plasma (ICP) spectrometer, fourier transform infrared (FT-IR) spectra, thermogravimetric analysis (TGA), single crystal X-ray diffraction analysis and powder X-ray diffraction (PXRD). The structure of 1 was determined to be three-dimensional, linked along Sm-O-Sm chains. The asymmetric unit consisted of one singly anionic fragment consisting of Sm(III) coordinated to two H2pydc ligands and one water, and one half of a protonated H2pip, which sits on an inversion center. 1 exhibited luminescence emission bands at 534 nm at room temperature when excited at 440 nm. Its thermal behavior and catalytic performance were investigated and the selectivity was measured as 100% for the oxidation of thymol to thymoquinone.

  15. The effect of substituted moiety on the optoelectronic and photophysical properties of tris (phenylbenzimidazolinato) Ir (III) carbene complexes and the OLED performance: a theoretical study

    NASA Astrophysics Data System (ADS)

    Srivastava, Ruby

    2015-06-01

    Density functional theory (DFT) and time-dependent density functional theory (TDDFT) are used to analyse theoretically the optoelectronic, photophysical properties and organic light-emitting diode performance of a series of fac-mer blue-emitting Iridium (III) carbene complexes. Swain-Lupton constant is used to discuss the substituents effect. 5d-orbital splitting and d-d* transitions are calculated to assess the efficiency of the studied complexes. The reorganisation energies (λ), transfer integrals, mobilities, radiative decay rate (kr), and triplet exciton generation fraction (χT) are also calculated. Due to the higher χT of these complexes, the formation of triplet exciton will be more and it will cause a faster intersystem crossing. Two host materials are proposed and host-guest match (Dexter-Förster energy) is also discussed. We hope that this unified work will surely help to design new blue-emitting phosphorescent materials in future.

  16. Comparative biochemical characterization of peroxidases (class III) tightly bound to the maize root cell walls and modulation of the enzyme properties as a result of covalent binding.

    PubMed

    Hadži-Tašković Šukalović, Vesna; Vuletić, Mirjana; Marković, Ksenija; Cvetić Antić, Tijana; Vučinić, Željko

    2015-01-01

    Comparative biochemical characterization of class III peroxidase activity tightly bound to the cell walls of maize roots was performed. Ionically bound proteins were solubilized from isolated walls by salt washing, and the remaining covalently bound peroxidases were released, either by enzymatic digestion or by a novel alkaline extraction procedure that released covalently bound alkali-resistant peroxidase enzyme. Solubilized fractions, as well as the salt-washed cell wall fragments containing covalently bound proteins, were analyzed for peroxidase activity. Peroxidative and oxidative activities indicated that peroxidase enzymes were predominately associated with walls by ionic interactions, and this fraction differs from the covalently bound one according to molecular weight, isozyme patterns, and biochemical parameters. The effect of covalent binding was evaluated by comparison of the catalytic properties of the enzyme bound to the salt-washed cell wall fragments with the corresponding solubilized and released enzyme. Higher thermal stability, improved resistance to KCN, increased susceptibility to H2O2, stimulated capacity of wall-bound enzyme to oxidize indole-3-acetic acid (IAA) as well as the difference in kinetic parameters between free and bound enzymes point to conformational changes due to covalent binding. Differences in biochemical properties of ionically and covalently bound peroxidases, as well as the modulation of the enzyme properties as a result of covalent binding to the walls, indicate that these two fractions of apoplastic peroxidases play different roles.

  17. Theoretical study on the electronic structures and phosphorescent properties of four Ir(III) complexes with different substituents on the ancillary ligand

    NASA Astrophysics Data System (ADS)

    Han, Deming; Shang, Xiaohong; Zhang, Gang; Zhao, Lihui

    2013-12-01

    The geometry structures, electronic structures, absorption and phosphorescent properties of four Ir(III) complexes {[(F2-ppy)2Ir(pta-X)], where F2-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = -CF3; -H; -CH3; -N(CH3)2}, are investigated using the density functional method. The results reveal that the electron-accepting group -CF3 has no obvious effect on absorption and emission properties, while the substitutive group -N(CH3)2 with strong electron-donating ability has obvious effect on the emission properties. The mobility of hole and electron were studied computationally based on the Marcus-Hush theory. Calculations of ionisation potential and electron affinity were used to evaluate the injection abilities of holes and electrons into these complexes. We hope that this theoretical work can provide a suitable guide to the future design and synthesis of novel phosphorescent materials for use in the organic light-emitting diodes.

  18. BIOPLUME III

    EPA Pesticide Factsheets

    BIOPLUME III is a two-dimensional finite difference model for simulating the natural attenuation of organic contaminants in groundwater due to the processes of advection, dispersion, sorption, and biodegradation.

  19. Effect of low temperature anneals and nonthermal treatments on the properties of gap fill oxides used in SiGe and III-V devices

    NASA Astrophysics Data System (ADS)

    Ryan, E. Todd; Morin, Pierre; Madan, Anita; Mehta, Sanjay

    2016-07-01

    Silicon dioxide is used to electrically isolate CMOS devices such as fin field effect transistors by filling gaps between the devices (also known as shallow trench isolation). The gap fill oxide typically requires a high temperature anneal in excess of 1000 °C to achieve adequate electrical properties and oxide densification to make the oxide compatible with subsequent fabrication steps such as fin reveal etch. However, the transition from Si-based devices to high mobility channel materials such as SiGe and III-V semiconductors imposes more severe thermal limitations on the processes used for device fabrication, including gap fill oxide annealing. This study provides a framework to quantify and model the effect of anneal temperature and time on the densification of a flowable silicon dioxide as measured by wet etch rate. The experimental wet etch rates allowed the determination of the activation energy and anneal time dependence for oxide densification. Dopant and self-diffusion can degrade the channel material above a critical temperature. We present a model of self-diffusion of Ge and Si in SiGe materials. Together these data allowed us to map the thermal process space for acceptable oxide wet etch rate and self-diffusion. The methodology is also applicable to III-V devices, which require even lower thermal budget. The results highlight the need for nonthermal oxide densification methods such as ultraviolet (UV) and plasma treatments. We demonstrate that several plasma treatments, in place of high temperature annealing, improved the properties of flowable oxide. In addition, UV curing prior to thermal annealing enables acceptable densification with dramatically reduced anneal temperature.

  20. Three-dimensional open-frameworks based on Ln(III) ions and open-/closed-shell PTM ligands: synthesis, structure, luminescence, and magnetic properties.

    PubMed

    Datcu, Angela; Roques, Nans; Jubera, Véronique; Imaz, Inhar; Maspoch, Daniel; Sutter, Jean-Pascal; Rovira, Concepció; Veciana, Jaume

    2011-03-21

    A series of isostructural open-framework coordination polymers formulated as [Ln(dmf)(3)(ptmtc)] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5); PTMTC = polychlorotriphenylmethyl tricarboxylate) and [Ln(dmf)(2)H(2)O(αH-ptmtc)] (Ln = Sm (1'), Eu (2'), Gd (3'), Tb (4'), Dy (5')) have been obtained by treating Ln(III) ions with PTMTC ligands with a radical (PTMTC(3-)) or a closed-shell character (αH-PTMTC(3-)). X-ray diffraction analyses reveal that these coordination polymers possess 3D architectures that combine large channels and fairly rare lattice complex T connectivity. In addition, these compounds show selective framework dynamic sorption properties. For both classes of ligands, the ability to act as an antenna in Ln sensitization processes has been investigated. No luminescence was observed for compounds 1-5, and 3' because of the PTMTC(3-) ligand and/or Gd(III) ion characteristics. Conversely, photoluminescence measurements show that 1', 2', 4', and 5' emit dark orange, red, green, and dark cyan metal-centered luminescence. The magnetic properties of all of these compounds have been investigated. The nature of the {Ln-radical} exchange interaction in these compounds has been assessed by comparing the behavior of the radical-based coordination polymers 1-5 with those of the compounds with the diamagnetic ligand set. While antiferromagnetic {Sm-radical} interactions are found in 1, ferromagnetic {Ln-radical} interactions propagate in the 3D architectures of 3, 4, and 5 (Ln = Gd, Tb, and Dy, respectively). This procedure also provided access to information on the {Ln-Ln} exchange existing in these magnetic systems.

  1. Monostotic fibrous dysplasia with Raynaud's phenomenon

    PubMed Central

    Kumar, K. V. S. Hari; Aravinda, K.; Narayanan, K.

    2015-01-01

    Fibrous dysplasia (FD) is a benign bone disorder characterized by alteration in bone morphology. Monostotic FD is the commonest variant and affects the craniofacial bones. Raynaud's phenomenon is recurrent vasospasm of the fingers and toes due to cold exposure. The disease is usually idiopathic or secondary to connective tissue disorders. Raynaud's phenomenon is not described previously with FD. We recently encountered two interesting patients of craniofacial monostotic FD with Raynaud's phenomenon and report the same in this report. PMID:26283854

  2. Monostotic fibrous dysplasia with Raynaud's phenomenon.

    PubMed

    Kumar, K V S Hari; Aravinda, K; Narayanan, K

    2015-01-01

    Fibrous dysplasia (FD) is a benign bone disorder characterized by alteration in bone morphology. Monostotic FD is the commonest variant and affects the craniofacial bones. Raynaud's phenomenon is recurrent vasospasm of the fingers and toes due to cold exposure. The disease is usually idiopathic or secondary to connective tissue disorders. Raynaud's phenomenon is not described previously with FD. We recently encountered two interesting patients of craniofacial monostotic FD with Raynaud's phenomenon and report the same in this report.

  3. Effect of Some Substituents Increasing the Solubility of Zn(II) and Al(III) Phthalocyanines on Their Photophysical Properties

    PubMed Central

    Chernonosov, A. A.; Ermilov, E. A.; Röder, B.; Solovyova, L. I.; Fedorova, O. S.

    2014-01-01

    Water solubility of phthalocyanines (Pcs) usually increases by the introduction of charged or carboxy substituents in the peripheral positions of the macrocycle. As a result, such structural changes influence their photophysical and photochemical properties as photosensitizers. Phthalocyanines substituted with four or eight terminal carboxyl groups and having in some cases additional eight positive charges (water soluble phthalocyanines) were studied in order to evaluate the spectroscopic and photophysical effects of these side residues on the chromophore properties. The quantum yield of singlet oxygen (1O2) generation, the triplet-triplet absorption, and the transient absorption spectra were measured and linked to the structure of the substituents. It was shown that charged substituents did not change the quantum yields of 1O2 generation but decrease its lifetimes. The introduction of the charged substituents not only increases the water solubility but also significantly changes absorption, fluorescence, and transient absorption spectra of water soluble Pcs. PMID:25302061

  4. The Isakower phenomenon revisited: a case study.

    PubMed

    Dann, O T

    1992-01-01

    The Isakower phenomenon is a situation in which an individual typically experiences perceptions of enlargement or thickening, altered states of consciousness, sensations of floating, and impressions of the emergence and disappearance of an oral mass. This paper defines the phenomenon, reviews the literature, and describes a case in which a patient experienced it. The patient manifested the phenomenon symptomatically in the aftermath of a toxic state, and the elements were analysed for several years. There was support for Isakower's original thesis that the regressive states serve to defend against threatening incestuous fantasies. However, the Isakower phenomenon in this patient was the result of a multiplicity of determinants, largely defensive, involving many developmental levels.

  5. Comparative studies on the structure and aggregative properties of the myosin molecule. III. The in vitro aggregative properties of the lobster myosin molecule.

    PubMed

    Siemankowski, R F; Zobel, C R

    1976-02-20

    The solubility of rabbit skeletal and lobster abdominal muscle myosin has been studied in monovalent salt solutions as a function of pH (over the range 4.75 to 8.5) and ionic strength (50-500 mM). Rabbit skeletal muscle myosin was found to precipitate over a narrower pH range than the lobster abdominal muscle myosin but at equivalent pH values and ionic strengths the former exhibited greater solubility. Comparison of the solubility of rabbit myosin, per se with that of light meromyosin and lobster myosin with its equivalent proteolytically produced fragment (fraction B1) showed that both rod fragments were more soluble than their parent molecules. Under conditions of low solubility (low ionic strength and pH) the quantitiy of protein in solution remained essentially constant with increasing total protein, thus suggesting that the aggregation phenomenon is of a phase transition type. Examination of the aggregates by electron microscopy revealed that rabbit myosin formed classical, elongate, spindle-shaped filaments similar to those previously observed by others. In contrast lobster myosin only formed short, dumbbell-shaped filaments 0.2-0.3 mum long. Consideration of the pH ranges over which aggregation occurred suggests that protonation of histidine residues may be involved in rabbit myosin filament formation while for lobster myosin, aggregation may involve protonation of epsilon-amino or guanidino groups. The possible relationship between the distribution of these groups along the rod portion of the myosin molecule and the formation of elongate filaments has been explored.

  6. Effect of V/III ratio on the structural and optical properties of self-catalysed GaAs nanowires

    NASA Astrophysics Data System (ADS)

    Ahtapodov, L.; Munshi, A. M.; Nilsen, J. S.; Reinertsen, J. F.; Dheeraj, D. L.; Fimland, B. O.; van Helvoort, A. T. J.; Weman, H.

    2016-11-01

    The performance of GaAs nanowire (NW) devices depends critically on the presence of crystallographic defects in the NWs such as twinning planes and stacking faults, and considerable effort has been devoted to understanding and preventing the occurrence of these. For self-catalysed GaAs NWs grown by molecular beam epitaxy (MBE) in particular, there are in addition other types of defects that may be just as important for NW-based optoelectronic devices. These are the point defects such as the As vacancy and the Ga antisite occurring due to the inherently Ga-rich conditions of the self-catalysed growth. Here we demonstrate experimentally the effects of these point defects on the optical properties of GaAs/AlGaAs core-shell NWs grown by self-catalysed MBE. The present results enable insight into the role of the point defects both on their own and in conjunction with crystallographic planar defects.

  7. Studies of Growth-In Defects and Transport Properties Versus Growth Parameters in III-V Compound Semiconductors.

    DTIC Science & Technology

    1982-06-10

    calls [1-51. For example, a cas- cade p-n junction solar cell structure with open circuit 273 I-$5iS/I2/11024VI] 0UM 0 I" AIME t 73 - *tj--e --.- I I f...electrical properties of the grown-in defects and their correlation to the performance character- istics of the AlxGalxAs/GaAs cascade solar cells . To achieve...as a window layer in the solar cell ’structure, and is much more heavily doped (S5xlO 18 cm- 3) than the undoped n-AlO. 3GaO.7As and n-GaAs LPE layers

  8. Influence of glass composition on the properties of glass polyalkenoate cements. Part III: influence of fluorite content.

    PubMed

    De Barra, E; Hill, R G

    2000-03-01

    The influence of fluorite content of the glass on the formation and properties of glass polyalkenoate cements was investigated. A series of glass powders based on 1.5SiO2 x 0.5P2O5 x Al2O3 x CaO x XCaF2 were synthesised. The glass transition temperature of the glass fell with increasing fluorite content. Setting and working times of the cement pastes decreased with increasing fluorite content of the glass. Compressive strength and un-notched fracture strength increased with increasing fluorite content of the glass. Fracture toughness and toughness of the cements were relatively insensitive to fluorite content.

  9. Diversity of lanthanide(III)-organic extended frameworks with a 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid ligand: syntheses, structures, and magnetic and luminescent properties.

    PubMed

    Liu, Qing-Yan; Wang, Wu-Fang; Wang, Yu-Ling; Shan, Zeng-Mei; Wang, Ming-Sheng; Tang, Jinkui

    2012-02-20

    A sulfonate-carboxylate ligand, 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (H(4)-DSNDA), and eight new lanthanide coordination polymers {[Pr(4)(OH)(4)(DSNDA)(2)(H(2)O)(12)](H(2)O)(10)}(n) (1), [Ln(H(2)-DSNDA)(0.5)(DSNDA)(0.5)(H(2)O)(5)](n) (Ln = La(2), Nd(3), Sm(4), Eu(5), Gd(6), and Dy(7)), and {[Er(H-DSNDA)(H(2)O)(4)](H(2)O)}(n) (8) have been synthesized. Detailed crystal structures of these compounds have been investigated. Compound 1 has a 3D framework featuring the unique cubane-shaped [Pr(4)(μ(3)-OH)(4)] clusters and is a binodal 4,8-connected network with (4(16)·6(12))(4(4)·6(2))(2) topology. Compounds 2-7 are isostructural and have 2D layered structures. Compound 8 is also a 2D layer but belongs to different structural types. The luminescence behavior of compound Eu(5) shows that the π-rich aromatic organic ligands efficiently transfer the absorbed light energy to the Eu(III) ions, thus enhancing the overall luminescent properties of compound Eu(5). The magnetic properties of all compounds except for the diamagnetic La(2) compound have been investigated. In addition, elemental analysis, IR spectra, and thermogravimetric analysis of these compounds are also described.

  10. Global Positioning System III (GPS III)

    DTIC Science & Technology

    2013-12-01

    Global Positioning System III ( GPS III) As of FY 2015 President’s Budget...00-00-2013 to 00-00-2013 4. TITLE AND SUBTITLE Global Positioning System III ( GPS III) 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT...Responsible Office References Program Name Global Positioning System III ( GPS III) DoD Component Air Force

  11. Correlating Reactivity and Selectivity to Cyclopentadienyl Ligand Properties in Rh(III)-Catalyzed C-H Activation Reactions: An Experimental and Computational Study.

    PubMed

    Piou, Tiffany; Romanov-Michailidis, Fedor; Romanova-Michaelides, Maria; Jackson, Kelvin E; Semakul, Natthawat; Taggart, Trevor D; Newell, Brian S; Rithner, Christopher D; Paton, Robert S; Rovis, Tomislav

    2017-01-25

    Cp(X)Rh(III)-catalyzed C-H functionalization reactions are a proven method for the efficient assembly of small molecules. However, rationalization of the effects of cyclopentadienyl (Cp(X)) ligand structure on reaction rate and selectivity has been viewed as a black box, and a truly systematic study is lacking. Consequently, predicting the outcomes of these reactions is challenging because subtle variations in ligand structure can cause notable changes in reaction behavior. A predictive tool is, nonetheless, of considerable value to the community as it would greatly accelerate reaction development. Designing a data set in which the steric and electronic properties of the Cp(X)Rh(III) catalysts were systematically varied allowed us to apply multivariate linear regression algorithms to establish correlations between these catalyst-based descriptors and the regio-, diastereoselectivity, and rate of model reactions. This, in turn, led to the development of quantitative predictive models that describe catalyst performance. Our newly described cone angles and Sterimol parameters for Cp(X) ligands served as highly correlative steric descriptors in the regression models. Through rational design of training and validation sets, key diastereoselectivity outliers were identified. Computations reveal the origins of the outstanding stereoinduction displayed by these outliers. The results are consistent with partial η(5)-η(3) ligand slippage that occurs in the transition state of the selectivity-determining step. In addition to the instructive value of our study, we believe that the insights gained are transposable to other group 9 transition metals and pave the way toward rational design of C-H functionalization catalysts.

  12. [3Fe-4S] <--> [4Fe-4S] cluster interconversion in Desulfovibrio africanus ferredoxin III: properties of an Asp14 --> Cys mutant.

    PubMed Central

    Busch, J L; Breton, J L; Bartlett, B M; Armstrong, F A; James, R; Thomson, A J

    1997-01-01

    The 8Fe ferredoxin III from Desulfovibrio africanus is a monomeric protein which contains two [4Fe-4S]2+/1+ clusters, one of which is labile and can readily and reversibly lose one Fe under oxidative conditions to yield a [3Fe-4S]1+/0 cluster. This 4Fe cluster has an S = 3/2 ground sping state insteaed of S = 1/2 in the reduced +1 state [George, Armstrong, Hatchikian and Thomson (1989) Biochem. J. 264, 275-284]. The co-ordination to this cluster is unusual in that an aspartate (Asp14, D14, is found where a cysteine residue normally occurs. Using a mutant protein obtained from the overexpression in Escherichia coli of a synthetic gene in which Asp14, the putative ligand to the removable Fe, has been changed to Cys, we have studied the cluster interconversion properties of the labile cluster. Analysis by EPR and magnetic-circular-dichroism spectroscopies showed that the Asp14 --> Cys (D14C) mutant contains two [4Fe-4S]2+/1+ clusters, both with S = 1/2 in the reduced state. Also, unlike in native 8Fe D. africanus ferredoxin III, the 4Fe <--> 3Fe cluster interconversion reaction was found to be sluggish and did not go to completion. It is inferred that the reversibility of the reaction in the native protein is due to the presence of the aspartate residue at position 14 and that this residue might protect the [3Fe-4S] cluster from further degradation. PMID:9173907

  13. [3Fe-4S] <--> [4Fe-4S] cluster interconversion in Desulfovibrio africanus ferredoxin III: properties of an Asp14 --> Cys mutant.

    PubMed

    Busch, J L; Breton, J L; Bartlett, B M; Armstrong, F A; James, R; Thomson, A J

    1997-04-01

    The 8Fe ferredoxin III from Desulfovibrio africanus is a monomeric protein which contains two [4Fe-4S]2+/1+ clusters, one of which is labile and can readily and reversibly lose one Fe under oxidative conditions to yield a [3Fe-4S]1+/0 cluster. This 4Fe cluster has an S = 3/2 ground sping state insteaed of S = 1/2 in the reduced +1 state [George, Armstrong, Hatchikian and Thomson (1989) Biochem. J. 264, 275-284]. The co-ordination to this cluster is unusual in that an aspartate (Asp14, D14, is found where a cysteine residue normally occurs. Using a mutant protein obtained from the overexpression in Escherichia coli of a synthetic gene in which Asp14, the putative ligand to the removable Fe, has been changed to Cys, we have studied the cluster interconversion properties of the labile cluster. Analysis by EPR and magnetic-circular-dichroism spectroscopies showed that the Asp14 --> Cys (D14C) mutant contains two [4Fe-4S]2+/1+ clusters, both with S = 1/2 in the reduced state. Also, unlike in native 8Fe D. africanus ferredoxin III, the 4Fe <--> 3Fe cluster interconversion reaction was found to be sluggish and did not go to completion. It is inferred that the reversibility of the reaction in the native protein is due to the presence of the aspartate residue at position 14 and that this residue might protect the [3Fe-4S] cluster from further degradation.

  14. Synthesis, Structure, and Magnetic Electrochemical Properties of a Family of Tungstoarsenates Containing Just Co(II) Centers or Both Co(II) and Fe(III) Centers.

    PubMed

    Ayingone Mezui, Charyle S; de Oliveira, Pedro; Teillout, Anne-Lucie; Marrot, Jérôme; Berthet, Patrick; Lebrini, Mounim; Mbomekallé, Israël M

    2017-02-20

    The three polyoxotungstates [(NaOH2)2Co(II)2(As2W15O56)2](18-) (1), [(NaOH2)(Co(II)OH2)Co(II)2(As2W15O56)2](17-) (2), and [(Co(II)OH2)2Co(II)2(As2W15O56)2](16-) (3) have been prepared in aqueous solution upon mixing cobalt(II) salts with the ligand [As2W15O56](12-). The reaction of 1 or 2 with the Fe(3+) ion leads invariably to the same species [(Fe(III)OH2)(Co(II)OH2)Co(II)2(As2W15O56)2](15-) (4) possessing three cobalt atoms and a single iron atom. However, if the Fe-containing homologue of compound 1, that is, the polyoxotungstate [(NaOH2)2Fe(III)2(As2W15O56)2](16-) (5), is employed instead to react with the Co(2+) ion, the species [(Co(II)OH2)2Fe(III)2(As2W15O56)2](14-) (6) is obtained, having two cobalt atoms and two iron atoms. The compounds 1, 2, 3, 4, and 6 are described for the first time and have been characterized by several physicochemical methods such as FTIR, UV-visible, ATG, and elemental analysis. Structural analysis by single-crystal X-ray diffraction has been carried out with compounds 2 (monoclinic space group P21/c, a = 17.0622(5) Å, b = 15.0828(4) Å, c = 32.0872(8) Å, β = 91.170(1)°, and Z = 2) and 3 (triclinic space group P1̅, a = 13.6137(7) Å, b = 13.8836(8) Å, c = 22.9276(6) Å, α = 89.906(3)°, β = 78.356(2)°, γ = 61.451(2)°, and Z = 1). Electrochemical studies undertaken with all the above-mentioned compounds and some of their homologues shed light on the influence of the chemical composition on their electrocatalytic properties toward substrates such as the nitrite ion and dioxygen. Magnetic measurements evidence anisotropic ferromagnetic interactions between Co(2+) ions and antiferromagnetic interactions between Fe(3+) ions. The nature and the strength of the Co(2+)-Fe(3+) interactions depend on the relative orientations of their 3d orbitals. The effective magnetic moment of the Co(2+) ions varies with the temperature and with the distortion of the octahedral sites in which they are located.

  15. Effect of thermal annealing on the structural and optical properties of tris-(8-hydroxyquinoline)aluminum(III) (Alq3 ) films.

    PubMed

    Cuba, M; Muralidharan, G

    2015-05-01

    Tris-(8-hydroxyquionoline)aluminum (Alq3 ) was synthesized and coated on to a glass substrate using the dip coating method. The structural and optical properties of the Alq3 film after thermal annealing from 50°C to 300°C in 50° steps was studied. The films have been prepared with 2 to 16 layers (42-324 nm). The thickness and thermal annealing of Alq3 films were optimized for maximum luminescence yield. The Fourier transform infrared spectrum confirms the formation of quinoline with absorption in the region 700 - 500/cm. Partial sublimation and decomposition of quinoline ion was observed with the Alq3 films annealed at 300°C. The X-ray diffraction pattern of the Alq3 film annealed at 50°C to 150°C reveals the amorphous nature of the films. The Alq3 film annealed above 150°C were crystalline nature. Film annealed at 150°C exhibits a photoluminescence intensity maximum at 512 nm when excited at 390 nm. The Alq3 thin film deposited with 10 layers (220 nm) at 150°C exhibited maximum luminescence yield.

  16. The MUSIC of Galaxy Clusters - III. Properties, evolution and Y-M scaling relation of protoclusters of galaxies

    NASA Astrophysics Data System (ADS)

    Sembolini, Federico; De Petris, Marco; Yepes, Gustavo; Foschi, Emma; Lamagna, Luca; Gottlöber, Stefan

    2014-06-01

    In this work, we study the properties of protoclusters of galaxies by employing the MultiDark SImulations of galaxy Clusters (MUSIC) set of hydrodynamical simulations, featuring a sample of 282 resimulated clusters with available merger trees up to z = 4. We study the characteristics and redshift evolution of the mass and the spatial distribution for all the protoclusters, which we define as the most massive progenitors of the clusters identified at z = 0. We extend the study of the baryon content to redshifts larger than 1 also in terms of gas and stars budgets: no remarkable variations with redshift are discovered. Furthermore, motivated by the proven potential of Sunyaev-Zel'dovich surveys to blindly search for faint distant objects, we compute the scaling relation between total object mass and integrated Compton y-parameter. We find that the slope of this scaling law is steeper than what expected for a self-similarity assumption among these objects, and it increases with redshift mainly when radiative processes are included. We use three different criteria to account for the dynamical state of the protoclusters, and find no significant dependence of the scaling parameters on the level of relaxation. We exclude the dynamical state as the cause of the observed deviations from self-similarity in protoclusters.

  17. Phonon and free-charge carrier properties in group-III nitride heterostructures investigated by spectroscopic ellipsometry and optical Hall effect

    NASA Astrophysics Data System (ADS)

    Schoeche, Stefan

    The material class of group-III nitrides gained tremendous technological importance for optoelectronic and high-power/high-frequency amplification devices. Tunability of the direct band gap from 0.65 eV (InN) to 6.2 eV (AlN) by alloying, high breakthrough voltages and intrinsic mobilities, as well as the formation of highly mobile 2d electron gases (2DEG) at heterointerfaces make these compounds ideal for many applications. GaN and Ga-rich alloys are well studied and current research is mainly device-oriented. For example, choice and quality of the gate dielectric significantly influence device performance in high-electron mobility transistors (HEMT) which utilize highly mobile 2DEGs at heterointerfaces. Experimental access to the 2DEG channel properties without influence from parasitic currents or contact properties are desirable. In- and Al-rich ternary alloys are less explored than Ga-rich compounds. For InN and In-rich alloys, while many material parameters such as stiffness constants or effective mass values are largely unknown, reliable p-type doping is a major challenge, also because p-type conducting channels are buried within highly conductive n-type material formed at the surface and interfaces preventing electrical characterization. For AlN and high-Al content alloys, doping mechanisms are not understood and reliable fabrication of material with high free-charge carrier (FCC) concentrations was achieved just recently. Difficulties to form ohmic contacts impair electrical measurements and optical characterization is impeded by lack of high-energy excitation sources. In this work, spectroscopic ellipsometry over the wide spectral range from the THz to VUV in combination with optical Hall effect (generalized ellipsometry with applied magnetic field) from THz to MIR are applied in order to investigate the phonon modes and FCC properties in group-III nitride heterostructures. Adequate model descriptions and analysis strategies are introduced which allow

  18. Welding III.

    ERIC Educational Resources Information Center

    Allegheny County Community Coll., Pittsburgh, PA.

    Instructional objectives and performance requirements are outlined in this course guide for Welding III, an advanced course in arc welding offered at the Community College of Allegheny County to provide students with the proficiency necessary for industrial certification. The course objectives, which are outlined first, specify that students will…

  19. Part III: lithium metasilicate (Li2SiO3)—mild condition hydrothermal synthesis, characterization and optical properties

    NASA Astrophysics Data System (ADS)

    Alemi, Abdolali; Khademinia, Shahin; Sertkol, Murat

    2015-02-01

    Li2SiO3 nanopowders were synthesized via a non-stoichiometric 2:3 (S1), 1:3 (S2), 1:4 (S3) and 1:5 (S4) Li/Si molar ratios via hydrothermal reaction for 72 h at 180 °C in an aqua solution using Li2CO3 and H2SiO3 as raw materials. The synthesized materials were characterized by powder X-ray diffraction (PXRD) technique and Fourier transform infrared spectroscopy. PXRD data showed that the crystal structure of the obtained materials is orthorhombic with the space group of Cmc21. Also, to investigate the effect of the Li/Si molar ratio on the morphology of the obtained materials, the morphologies of the synthesized materials were studied by field emission scanning electron microscopy. The technique showed that with changing the Li/Si molar ratio from S1 to S4, the morphology of as-prepared samples changed from flower structures to microrod-microsphere and then to a non-homogenous layer-like structure. Ultraviolet-visible spectra showed that the nanostructure lithium silicate powders had good light absorption properties in the ultraviolet light region. It showed that with changing the Li/Si molar ratio from S1 to S4, the calculated band gap was decreased. Also, cell parameter refinement showed that with changing the Li/Si molar ratio from S1 to S4 the cell parameters decreased. Photoluminescence analysis of the obtained materials was studied at the excitation wavelength of 247 nm. It showed that the emission spectra of the obtained materials had a blue shift from S1 to S4.

  20. Piezo- and elasto-optic properties of liquids under high pressure. III. Results on twelve more liquids

    NASA Astrophysics Data System (ADS)

    Chen, C. C.; Vedam, K.

    1980-11-01

    Precision optical interferometric measurements at high pressures have been made on twelve liquids. The liquids studied are chloroform, carbon disulfide, o-xylene, m-xylene, 1-3-5-trimethyl benzene, cumene, methyl cyclohexane, ethyl bromide, ethyl iodide, isobutyl alcohol, ethyl acohol, and deuterium oxide. The piezo- and elasto-optic properties of these liquids are found to be similar to those of other liquids described in Papers I and II of this series. For all these liquids, the data reveal pronounced nonlinear piezo-optical (Δn vs P) behavior, but linear elasto-optical (Δn vs ɛ, when ɛ is the Eulerian strain) relationship. Thus, the Eulerian representation of strain is advantageous in describing the elasto-optic behavior of liquids, irrespective of the shape, size, and composition of the molecules of the liquid. The linear relationship between Δn and Eulerian strain can be used to discriminate between the various equations of state. It may also provide a simple empirical expression for the computation of density from the accurately measured values of the changes in refractive index of liquids. The various expressions prevalent in the literature for the relationship between refractive index and density were analyzed by least-squares analysis technique. It is shown that the Drude and Lorentz-Lorenz equations (which are most widely used in the literature on such studies) give either too low or too high values of Δn. Kirkwood-Brown and Omini equations which were derived using detailed statistical mechanical approach, appear to yield values in moderately good agreement with experimental values.

  1. A classical case of the Gasul phenomenon.

    PubMed

    Sabnis, Girish R; Phadke, Milind S; Kerkar, Prafulla G

    2016-02-01

    This case demonstrates the development of secondary infundibular stenosis in a 10-year-old male child with documented large non-restrictive perimembranous ventricular septal defect in infancy - the classical Gasul phenomenon.

  2. Partitioned Image Filtering for Reduction of the Gibbs Phenomenon

    PubMed Central

    Zeng, Gengsheng L.; Allred, Richard J.

    2017-01-01

    The aim of this paper is to propose a partitioned-image filtering technique that is a new way of reducing the Gibbs phenomenon in filtered images. Methods This technique relies on exploiting the properties of the Gibbs phenomenon and on assumptions about the structure of the image. The amplitude of the Gibbs ringing is directly proportional to the height of the image discontinuity. If the height of the discontinuity can be reduced, then the subsequent ringing will also be reduced. Separating the image into stratified layers or partitions reduces the height of the discontinuity significantly. Each partition is filtered separately and recombined nonlinearly to yield the final filtered image. This method weakens filtering of image edges that have large discontinuities, thus reducing the Gibbs phenomenon while simultaneously reducing the image noise. Results The proposed filtering method has been applied to a simple image with only 2 intensity values to illustrate the implementation steps. The method has also been applied to 2 SPECT patient studies to show the effectiveness of the proposed filtering method, which can significantly reduce the Gibbs artifacts. Conclusion The Gibbs phenomenon in a filtered image can be reduced by partitioning the image so that the amplitude of the discontinuity is controlled. The proposed method is efficient and simple in implementation, with fast Fourier transform. PMID:19447854

  3. Validation of the Impostor Phenomenon among Managers

    PubMed Central

    Rohrmann, Sonja; Bechtoldt, Myriam N.; Leonhardt, Mona

    2016-01-01

    Following up on earlier investigations, the present research aims at validating the construct impostor phenomenon by taking other personality correlates into account and to examine whether the impostor phenomenon is a construct in its own right. In addition, gender effects as well as associations with dispositional working styles and strain are examined. In an online study we surveyed a sample of N = 242 individuals occupying leadership positions in different sectors. Confirmatory factor analyses provide empirical evidence for the discriminant validity of the impostor phenomenon. In accord with earlier studies we show that the impostor phenomenon is accompanied by higher levels of anxiety, dysphoric moods, emotional instability, a generally negative self-evaluation, and perfectionism. The study does not reveal any gender differences concerning the impostor phenomenon. With respect to working styles, persons with an impostor self-concept tend to show perfectionist as well as procrastinating behaviors. Moreover, they report being more stressed and strained by their work. In sum, the findings show that the impostor phenomenon constitutes a dysfunctional personality style. Practical implications are discussed. PMID:27313554

  4. PP composites with Hybrid Nanofillers: NTC phenomenon

    NASA Astrophysics Data System (ADS)

    Sarlin, Juha; Immonen, Kirsi

    2010-06-01

    Electric conductive plastic composites have a wide potential for commercial applications, some examples are EMI shielding housings and components in automotive industry and in consumer electronics, equipments in health care sector and fuel cell components. A phenomenon in conductive composites, especially in composites with carbon based fillers, is change of thermal induced change in conductivity as a result of morphological transitions. Usually the observed changes are practically irreversible. The phenomenon may cause increasing resistivity, usually called as "positive temperature coefficient" (PTC) or decreasing resistivity, called "negative temperature coefficient (NTC), where the new morphology created by heat treatment is more favorable for electric conductivity compared to the original state. The existence of NTC is a sing of the lost potential in material design and processing. Therefore detailed information about the phenomenon gives us tools to develop high performance conductive materials. It this paper we discuss about NTC phenomenon observed in PP composites with CNT or in-situ synthesized CNT-PANi hybrid nanofiller with an amphiphilic dispersing agent. The goal of the paper is not to present a comprehensive model of this phenomenon; we present some experimental results which may be related to polymer-filler interactions. These details are a part of this complicated phenomenon.

  5. Influence of chloride in mortar made of Portland cement types II, III, and V on the near-field microwave reflection properties

    NASA Astrophysics Data System (ADS)

    Hu, Cairong; Benally, Aaron D.; Case, Tobias; Zoughi, Reza; Kurtis, Kimberly

    2000-07-01

    Corrosion of steel rebar in reinforced concrete structures, can be induced by the presence of chloride in the structure. Corrosion of steel rebar is a problematic issue in the construction industry as it compromises the strength and integrity of the structure. Although techniques exist for chloride detection and its migration into a structure, they are destructive, time consuming and cannot be used for the interrogation of large surfaces. In this investigation three different portland cement types; namely, ASTM types II, III and V were used, and six cubic (8' X 8' X 8') mortar specimens were produced all with water-to-cement (w/c) ratio of 0.6 and sand-to-cement (s/c) ratio of 1.5. Tap water was used when producing three of these specimens (one of each cement type). For the other three specimens calcium chloride was added to the mixing tap water resulting in a salinity of 2.5%. These specimens were placed in a hydration room for one day and thereafter left it the room temperature with low humidity. The reflection properties of these specimens, using an open-ended rectangular waveguide probe, were monitored daily at 3 GHz (S-band) and 10 GHz (X-band). The results show the influence of cement type on the reflection coefficient as well as the influence of chloride on the curing process and setting time.

  6. A comprehensive study of the magnetic, structural, and transport properties of the III-V ferromagnetic semiconductor InMnP

    SciTech Connect

    Khalid, M.; Hübner, R.; Baehtz, C.; Skorupa, W.; Zhou, Shengqiang; Gao, Kun; Helm, M.; Weschke, E.; Gordan, O.; Salvan, G.; Zahn, D. R. T.

    2015-01-28

    The manganese induced magnetic, electrical, and structural modification in InMnP epilayers, prepared by Mn ion implantation and pulsed laser annealing, are investigated in the following work. All samples exhibit clear hysteresis loops and strong spin polarization at the Fermi level. The degree of magnetization, the Curie temperature, and the spin polarization depend on the Mn concentration. The bright-field transmission electron micrographs show that InP samples become almost amorphous after Mn implantation but recrystallize after pulsed laser annealing. We did not observe an insulator-metal transition in InMnP up to a Mn concentration of 5 at. %. Instead all InMnP samples show insulating characteristics up to the lowest measured temperature. Magnetoresistance results obtained at low temperatures support the hopping conduction mechanism in InMnP. We find that the Mn impurity band remains detached from the valence band in InMnP up to 5 at. % Mn doping. Our findings indicate that the local environment of Mn ions in InP is similar to GaMnAs, GaMnP, and InMnAs; however, the electrical properties of these Mn implanted III-V compounds are different. This is one of the consequences of the different Mn binding energy in these compounds.

  7. The Dickeya dadantii biofilm matrix consists of cellulose nanofibres, and is an emergent property dependent upon the type III secretion system and the cellulose synthesis operon.

    PubMed

    Jahn, Courtney E; Selimi, Dija A; Barak, Jeri D; Charkowski, Amy O

    2011-10-01

    Dickeya dadantii is a plant-pathogenic bacterium that produces cellulose-containing biofilms, called pellicles, at the air-liquid interface of liquid cultures. D. dadantii pellicle formation appears to be an emergent property dependent upon at least three gene clusters, including cellulose synthesis, type III secretion system (T3SS) and flagellar genes. The D. dadantii cellulose synthesis operon is homologous to that of Gluconacetobacter xylinus, which is used for industrial cellulose production, and the cellulose nanofibres produced by D. dadantii were similar in diameter and branching pattern to those produced by G. xylinus. Salmonella enterica, an enterobacterium closely related to D. dadantii, encodes a second type of cellulose synthesis operon, and it produced biofilm strands that differed in width and branching pattern from those of D. dadantii and G. xylinus. Unlike any previously described cellulose fibre, the D. dadantii cellulose nanofibres were decorated with bead-like structures. Mutation of the cellulose synthesis operon genes resulted in loss of cellulose synthesis and production of a cellulase-resistant biofilm. Mutation of other genes required for pellicle formation, including those encoding FliA (a sigma factor that regulates flagella production), HrpL (a sigma factor that regulates the T3SS), and AdrA, a GGDEF protein, affected both biofilm and cell morphology. Mutation of the cellulose synthase bcsA or of bcsC resulted in decreased accumulation of the T3SS-secreted protein HrpN.

  8. Synthesis, photophysical, electrochemical and electroluminescent properties of a novel iridium(III) complex based on 2-phenylbenzo[d]oxazole derivative.

    PubMed

    Li, Xiao; Yu, Xiao-Ting; Chi, Hai-Jun; Dong, Yan; Xiao, Guo-Yong; Lei, Peng; Zhang, Dong-Yu; Cui, Zheng

    2013-12-01

    A new phosphorescent iridium (III) complex based on 2-(4-tert-butylphenyl)-5-methylbenzo[d]oxazole as main ligand, i.e. bis(2-(4-tert-butylphenyl)-5-methylbenzo[d]oxazole-N,C(2'))iridium(acetylacetonate) [(tmbo)2Ir(acac)], was synthesized for organic light-emitting diodes (OLEDs), and its photophysical, electrochemical and electroluminescent properties were investigated. The complex displayed strong phosphorescence emission, high decomposition temperature, short phosphorescent lifetime and reversible redox electrochemical behavior. The OLEDs based on (tmbo)2Ir(acac) as dopant emitter exhibited maximum luminance efficiency of 26.1cdA(-1) and high luminance of 16,445 cd m(-2). Interestingly, highly doped device based on (tmbo)2Ir(acac) showed high efficiency with negligible roll-off under a wide range of driving current density, which was mainly attributed to the effect of bulky steric hindrance of multi-methyl groups on this complex and its short phosphorescent lifetime.

  9. Synthesis, photophysical, electrochemical and electroluminescent properties of a novel iridium(III) complex based on 2-phenylbenzo[d]oxazole derivative

    NASA Astrophysics Data System (ADS)

    Li, Xiao; Yu, Xiao-Ting; Chi, Hai-Jun; Dong, Yan; Xiao, Guo-Yong; Lei, Peng; Zhang, Dong-Yu; Cui, Zheng

    2013-12-01

    A new phosphorescent iridium (III) complex based on 2-(4-tert-butylphenyl)-5-methylbenzo[d]oxazole as main ligand, i.e. bis(2-(4-tert-butylphenyl)-5-methylbenzo[d]oxazole-N,C2‧)iridium(acetylacetonate) [(tmbo)2Ir(acac)], was synthesized for organic light-emitting diodes (OLEDs), and its photophysical, electrochemical and electroluminescent properties were investigated. The complex displayed strong phosphorescence emission, high decomposition temperature, short phosphorescent lifetime and reversible redox electrochemical behavior. The OLEDs based on (tmbo)2Ir(acac) as dopant emitter exhibited maximum luminance efficiency of 26.1 cd A-1 and high luminance of 16,445 cd m-2. Interestingly, highly doped device based on (tmbo)2Ir(acac) showed high efficiency with negligible roll-off under a wide range of driving current density, which was mainly attributed to the effect of bulky steric hindrance of multi-methyl groups on this complex and its short phosphorescent lifetime.

  10. Role of the N-terminal starch-binding domains in the kinetic properties of starch synthase III from Arabidopsis thaliana.

    PubMed

    Valdez, Hugo A; Busi, Maria V; Wayllace, Nahuel Z; Parisi, Gustavo; Ugalde, Rodolfo A; Gomez-Casati, Diego F

    2008-03-04

    Starch synthase III (SSIII), one of the SS isoforms involved in plant starch synthesis, has been reported to play a regulatory role in the synthesis of transient starch. SSIII from Arabidopsis thaliana contains 1025 amino acid residues and has an N-terminal transit peptide for chloroplast localization which is followed by three repeated starch-binding domains (SBDs; SSIII residues 22-591) and a C-terminal catalytic domain (residues 592-1025) similar to bacterial glycogen synthase. In this work, we constructed recombinant full-length and truncated isoforms of SSIII, lacking one, two, or three SBDs, and recombinant proteins, containing three, two, or one SBD, to investigate the role of these domains in enzyme activity. Results revealed that SSIII uses preferentially ADPGlc, although UDPGlc can also be used as a sugar donor substrate. When ADPGlc was used, the presence of the SBDs confers particular properties to each isoform, increasing the apparent affinity and the V max for the oligosaccharide acceptor substrate. However, no substantial changes in the kinetic parameters for glycogen were observed when UDPGlc was the donor substrate. Under glycogen saturating conditions, the presence of SBDs increases progressively the apparent affinity and V max for ADPGlc but not for UDPGlc. Adsorption assays showed that the N-terminal region of SSIII, containing three, two, or one SBD module have increased capacity to bind starch depending on the number of SBD modules, with the D23 protein (containing the second and third SBD module) being the one that makes the greatest contribution to binding. The results presented here suggest that the N-terminal SBDs have a regulatory role, showing a starch binding capacity and modulating the catalytic properties of SSIII.

  11. Tuning of chain chirality by interchain stacking forces and the structure-property relationship in coordination systems constructed by meridional Fe(III) cyanide and Mn(III) Schiff bases.

    PubMed

    Sohn, Ah Ram; Lim, Kwang Soo; Kang, Dong Won; Song, Jeong Hwa; Koh, Eui Kwan; Moon, Dohyun; Hong, Chang Seop

    2016-12-06

    We synthesized six Fe(iii)-Mn(iii) bimetallic compounds by self-assembling the newly developed mer-Fe cyanide PPh4[Fe(Clqpa)(CN)3]·H2O (1) and PPh4[Fe(Brqpa)(CN)3]·H2O (2) with Mn Schiff base Mn(5-Xsalen)(+) cations. These compounds include [Fe(Xqpa)(CN)3][Mn(5-Ysalen)]·pMeOH·qH2O [qpaH2 = N-(quinolin-8-yl)picolinamide; salen = N,N'-ethylenebis(salicylideneiminato) dianion; X = Cl, Y = H (3); X = Cl, Y = Br (4); X = Br, Y = H (5); X = Br, Y = F (6); X = Br, Y = Cl (7); X = Br, Y = Br (8)]. When precursor 1 was used, compounds 3 and 4 were isolated to give a dinuclear entity and a linear chain structure, respectively. The reaction of precursor 2 with the Schiff bases afforded four linear Fe(iii)-Mn(iii) chain complexes. Chain chirality with P- and M-helicity emerges in 4, 7, and 8, while 5 exhibits chain helicity opposite to the previous chain complexes and 6 presents no chain helicity. Such a structural feature is heavily dependent on the interchain π-π contacts and the Fe precursor bridging unit. Chiral induction from a local ethylenediamine link of Y-salen is propagated over the chain via noncovalent π-π interactions. All the bimetallic compounds show antiferromagnetic interactions transmitted by the cyanide linkage. A field-induced metamagnetic transition is involved in 4, 7, and 8, while a field-induced two-step transition is evident in 6. From a magnetostructural viewpoint, the coupling constant is primarily governed by the Mn-Nax-Cax angle (ax = axial) in the bimetallic chain complexes composed of mer-Fe(iii) tricyanides, although the torsion angle plays a role.

  12. Synthesis, Properties, and Light-Emitting Electrochemical Cell (LEEC) Device Fabrication of Cationic Ir(III) Complexes Bearing Electron-Withdrawing Groups on the Cyclometallating Ligands

    PubMed Central

    2016-01-01

    The structure–property relationship study of a series of cationic Ir(III) complexes in the form of [Ir(C^N)2(dtBubpy)]PF6 [where dtBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine and C^N = cyclometallating ligand bearing an electron-withdrawing group (EWG) at C4 of the phenyl substituent, i.e., −CF3 (1), −OCF3 (2), −SCF3 (3), −SO2CF3 (4)] has been investigated. The physical and optoelectronic properties of the four complexes were comprehensively characterized, including by X-ray diffraction analysis. All the complexes exhibit quasireversible dtBubpy-based reductions from −1.29 to −1.34 V (vs SCE). The oxidation processes are likewise quasireversible (metal + C^N ligand) and are between 1.54 and 1.72 V (vs SCE). The relative oxidation potentials follow a general trend associated with the Hammett parameter (σ) of the EWGs. Surprisingly, complex 4 bearing the strongest EWG does not adhere to the expected Hammett behavior and was found to exhibit red-shifted absorption and emission maxima. Nevertheless, the concept of introducing EWGs was found to be generally useful in blue-shifting the emission maxima of the complexes (λem = 484–545 nm) compared to that of the prototype complex [Ir(ppy)2(dtBubpy)]PF6 (where ppy = 2-phenylpyridinato) (λem = 591 nm). The complexes were found to be bright emitters in solution at room temperature (ΦPL = 45–66%) with microsecond excited-state lifetimes (τe = 1.14–4.28 μs). The photophysical properties along with density functional theory (DFT) calculations suggest that the emission of these complexes originates from mixed contributions from ligand-centered (LC) transitions and mixed metal-to-ligand and ligand-to-ligand charge transfer (LLCT/MLCT) transitions, depending on the EWG. In complexes 1, 3, and 4 the 3LC character is prominent over the mixed 3CT character, while in complex 2, the mixed 3CT character is much more pronounced, as demonstrated by DFT calculations and the observed positive solvatochromism

  13. Synthesis, Properties, and Light-Emitting Electrochemical Cell (LEEC) Device Fabrication of Cationic Ir(III) Complexes Bearing Electron-Withdrawing Groups on the Cyclometallating Ligands.

    PubMed

    Pal, Amlan K; Cordes, David B; Slawin, Alexandra M Z; Momblona, Cristina; Ortı, Enrique; Samuel, Ifor D W; Bolink, Henk J; Zysman-Colman, Eli

    2016-10-17

    The structure-property relationship study of a series of cationic Ir(III) complexes in the form of [Ir(C^N)2(dtBubpy)]PF6 [where dtBubpy = 4,4'-di-tert-butyl-2,2'-bipyridine and C^N = cyclometallating ligand bearing an electron-withdrawing group (EWG) at C4 of the phenyl substituent, i.e., -CF3 (1), -OCF3 (2), -SCF3 (3), -SO2CF3 (4)] has been investigated. The physical and optoelectronic properties of the four complexes were comprehensively characterized, including by X-ray diffraction analysis. All the complexes exhibit quasireversible dtBubpy-based reductions from -1.29 to -1.34 V (vs SCE). The oxidation processes are likewise quasireversible (metal + C^N ligand) and are between 1.54 and 1.72 V (vs SCE). The relative oxidation potentials follow a general trend associated with the Hammett parameter (σ) of the EWGs. Surprisingly, complex 4 bearing the strongest EWG does not adhere to the expected Hammett behavior and was found to exhibit red-shifted absorption and emission maxima. Nevertheless, the concept of introducing EWGs was found to be generally useful in blue-shifting the emission maxima of the complexes (λem = 484-545 nm) compared to that of the prototype complex [Ir(ppy)2(dtBubpy)]PF6 (where ppy = 2-phenylpyridinato) (λem = 591 nm). The complexes were found to be bright emitters in solution at room temperature (ΦPL = 45-66%) with microsecond excited-state lifetimes (τe = 1.14-4.28 μs). The photophysical properties along with density functional theory (DFT) calculations suggest that the emission of these complexes originates from mixed contributions from ligand-centered (LC) transitions and mixed metal-to-ligand and ligand-to-ligand charge transfer (LLCT/MLCT) transitions, depending on the EWG. In complexes 1, 3, and 4 the (3)LC character is prominent over the mixed (3)CT character, while in complex 2, the mixed (3)CT character is much more pronounced, as demonstrated by DFT calculations and the observed positive solvatochromism effect. Due to the

  14. Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

    PubMed

    Díaz-Gallifa, Pau; Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2014-06-16

    Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges.

  15. Docetaxel-induced photo-recall phenomenon.

    PubMed

    Droitcourt, Catherine; Le Hô, Hélêne; Adamski, Henri; Le Gall, François; Dupuy, Alain

    2012-08-01

    Photo-recall phenomenon is a phototoxic eruption occurring on areas of previous ultraviolet-induced solar erythema following a systemic administration of a drug. It has been mostly described with methotrexate but remains rare with other antineoplastic drugs. We describe a case of docetaxel-induced photo-recall skin rash in a woman treated for a non-small-cell lung cancer. Although the patient has refused to receive a second infusion, chemotherapy can be carried on with photoprotection and the use of topical and/or systemic corticosteroids. In contrast, radiation recall is a well-known reaction by oncologists, most of them may not be aware of a similar phenomenon called photo-recall phenomenon. Recognizing this entity may avoid misdiagnosing a drug allergy and should avoid inappropriate decisions of drug discontinuation.

  16. Europium(III)-doped A2Hf2O7 (A = Y, Gd, Lu) nanoparticles: Influence of annealing temperature, europium(III) concentration and host cation on the luminescent properties

    NASA Astrophysics Data System (ADS)

    Papan, Jelena; Jovanović, Dragana J.; Vuković, Katarina; Smits, Krisjanis; Đorđević, Vesna; Dramićanin, Miroslav

    2016-11-01

    The detailed analyses of structure and luminescence of europium(III)-doped A2Hf2O7 (A = Y, Gd, Lu) nanoparticles is presented. Samples were prepared by time and cost effective combustion method that utilize polyethylene glycol both as a chelating agent and as a fuel, with different europium(III) concentrations (from 1 to 12 at.%), annealed at temperatures ranging from 800 to 1400 °C, and with alternating A3+ cation in the A2Hf2O7 host. Then, structural variations between materials were analysed by X-ray diffraction and structural refinement, while the changes in the luminescence were assessed from the Judd-Ofelt analyses of emission spectra. Nanoparticles prepared at the lowest temperature (800 °C) had the smallest particle size of ∼6 nm and showed the highest quantum efficiency when doped with 1 and 2 at.% of europium(III). Radiative transition rate and quantum efficiency of emission showed Lu2Hf2O7 > Gd2Hf2O7 > Y2Hf2O7 trend.

  17. Synthesis and luminescent properties of a novel green-emitting Tb(III) complex and the excellent thermal stability for application

    NASA Astrophysics Data System (ADS)

    Yuan, Chen; Xie, Hongde; Cai, Haijun; Chen, Cuili; Cai, Peiqing; Seo, Hyo Jin

    2016-04-01

    A green-emitting Tb(III) complex based on siloxane-modified pressure sensitive adhesives (SPSA-Tb(III)) was successfully synthesized by emulsion polymerization. Siloxane-modified pressure sensitive adhesives (SPSA) were used as host materials. The structural coordination, photoluminescence excitation (PLE) and luminescence (PL) spectra, and thermal characterization of this luminescent polymer were investigated. The result from the FT-IR spectra reveals that SPSA have successfully coordinated with the Tb(III) ions. The luminescent analysis indicates that SPSA-Tb(III) displays Tb(III) typical emission peaks at 489, 545, 583, and 622 nm under the excitation of 369 nm. When monitored at 545 nm, strong and sharp excitation bands appear from 300 to 500 nm. And SPSA-Tb(III) has short lifetime (0.25 ms). Meanwhile, SPSA-Tb(III) exhibits high thermal stability (Td = 402 °C) owing to the high bond dissociation energy of Sisbnd O bonds. All the results suggest that it is expected to be used as a superior green-emitting material under high temperature.

  18. Structural, magnetic and phonon properties of Cr(III)-doped perovskite metal formate framework [(CH3)2NH2][Mn(HCOO)3

    NASA Astrophysics Data System (ADS)

    Mączka, Mirosław; Gągor, Anna; Hermanowicz, Krzysztof; Sieradzki, Adam; Macalik, Lucyna; Pikul, Adam

    2016-05-01

    We have incorporated Cr(III) into [(CH3)2NH2][Mn(HCOO)3] (DMMn) multiferroic metal organic framework (MOF). The highest concentration of Cr(III) in the synthesized samples reached 15.9 mol%. The obtained samples were characterized by powder and single-crystal X-ray diffraction, DSC, magnetic susceptibility, dielectric, EPR, Raman and IR methods. These methods and the performed chemical analysis revealed that electrical charge neutrality after substitution of Cr(III) for Mn(II) is maintained by partial replacement of dimethylammonium (DMA+) cations by neutral HCOOH molecules. These changes in the chemical composition are responsible for weakening of the hydrogen bonds and decreased flexibility of the framework. This in turn leads to lowering of the ferroelectric phase transition temperature, observed around 185 K for undoped DMMn and around 155 K for the sample containing 3.1 mol% of Cr(III), and lack of macroscopic phase transition for the samples with Cr(III) content of 8.2 and 15.9 mol %. Another interesting effect observed for the studied samples is pronounced strengthening of the weak ferromagnetism of in Cr(III)-doped samples, associated with slight decrease of the ferromagnetic ordering temperature from 8.5 K for DMMn to 7.0 K for the sample with 15.9 mol % Cr(III) content.

  19. Aging phenomenon of stabilized bismuth oxides

    SciTech Connect

    Jiang, N.; Buchanan, R.M.; Henn, F.E.G.; Marshall, A.F.; Stevenson, D.A. . Dept. of Materials Science and Engineering); Washsman, E.D. . Materials Research Center)

    1994-03-01

    Stabilized bismuth oxides exhibit a decay in conductivity when annealed at temperatures below 600 C. The authors refer to this phenomenon as aging and it is distinct from a conventional crystallographic phase transformation. This phenomenon is revealed by an endotherm from DSC thermal analysis and results in the formation of a superstructure observable by TEM diffraction patterns, yet no change in structure is observable by XRD. Since oxygen vacancies are the mobile defects responsible for ionic conductivity, the authors attribute the aging process to the ordering of oxygen vacancies by an order-disorder transition below [approximately]600 C.

  20. First time description of dismantling phenomenon

    PubMed Central

    Barrer, Laurence; Gimenez, Guy

    2015-01-01

    Dismantling is a complex psychic phenomenon, which is not easy to define, and little interest has been shown in the subject. The authors of this paper want to demonstrate that dismantling is the main defense mechanism in autism, bringing about de-consensus of senses. The effects perceived in a child with autistic disorder are passivity and lack of thought. The authors’ purpose here is to define the dismantled state and reveal its underlying process. This paper will therefore describe for the first time in literature, the dismantling phenomenon and will submit a metapsychological approach of this defense mechanism. PMID:25999871

  1. Effects of the frontier orbitals on the electrochemical and electrochemiluminescent properties of the bis-cyclometalated iridium(III) complexes with different ligands

    NASA Astrophysics Data System (ADS)

    Zhu, Shengnan; Song, Qijun; Zhang, Songlin; Ding, Yuqiang

    2013-03-01

    The electrochemical and electrochemiluminescent (ECL) properties of six bis-cyclometalated iridium(III) complexes (ppy)2Ir(N-phenylacetamide) (1), (ppy)2Ir(N-phenylbenzamide) (2), (ppy)2Ir(N-naphthylbenzamide) (3), (ppy)2Ir(N-phenylmethacrylamide) (4), (pq)2Ir(N-phenylmethacrylamide) (5) and (pq)2Ir(acac) (6) were studied in acetonitrile, where ppy is phenylpyridine anion, pq is phenylquinoline anion and acac is acetylacetone anion. These complexes exhibited quasi-reversible one-electron oxidation waves with the oxidation potentials varied from 0.95 to 1.51 V (vs. SCE) and the first irreversible reduction peaks fell into the range of -1.58 to -1.86 V. The effects of the different ligands on the redox potentials and electrochemical reversibility were elucidated by the energies and compositions of the frontier orbitals. The relative ECL efficiencies of the complexes 1-6 were 0.032, 0.020, 0.014, 0.041, 0.11 and 26.0 respectively when referenced to Ru(bpy)32+ and the differences in ECL efficiency were rationalized by the density functional theory (DFT) calculations. The energy gap between the lowest unoccupied molecular orbital (LUMO) of anodic product (M+rad ) and the deprotonated product (TPArad ) determined the electron transfer efficiency to generate the excited states. Other factors such as the lifetime of the radical intermediates, the oxidation potential gaps between the M and TPA, the amount of M+rad generation and the luminescence efficiency (Φem) were also considered in comparison of different ECL systems.

  2. The distal ExsA-binding site in Pseudomonas aeruginosa type III secretion system promoters is the primary determinant for promoter-specific properties.

    PubMed

    Brutinel, Evan D; King, Jessica M; Marsden, Anne E; Yahr, Timothy L

    2012-05-01

    Transcription of the Pseudomonas aeruginosa type III secretion system is controlled by ExsA, a member of the AraC/XylS family of regulators. Each ExsA-dependent promoter contains two adjacent binding sites for monomeric ExsA. The promoter-proximal site (binding site 1) consists of highly conserved GnC and TGnnA sequences that are individually recognized by the two helix-turn-helix (HTH) DNA-binding motifs of an ExsA monomer. While the GnC and TGnnA sequences are important for binding to site 1, the promoter-distal binding sites (site 2) lack obvious similarity among themselves or with binding site 1. In the present study, we demonstrate that site 2 in the P(exsC) promoter region contains a GnC sequence that is functionally equivalent to the GnC in site 1 and recognized by the first HTH motif of an ExsA monomer. Likewise, the second HTH interacts with an adenine residue in binding site 2. Although several candidate GnC sequences are also present in site 2 of the P(exsD), P(exoT), and P(pcrG) promoters, the GnC sequences were not required for ExsA-dependent transcription or ExsA binding. A comparison of hybrid promoters composed of binding site 2 from one promoter fused to binding site 1 derived from another promoter indicates that ExsA-binding affinity, promoter strength, and the degree of promoter bending are properties that are largely determined by binding site 2. Based on these data, we propose that the manner in which ExsA interacts with binding site 2 at the P(exsC) promoter is distinct from the interactions occurring at other promoters.

  3. Synthesis and luminescence properties of polymeric complexes of Cu(II), Zn(II) and Al(III) with 8-hydroxyquinoline side group-containing polystyrene

    NASA Astrophysics Data System (ADS)

    Gao, Baojiao; Wei, Xiaopeng; Zhang, Yanyan

    2013-01-01

    Three kinds of metalloquinolate-containing polystyrene were prepared via a polymer reaction and a coordination reaction. 5-Chloromethyl-8-hydroxyquinoline (CHQ) was first prepared through the chloromethylation reaction of 8-hydroxyquinoline (HQ) with 1,4-bichloromethoxy-butane as chloromethylation reagent. A polymer reaction, Friedel-Crafts alkylation reaction, was carried out between polystyrene (PS) and CHQ in the presence of Lewis catalyst, and HQ was bonded onto the side chains of PS, obtaining 8-hydroxyquinoline-functionalized Polystyrene, HQ-PS. And then, by using one-pot method with two-stage procedures, the coordination reaction of HQ-PS and small molecule HQ with metal ions including Al(III), Zn(II) and Cu(II) ions, was allowed to be carried out, and three polymeric metalloquinolates, AlQ3-PS, ZnQ2-PS and CuQ2-PS, were successfully prepared, respectively. In the chemical structures of these polymeric metalloquinolates, metalloquinolates were chemically attached onto the side chains of PS. HQ-PS and three polymeric metalloquinolates were fully characterized by FTIR, 1H NMR and TGA. The luminescence properties of the three polymeric metalloquinolates were mainly investigated by UV/Vis absorption spectra and fluorescence emission spectra in solutions and in solid film states. When excited by the ray at about 365 nm, the three polymeric metalloquinolates have blue-green luminescence, and the main emission peaks in the DMF solutions are located at 490, 482 and 502 nm for AlQ3-PS, ZnQ2-PS and CuQ2-PS, respectively. As compared with their emissions in solutions, the emissions in solid film states are red-shifted to some extent, and the main emission peaks are located at 500, 488 and 510 nm for AlQ3-PS, ZnQ2-PS and CuQ2-PS, respectively. Besides, these polymeric metalloquinolates have higher thermal stability than PS as polymeric skeleton.

  4. Manipulating Surface States of III-V Nanowires with Uniaxial Stress.

    PubMed

    Signorello, G; Sant, S; Bologna, N; Schraff, M; Drechsler, U; Schmid, H; Wirths, S; Rossell, M D; Schenk, A; Riel, H

    2017-04-10

    III-V compound semiconductors are indispensable materials for today's high-end electronic and optoelectronic devices and are being explored for next-generation transistor logic and quantum technologies. III-V surfaces and interfaces play the leading role in determining device performance, and therefore, methods to control their electronic properties have been developed. Typically, surface passivation studies demonstrated how to limit the density of surface states. Strain has been widely used to improve the electronic transport properties and optoelectronic properties of III-Vs, but the potential of this technology to modify the surface properties still remains to be explored. Here we show that uniaxial stress induces a shift in the energy of the surface states of III-V nanowires, modifying their electronic properties. We demonstrate this phenomenon by modulating the conductivity of InAs nanowires over 4 orders of magnitude with axial strain ranging between -2.5% in compression and 2.1% in tension. The band bending at the surface of the nanostructure is modified from accumulation to depletion reversibly and reproducibly. We provide evidence of this physical effect using a combination of electrical transport measurement, Raman spectroscopy, band-structure modeling, and technology computer aided design (TCAD) simulations. With this methodology, the deformation potentials for the surface states are quantified. These results reveal that strain technology can be used to shift surface states away from energy ranges in which device performance is negatively affected and represent a novel route to engineer the electronic properties of III-V devices.

  5. Facilitated Communication: The Clinical and Social Phenomenon.

    ERIC Educational Resources Information Center

    Shane, Howard C., Ed.

    This text explains the phenomenon of facilitated communication (FC) from an empirical, data-based, and/or clinical perspective. It is not a how-to-facilitate text, but one that explores the clinical and sociological reality of FC. A common theme running through each of the papers in the book is the question of FC's legitimacy. The papers reveal…

  6. A Phenomenon of Overqualification in Personnel Psychology

    ERIC Educational Resources Information Center

    Fine, Saul; Nevo, Baruch

    2007-01-01

    This study examines the concept of overqualification as a phenomenon of nonlinearity in the upper deciles of the ability-performance relationship. In three job contexts (military, academic, and industrial), the ability-performance relationship is characterized by a strong linear component below the mean and a ceiling effect at various points above…

  7. LED's and the "Fluttering Heart" Phenomenon.

    ERIC Educational Resources Information Center

    Jewett, John W., Jr.

    1993-01-01

    Describes the nineteenth-century parlor trick entitled the Fluttering Heart phenomenon which uses a red heart on a bright blue background. Discusses theories concerning the apparent fluttering. Suggests doing the trick with a red light-emitting diode in a darkened room. (MVL)

  8. Critical Barriers Phenomenon in Elementary Science.

    ERIC Educational Resources Information Center

    Apelman, Maja; And Others

    Conceptual obstacles which inhibit scientific understanding are examined in this monograph. Perspectives are offered on theoretical aspects, research directions, and educational implications on the problem area known as the critical barriers phenomenon. Papers included are: "Nature of the Problem" (by David Hawkins), which describes the…

  9. Bullying: Description and Analysis of the Phenomenon

    ERIC Educational Resources Information Center

    Benitez, Juan Luis; Justicia, Fernando

    2006-01-01

    This article purports to present this Special Issue about Bullying and, at the same time, to introduce the phenomenon of bullying in order to facilitate readers an updated vision about the problem that will be worked from different perspectives by researchers from national and international scope. With this purpose, we present some controversial…

  10. Feature extraction of arc tracking phenomenon

    NASA Technical Reports Server (NTRS)

    Attia, John Okyere

    1995-01-01

    This document outlines arc tracking signals -- both the data acquisition and signal processing. The objective is to obtain the salient features of the arc tracking phenomenon. As part of the signal processing, the power spectral density is obtained and used in a MATLAB program.

  11. Homocysteine and Raynaud's phenomenon: a review.

    PubMed

    Lazzerini, Pietro Enea; Capecchi, Pier Leopoldo; Bisogno, Stefania; Cozzalupi, Mauro; Rossi, Pier Carlo; Pasini, Franco Laghi

    2010-01-01

    Raynaud's phenomenon, categorized as primary and secondary when occurring isolated or in association with an underlying disease, respectively, is a paroxysmal and recurrent acral ischemia resulting from an abnormal arterial vasospastic response to cold or emotional stress. The key issue in the pathogenesis of Raynaud's phenomenon is presumed to be a dysregulation in the mechanisms of vascular motility resulting in an imbalance between vasodilatation and vasoconstriction. Homocysteine, a non-protein forming sulphured amino acid proposed as an independent risk factor for atherothrombosis in the general population, clearly demonstrated to produce vascular damage through mechanisms also including endothelial injury and modifications in circulating mediators of vasomotion. The rationale for homocysteine involvement in the pathogenesis of Raynaud's phenomenon led some authors to investigate the possible association between mild hyperhomocysteinemia and such a vascular disturbance, particularly in the course of connective tissue disease. Here we review data regarding this putative association and the supposed mechanisms involved, also discussing the emblematic case of a patient with new-onset severe Raynaud's phenomenon and markedly elevated homocysteinemia.

  12. Concept "Medical Museum" as a Sociocultural Phenomenon

    ERIC Educational Resources Information Center

    Chizh, Nina V.; Slyshkin, Gennady G.; Zheltukhina, Marina R.; Privalova, Irina V.; Kravchenko, Olga A.

    2016-01-01

    The article examines the concept "medical museum" as a sociocultural phenomenon. The register of medical museums in Russia makes the material of research. The complex methods of analysis of the concept "medical museum" are used. The philosophical, historical, cultural, structural, communicative and semantic analysis is carried…

  13. Antioxidation and DNA-binding properties of binuclear Er(III) complexes with Schiff-base ligands derived from 8-hydroxyquinoline-2-carboxaldehyde and four aroylhydrazines.

    PubMed

    Liu, Yong-Chun; Yang, Zheng-Yin

    2010-03-01

    The Er(III) complexes are prepared from Er(NO(3))(3).6H(2)O and Schiff-base ligands derived from 8-hydroxyquinoline-2-carboxaldehyde with four aroylhydrazines, including benzoylhydrazine, 2-hydroxybenzoylhydrazine, 4-hydroxybenzoylhydrazine and isonicotinylhydrazine, respectively. X-ray crystal and other structural analyses indicate that Er(III) and every ligand can form a binuclear Er(III) complex with nine-coordination and 1: 1 metal-to-ligand stoichiometry at the Er(III) centre. All the Er(III) complexes can bind to calf thymus DNA through intercalation with the binding constants at the order of magnitude 10(6) M(-1), and they may be used as potential anticancer drugs. All the Er(III) complexes have strong scavenging effects for hydroxyl radicals and superoxide radicals; however, complex containing active phenolic hydroxyl group shows stronger scavenging effects for hydroxyl radicals and complex containing N-heteroaromatic substituent shows stronger scavenging effects for superoxide radicals.

  14. Statin escape phenomenon: Fact or fiction?

    PubMed Central

    Barkas, Fotios; Elisaf, Moses; Klouras, Eleftherios; Dimitriou, Theodora; Tentolouris, Nikolaos; Liberopoulos, Evangelos

    2017-01-01

    AIM To evaluate the presence of the so called “statin escape” phenomenon among hyperlipidemic subjects attending a lipid clinic. METHODS This was a retrospective analysis of 1240 hyperlipidemic individuals followed-up for ≥ 3 years. We excluded those individuals meeting one of the following criteria: Use of statin therapy at baseline visit, discontinuation of statin treatment at most recent visit, change in statin treatment during follow-up and poor compliance to treatment. Statin escape phenomenon was defined as an increase in low-density lipoprotein cholesterol (LDL-C) levels at the most recent visit by > 10% compared with the value at 6 mo following initiation of statin treatment. RESULTS Of 181 eligible subjects, 31% exhibited the statin escape phenomenon. No major differences regarding baseline characteristics were found between statin escapers and non-statin escapers. Both escapers and non-escapers had similar baseline LDL-C levels [174 (152-189) and 177 (152-205) mg/dL, respectively]. In comparison with non-escapers, statin escapers demonstrated lower LDL-C levels at 6 mo after treatment initiation [88 (78-97) mg/dL vs 109 (91-129) mg/dL, P < 0.05], but higher levels at the most recent visit [103 (96-118) mg/dL vs 94 (79-114) mg/dL, P < 0.05]. CONCLUSION These data confirm the existence of an escape phenomenon among statin-treated individuals. The clinical significance of this phenomenon remains uncertain. PMID:28261552

  15. Synthesis and magnetic properties of a new family of macrocyclic M(II)3Ln(III) complexes: insights into the effect of subtle chemical modification on single-molecule magnet behavior.

    PubMed

    Feltham, Humphrey L C; Clérac, Rodolphe; Ungur, Liviu; Vieru, Veacheslav; Chibotaru, Liviu F; Powell, Annie K; Brooker, Sally

    2012-10-15

    Thirteen tetranuclear mixed-metal complexes of the hexaimine macrocycle (L(Pr))(6-) have been prepared in a one-pot 3:1:3:3 reaction of copper(II) acetate hydrate, the appropriate lanthanide(III) nitrate hydrate, 1,4-diformyl-2,3-dihydroxybenzene (1), and 1,3-diaminopropane. The resulting family of copper(II)-lanthanide(III) macrocyclic complexes has the general formula Cu(II)(3)Ln(III)(L(Pr))(NO(3))(3)·solvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Tb, Ho, Er, Tm, or Yb). X-ray crystal structure determinations carried out on [Cu(3)Ce(L(Pr))(NO(3))(3)(MeOH)(3)] and [Cu(3)Dy(L(Pr))(NO(3))(3)(MeOH)(3)] confirmed that the large Ln(III) ion is bound in the central O(6) site and the three square pyramidal Cu(II) ions in the outer N(2)O(2) sites (apical donor either nitrate anion or methanol molecule) of the Schiff base macrocycle. Only the structurally characterized Cu(3)Tb complex, reported earlier, is a single-molecule magnet (SMM): the other 12 complexes do not exhibit an out-of-phase ac susceptibility signal or hysteresis of magnetization in a dc field. Ab initio calculations allowed us to rationalize the observed magnetic properties, including the significant impact of subtle chemical modification on SMM behavior. Broken-symmetry density functional theory (BS-DFT) calculations show there is a subtle structural balance as to whether the Cu···Cu exchange coupling is ferro- or antiferromagnetic. Of the family of 13 magnetically characterized tetranuclear Cu(II)(3)Ln(III) macrocyclic complexes prepared, only the Tb(III) complex is an SMM: the theoretical reasons for this are discussed.

  16. Chlorine and temperature directed self-assembly of Mg-Ru2(ii,iii) carbonates and particle size dependent magnetic properties.

    PubMed

    Yang, Jian-Hui; Cheng, Ru-Mei; Jia, Yan-Yan; Jin, Jin; Yang, Bing-Bing; Cao, Zhi; Liu, Bin

    2016-02-21

    A series of heterometallic magnesium diruthenium(ii,iii) carbonates, namely K{Mg(H2O)6}2[Ru2(CO3)4Cl2]·4H2O (1), K2[{Mg(H2O)4}2Ru2(CO3)4(H2O)Cl]Cl2·2H2O (2), K[Mg(H2O)5Ru2(CO3)4]·5H2O (3) and K[Mg(H2O)4Ru2(CO3)4]·H2O (4), were synthesized from the reaction of Ru2(CO3)4(3-) and Mg(2+) in aqueous solution. Compound 1 is composed of ionic crystals with the Ru2(CO3)4Cl2(5-) : Mg(H2O)6(2+) : K(+) ratio of 1 : 2 : 1. Compound 2 consists of two dimensional layer structures, in which each octahedral environment Mg(H2O)4(2+) bonds to two [Ru2(CO3)4(H2O)Cl](4-) units in a cis manner forming a neutral square-grid layer {Mg(H2O)4Ru2(CO3)4(H2O)Cl}n. For compound 3, one water molecule of each Mg(H2O)6(2+) is substituted by an oxygen atom of Ru2(CO3)4(3-) forming [Mg(H2O)5Ru2(CO3)4](-), and then the neighboring Ru2 dimers are linked together by the rest of the two oxygen atoms of carbonates to form a layer structure {Mg(H2O)5Ru2(CO3)4}n(n-). In compound 4, the neighboring squared-grid layers {Ru2(CO3)4}n(3n-), similar to those in compound 3, are linked by each octahedral environment Mg(H2O)4(2+) in a cis manner forming the three-dimensional network {Mg(H2O)4Ru2(CO3)4}n(n-). Compound 3 shows ferromagnetic coupling between Ru2 dimers, and a long-range ordering is observed below 3.8 K. Compound 4 displays a magnetic ordering below 3.5 K, and a systematic study of the size-dependent magnetic properties of compound 4 reveals that the coercivity of 4 has been improved with reduced sample particle size from the micrometer to the nanometer scale.

  17. Synthetic control to achieve lanthanide(III)/pyrimidine-4,6-dicarboxylate compounds by preventing oxalate formation: structural, magnetic, and luminescent properties.

    PubMed

    Cepeda, Javier; Balda, Rolindes; Beobide, Garikoitz; Castillo, Oscar; Fernández, Joaquín; Luque, Antonio; Pérez-Yáñez, Sonia; Román, Pascual

    2012-07-16

    Control over the synthetic conditions in many metal/diazinedicarboxylato systems is crucial to prevent oxalate formation, since dicarboxylato ligands easily undergo degradation in the presence of metal salts. We report here an efficient route to obtain oxalato-free compounds for the lanthanide/pyrimidine-4,6-dicarboxylato (pmdc) system on the basis of the reaction temperature and nonacidic pH or oxygen free atmosphere. Two different crystal architectures have been obtained: {[Ln(μ-pmdc)(1.5)(H(2)O)(3)]·xH(2)O}(n) (1-Ln) and {[Ln(2)(μ(4)-pmdc)(2)(μ-pmdc)(H(2)O)(2)]·H(2)O}(n) (2-Ln) with Ln(III) = La-Yb, except Pm. Both crystal structures are built from distorted two-dimensional honeycomb networks based on the recurrent double chelating mode established by the pmdc. In compounds 1-Ln, the tricapped trigonal prismatic coordination environment of the lanthanides is completed by three water molecules, precluding a further increase in the dimensionality. Crystallization water molecules are arranged in the interlamellar space, giving rise to highly flexible supramolecular clusters that are responsible for the modulation found in compound 1-Gd. Two of the coordinated water molecules are replaced by nonchelating carboxylate oxygen atoms of pmdc ligands in compounds 2-Ln, joining the metal-organic layers together and thus providing a compact three-dimensional network. The crystal structure of the compounds is governed by the competition between two opposing factors: the ionic size and the reaction temperature. The lanthanide contraction rejects the sterically hindered coordination geometries whereas high-temperature entropy driven desolvation pathway favors the release of solvent molecules leading to more compact frameworks. The characteristic luminescence of the Nd, Eu, and Tb centers is improved when moving from 1-Ln to 2-Ln compounds as a consequence of the decrease of the O-H oscillators. The magnetic properties of the compounds are dominated by the spin

  18. Synthesis, Crystal Structures, and Magnetic Properties of Two Novel Cyanido-Bridged Heterotrimetallic {Cu(II)Mn(II)Cr(III)} Complexes.

    PubMed

    Alexandru, Maria-Gabriela; Visinescu, Diana; Shova, Sergiu; Andruh, Marius; Lloret, Francesc; Julve, Miguel

    2017-02-20

    The self-assembly process between the heteroleptic [Cr(III)(phen)(CN)4](-) and [Cr(III)(ampy)(CN)4](-) metalloligands and the heterobimetallic {Cu(II)(valpn)Mn(II)}(2+) tecton afforded two heterotrimetallic complexes of formula [{Cu(II)(valpn)Mn(II)(μ-NC)2Cr(III)(phen)(CN)2}2{(μ-NC)Cr(III)(phen)(CN)3}2]·2CH3CN (1) and {[Cu(II)(valpn)Mn(II)(μ-NC)2Cr(III)(ampy)(CN)2]2·2CH3CN}n (2) [phen = 1,10-phenanthroline, ampy = 2-aminomethylpyridine, and H2valpn = 1,3-propanedyilbis(2-iminomethylene-6-methoxyphenol)]. The crystal structure of 1 consists of neutral Cu(II)2Mn(II)2Cr(III)4 octanuclear units, where two [Cr(phen)(CN)4](-) anions act as bis-monodentate ligands through cyanide groups toward two manganese(II) ions from two [Cu(II)(valpn)Mn(II)](2+) units to form a [{Cu(valpn)Mn}2Cr2(CN)4](6+) square motif. Two [Cr(phen)(CN)4](-) pendant anions in 1 are bound to the copper(II) ions with cis-trans geometry with respect to the bridging [Cr(phen)(CN)4](-) anion. Compound 2 is a sheet-like coordination polymer, where chains constituted by {Cr(III)(ampy)(CN)4} spacers act as bis-monodentate ligands toward the manganese(II) ions belonging to the {Cu(II)(valpn)Mn(II)} nodes, which are interlinked by another {Cr(III)(ampy)(CN)4} unit that acts as a bridge between the copper(II) and manganese(II) ions of adjacent chains. Magnetic susceptibility measurements in the temperature range of 1.9-300 K were performed for 1 and 2. An overall antiferromagnetic behavior is observed for 1, the ground spin state being described by a spin triplet from the square motif plus two magnetically isolated spin triplets from the two peripheral chromium(III) ions. Ferrimagnetic chains with interacting spins 1/2 (resulting spin of the trimetallic {Cu(II)(valpn)Mn(II)(μ-NC)Cr(III)} fragment) and 3/2 (spin from the bis-monodentate [Cr(III)(ampy)(CN)4](-) with weak interchain ferromagnetic interactions across the cyanide bridge between the chromium(III) and the copper(II) ion from adjacent chains [

  19. Single transistor latch phenomenon in junctionless transistors

    NASA Astrophysics Data System (ADS)

    Singh Parihar, Mukta; Ghosh, Dipankar; Kranti, Abhinav

    2013-05-01

    In this work, we report on the single transistor latch phenomenon in junctionless transistors. In the latch condition, the device is unable to turn-off despite a reduction in gate bias. It is shown that impact ionization induced latch condition can occur due to an increase in drain bias, silicon film thickness, gate oxide thickness, and doping concentration. The latch phenomenon is explained in terms of generation-recombination rates, electrostatic potential, electric field distribution and product of current density and electric field (J.E). As latch condition is undesirable for dynamic memory applications, the work highlights the significance of (J.E) as a performance metric to avoid the junctionless transistor being driven into the latch mode.

  20. Introduction to the B[e] Phenomenon

    NASA Astrophysics Data System (ADS)

    Oudmaijer, R. D.; Miroshnichenko, A. S.

    2017-02-01

    In this contribution we introduce the topic of this workshop with a brief history of studies of objects with the B[e] phenomenon, including its discovery and evolution of our understanding of the phenomenon. We will also review the most prominent results on selected objects published prior to the previous B[e] star conference in 2005. These include the discovery of B[e] supergiants in the Magellanic Clouds, detection of maser and laser lines in the spectrum of MWC 349A, studies of η Carinae, and a few more. This talk is planned to set up the stage for discussion of more recent results that will be presented at the conference.

  1. Ringing phenomenon of the fiber ring resonator.

    PubMed

    Ying, Diqing; Ma, Huilian; Jin, Zhonghe

    2007-08-01

    A resonator fiber-optic gyro (R-FOG) is a high-accuracy inertial rotation sensor based on the Sagnac effect. A fiber ring resonator is the core sensing element in the R-FOG. When the frequency of the fiber ring resonator input laser is swept linearly with time, ringing of the output resonance curve is observed. The output field of the fiber ring resonator is derived from the superposition of the light transmitted through the directional coupler directly and the multiple light components circulated in the fiber ring resonator when the frequency of the laser is swept. The amplitude and phase of the output field are analyzed, and it is found that the difference in time for different light components in the fiber ring resonator to reach a point of destructive interference causes the ringing phenomenon. Finally the ringing phenomenon is observed in experiments, and the experimental results agree with the theoretical analysis well.

  2. The phenomenon of fluorescence in immunosensors.

    PubMed

    Kłos-Witkowska, Aleksandra

    2016-01-01

    The phenomenon of fluorescence in immunosensors is described in this paper. Both structure and characteristics of biosensors and immunosensors are presented. Types of immunosensors and the response of bioreceptor layers to the reaction with analytes as well as measurements of electrochemical, piezoelectric and optical parameters in immunosensors are also presented. In addition, detection techniques used in studies of optical immunosensors based on light-matter interactions (absorbance, reflectance, dispersion, emission) such as: UV/VIS spectroscopy, reflectometric interference spectroscopy (RIfs), surface plasmon resonance (SPR), optical waveguide light-mode spectroscopy (OWLS), fluorescence spectroscopy. The phenomenon of fluorescence in immunosensors and standard configurations of immunoreactions between an antigen and an antibody (direct, competitive, sandwich, displacement) is described. Fluorescence parameters taken into account in analyses and fluorescence detection techniques used in research of immunosensors are presented. Examples of immunosensor applications are given.

  3. Phase transition phenomenon: A compound measure analysis

    NASA Astrophysics Data System (ADS)

    Kang, Bo Soo; Park, Chanhi; Ryu, Doojin; Song, Wonho

    2015-06-01

    This study investigates the well-documented phenomenon of phase transition in financial markets using combined information from both return and volume changes within short time intervals. We suggest a new measure for the phase transition behaviour of markets, calculated as a return distribution conditional on local variance in volume imbalance, and show that this measure successfully captures phase transition behaviour under various conditions. We analyse the intraday trade and quote dataset from the KOSPI 200 index futures, which includes detailed information on the original order size and the type of each initiating investor. We find that among these two competing factors, the submitted order size yields more explanatory power on the phenomenon of market phase transition than the investor type.

  4. The cutoff phenomenon in finite Markov chains.

    PubMed Central

    Diaconis, P

    1996-01-01

    Natural mixing processes modeled by Markov chains often show a sharp cutoff in their convergence to long-time behavior. This paper presents problems where the cutoff can be proved (card shuffling, the Ehrenfests' urn). It shows that chains with polynomial growth (drunkard's walk) do not show cutoffs. The best general understanding of such cutoffs (high multiplicity of second eigenvalues due to symmetry) is explored. Examples are given where the symmetry is broken but the cutoff phenomenon persists. PMID:11607633

  5. Spectral and thermodynamic properties of Ag(I), Au(III), Cd(II), Co(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(IV), and Zn(II) binding by methanobactin from Methylosinus trichosporium OB3b.

    PubMed

    Choi, Dong W; Do, Young S; Zea, Corbin J; McEllistrem, Marcus T; Lee, Sung-W; Semrau, Jeremy D; Pohl, Nicola L; Kisting, Clint J; Scardino, Lori L; Hartsel, Scott C; Boyd, Eric S; Geesey, Gill G; Riedel, Theran P; Shafe, Peter H; Kranski, Kim A; Tritsch, John R; Antholine, William E; DiSpirito, Alan A

    2006-12-01

    Methanobactin (mb) is a novel chromopeptide that appears to function as the extracellular component of a copper acquisition system in methanotrophic bacteria. To examine this potential physiological role, and to distinguish it from iron binding siderophores, the spectral (UV-visible absorption, circular dichroism, fluorescence, and X-ray photoelectron) and thermodynamic properties of metal binding by mb were examined. In the absence of Cu(II) or Cu(I), mb will bind Ag(I), Au(III), Co(II), Cd(II), Fe(III), Hg(II), Mn(II), Ni(II), Pb(II), U(VI), or Zn(II), but not Ba(II), Ca(II), La(II), Mg(II), and Sr(II). The results suggest metals such as Ag(I), Au(III), Hg(II), Pb(II) and possibly U(VI) are bound by a mechanism similar to Cu, whereas the coordination of Co(II), Cd(II), Fe(III), Mn(II), Ni(II) and Zn(II) by mb differs from Cu(II). Consistent with its role as a copper-binding compound or chalkophore, the binding constants of all the metals examined were less than those observed with Cu(II) and copper displaced other metals except Ag(I) and Au(III) bound to mb. However, the binding of different metals by mb suggests that methanotrophic activity also may play a role in either the solubilization or immobilization of many metals in situ.

  6. Thiol-functionalized Fe3O4/SiO2 microspheres with superparamagnetism and their adsorption properties for Au(III) ion separation

    NASA Astrophysics Data System (ADS)

    Peng, Xiangqian; Zhang, Wei; Gai, Ligang; Jiang, Haihui; Tian, Yan

    2016-08-01

    Thiol-functionalized Fe3O4/SiO2 microspheres (Fe3O4/SiO2-SH) with high saturation magnetization (69.3 emu g-1), superparamagnetism, and good dispersibility have been prepared by an ethylene glycol reduction method in combination with a modified Stöber method. The as-prepared composite magnetic spheres are characterized with fourier transform infrared spectroscopy (FT-IR), zeta potential, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and superconducting quantum interference magnetometer, and tested in separation of Au(III) ions from aqueous solutions. The data for Au(III) adsorption on Fe3O4/SiO2-SH are analyzed with the Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm models, and the pseudo-first-order, pseudo-second-order, and intraparticle diffusion kinetics models. The adsorption behaviors of Au(III) on Fe3O4/SiO2-SH follow the Langmuir isotherm model, and the adsorption process conforms to the pseudo-second-order kinetic model. The maximum adsorption capacity of Au(III) on Fe3O4/SiO2-SH is 43.7 mg g-1. Acetate anions play an important role yet Cu(II) ions have little interference in the adsorption of Au(III) on the adsorbent. A satisfactory recovery percentage of 89.5% is acquired by using an eluent with 1 M thiourea and 5% HCl, although thiols have a high affinity to Au(III) ions based on the hard-soft acid-base (HSAB) theory by Pearson.

  7. Characterization and Properties of Activated Carbon Prepared from Tamarind Seeds by KOH Activation for Fe(III) Adsorption from Aqueous Solution.

    PubMed

    Mopoung, Sumrit; Moonsri, Phansiri; Palas, Wanwimon; Khumpai, Sataporn

    2015-01-01

    This research studies the characterization of activated carbon from tamarind seed with KOH activation. The effects of 0.5 : 1-1.5 : 1 KOH : tamarind seed charcoal ratios and 500-700°C activation temperatures were studied. FTIR, SEM-EDS, XRD, and BET were used to characterize tamarind seed and the activated carbon prepared from them. Proximate analysis, percent yield, iodine number, methylene blue number, and preliminary test of Fe(III) adsorption were also studied. Fe(III) adsorption was carried out by 30 mL column with 5-20 ppm Fe(III) initial concentrations. The percent yield of activated carbon prepared from tamarind seed with KOH activation decreased with increasing activation temperature and impregnation ratios, which were in the range from 54.09 to 82.03 wt%. The surface functional groups of activated carbon are O-H, C=O, C-O, -CO3, C-H, and Si-H. The XRD result showed high crystallinity coming from a potassium compound in the activated carbon. The main elements found in the activated carbon by EDS are C, O, Si, and K. The results of iodine and methylene blue adsorption indicate that the pore size of the activated carbon is mostly in the range of mesopore and macropore. The average BET pore size and BET surface area of activated carbon are 67.9764 Å and 2.7167 m(2)/g, respectively. Finally, the tamarind seed based activated carbon produced with 500°C activation temperature and 1.0 : 1 KOH : tamarind seed charcoal ratio was used for Fe(III) adsorption test. It was shown that Fe(III) was adsorbed in alkaline conditions and adsorption increased with increasing Fe(III) initial concentration from 5 to 20 ppm with capacity adsorption of 0.0069-0.019 mg/g.

  8. Novel polycarboxylated EDTA-type cyclodextrins as ligands for lanthanide binding: study of their luminescence, relaxivity properties of Gd(iii) complexes, and PM3 theoretical calculations.

    PubMed

    Maffeo, Davide; Lampropoulou, Maria; Fardis, Michael; Lazarou, Yannis G; Mavridis, Irene M; Mavridou, Despoina A I; Urso, Elena; Pratsinis, Harris; Kletsas, Dimitris; Yannakopoulou, Konstantina

    2010-04-21

    Novel -type cyclodextrin (CD) derivatives, , and , bearing 6, 7 and 8 bis(carboxymethyl)amino (iminodiacetic acid) groups, respectively, were prepared, and their complexation with Eu(iii), Tb(iii) and Gd(iii) ions was studied. Luminescence titrations and mass spectrometry showed formation of multimetal complexes ( 2 to 3, mainly 3 and exactly 4 metal ions), whereas luminescence lifetime measurements revealed the presence of exchangeable water molecules. Semiempirical quantum mechanical calculations, performed by the PM3 method and assessed by DFT calculations on model ligands, indicated efficient multi-metal complexation, in agreement with the experiment. The structures showed coordination of the metal ions in the outer primary side of the CDs via 4 carboxylate O atoms, 2 N atoms and a glucopyranose O atom per metal ion. Coordination of water molecules was also predicted, in accordance with experimental results. Calculated bond lengths and angles were in agreement with literature experimental values of lanthanide complexes. Calculated energies showed that complex stability decreases in the order > > . (1)H NMR molecular relaxivity measurements for the Gd(iii) complexes of , or in water afforded values 4 to 10 times higher than the relaxivity of a commercial contrast agent at 12 MHz, and 6 to 20 times higher at 100 MHz. Solutions of and Gd(iii) complexes in human blood plasma displayed relaxivity values at 100 MHz 7 and 12 times, respectively, higher than the commercial agent. MTT tests of the Gd(iii) complexes using human skin fibroblasts did not show toxicity. Attempts to supramolecularly sensitize the luminescence of the lanthanide complexes using various aromatic CD guests were ineffective, evidently due to large guest-metal distances and inefficient inclusion. The described lanthanide complexes, could be useful as contrast agents in MRI.

  9. Mechanisms of the warm-up phenomenon.

    PubMed

    Tomai, F; Crea, F; Danesi, A; Perino, M; Gaspardone, A; Ghini, A S; Cascarano, M T; Chiariello, L; Gioffrè, P A

    1996-07-01

    The warm-up phenomenon, described in patients with coronary artery disease, refers to the improved performance following a first exercise test. The aim of this study was to investigate the causes of the warm-up phenomenon. Fifteen patients with coronary artery disease and positive exercise test were enrolled. Patients were off treatment throughout the study. They underwent two consecutive treadmill exercise tests according to the Bruce protocol, with a recovery period of 10 min to re-establish baseline conditions. A third exercise test was then performed 2 h later. Before the onset of ischaemia, the rate-pressure product for a similar degree of workload was similar during the first and second exercise test, while it was lower during the third test (P < 0.05). Time to 1.5 mm ST-segment depression during the second and third exercise test was greater than during the first test (454 +/- 133 and 410 +/- 161 vs 354 +/- 127 s, P < 0.01, respectively). Similarly, the time to anginal pain onset was increased during the second and third exercise tests, compared to the first test (356 +/- 208 and 310 +/- 203 vs 257 +/- 204 s, P < 0.01, respectively). In contrast, rate-pressure product at 1.5 mm ST-segment depression during the second test was higher than that during the first test (232 +/- 47 vs 210 +/- 39 beats.min-1.mmHg.10(2), P < 0.01), while in the third test it was similar to that during the first (209 +/- 43 beats.min-1.mmHg.10(2), P = ns). The warm-up phenomenon observed a few minutes after exercise is characterized by an increase of both time to ischaemia and ischaemic threshold; this adaptation to ischaemia may be due to an improvement of myocardial perfusion or to preconditioning. Conversely, the warm-up phenomenon observed a few hours after repeated exercise is characterized by an increase of time to ischaemia but not of ischaemic threshold and is caused by a slower increase of cardiac workload. Thus, the mechanisms of the warm-up phenomenon may be different

  10. Isolation: analysis and properties of three bradykinin-potentiating peptides (BPP-II, BPP-III, and BPP-V) from Bothrops neuwiedi venom.

    PubMed

    Ferreira, L A; Galle, A; Raida, M; Schrader, M; Lebrun, I; Habermehl, G

    1998-04-01

    In the course of systematic investigations on low-molecular-weight compounds from the venom of Crotalidae and Viperidae, we have isolated and characterized at least three bradykinin-potentiating peptides (BPP-II, BPP-III, and BPP-V) from Bothrops neuwiedi venom by gel filtration on Sephadex G-25 M, Sephadex G-10 followed by HPLC. The peptides showed bradykinin-potentiating action on isolated guinea-pig ileum, for which the BPP-V was more active than of BPP-II, and BPP-III, rat arterial blood pressure, and a relevant angiotensin-converting enzyme (ACE) competitive inhibiting activity. The kinetic studies showed a Ki of the order of 9.7 x 10(-3) microM to BPP-II, 7 x 10(-3) microM to BPP-III, and 3.3 x 10(-3) microM to BPP-V. The amino acid sequence of the BPP-III has been determined to be pGlu-Gly-Gly-Trp-Pro-Arg-Pro-Gly-Pro-Glu-Ile-Pro-Pro, and the amino acid compositions of the BPP-II and BPP-V by amino acid analysis were 2Glu-2Gly-1Arg-4Pro-1Ile and 2Glu-2Gly-1Ser-3Pro-2Val-1Ile, with molecular weight of 1372, 1046, and 1078, respectively.

  11. Synthesis, spectroscopic, photoluminescence properties and biological evaluation of novel Zn(II) and Al(III) complexes of NOON tetradentate Schiff bases.

    PubMed

    Abdel Aziz, Ayman A; Badr, Ibrahim H A; El-Sayed, Ibrahim S A

    2012-11-01

    Novel mononuclear Zn(II) and Al(III) complexes were synthesized from the reactions of Zn(OAc)(2).2H(2)O and anhydrous AlCl(3) with neutral N2O2 donor tetradentate Schiff bases; N,N'bis(salicylaldehyde)4,5-dimethyl-1,2-phenylenediamine (H(2)L(1)) and N,N'bis(salicylaldehyde)4,5-dichloro-1,2-phenylenediamine (H(2)L(2)). The new complexes were fully characterized by using micro analyses (CHN), FT-IR, (1)H NMR, UV-Vis spectra and thermal analysis. The analytical data have been showed that, the stoichiometry of the complexes is 1:1. Spectroscopic data suggested tetrahedral and square pyramidal geometries for Zn(II) and Al(III) complexes, respectively. The synthesized Zn(II), and Al(III) complexes exhibited intense fluorescence emission in the visible region upon UV-excitation in methylene chloride solution at ambient temperature. This high fluorescence emission was assigned to the strong coordination of the ligands to the small and the highly charged Zn(II) and Al(III) ions. Such strong coordination seems to extend the π-conjugation of the complexes. Thermal analysis measurements indicated that the complexes have good thermal stability. As a potential application the biological activity (e.g., antimicrobial action) of the prepared ligands and complexes was assessed by in-vitro testing of their effect on the growth of various strains of bacteria and fungi.

  12. Axial thiophenolate coordination on diiron(III)bisporphyrin: influence of heme-heme interactions on structure, function and electrochemical properties of the individual heme center.

    PubMed

    Sil, Debangsu; Tuglak Khan, Firoz Shah; Rath, Sankar Prasad

    2014-11-17

    The binding of a series of substituted thiophenols as axial ligands on a highly flexible ethane-bridged diiron(III)bisporphyrin framework has been investigated as a model of diheme proteins. Spectroscopic characterization reveals a high-spin (S = 5/2) state of iron for all of the pentacoordinate thiophenolato complexes. In the UV-visible spectra of the complexes, the positions of the Soret and band I have been found to be dependent on the pKa of thiophenols. The alternating shift pattern, which has opposite sign of the chemical shifts for meta- vs. ortho- and para-protons in the (1)H NMR spectra, is attributed to negative and positive spin densities, respectively, on thiophenolate carbon atoms and is indicative of π-spin delocalization to the bound thiophenolate ligand. The Fe(III)/Fe(II) redox couple of the complexes bears a linear relationship with the pKa of thiophenol and is found to be positively shifted with decreasing pKa. The effect of the electronic nature of the substituent on the thiophenolate ring has also been demonstrated in which a large potential range of 540 mV was observed (in contrast to the value of only 270 mV in case of monoheme analogues) for the Fe(III)/Fe(II) redox couple on going from monoheme to diheme and is attributed to the interheme interaction. Also, the Fe(III)/Fe(II) redox potential of the thiophenolato complexes has been found to be more positively shifted compared to their phenolato analogues, which was further supported by DFT calculation. The addition of another thiophenol at the sixth axial position of the five-coordinate thiophenolato complex causes a change in iron spin from high (S = 5/2) to low (S = 1/2) along with a large positive shift of 490 mV for the Fe(III)/Fe(II) redox couple.

  13. Regioselective aromatic substitution reactions of cyclometalated Ir(III) complexes: synthesis and photochemical properties of substituted Ir(III) complexes that exhibit blue, green, and red color luminescence emission.

    PubMed

    Aoki, Shin; Matsuo, Yasuki; Ogura, Shiori; Ohwada, Hiroki; Hisamatsu, Yosuke; Moromizato, Shinsuke; Shiro, Motoo; Kitamura, Masanori

    2011-02-07

    In this manuscript, the regioselective halogenation, nitration, formylation, and acylation of Ir(tpy)(3) and Ir(ppy)(3) (tpy = 2-(4'-tolyl)pyridine and ppy = 2-phenylpyridine) and the subsequent conversions are described. During attempted bromination of the three methyl groups in fac-Ir(tpy)(3) using N-bromosuccinimide (NBS) and benzoyl peroxide (BPO), three protons at the 5'-position (p-position with respect to the C-Ir bond) of phenyl rings in tpy units were substituted by Br, as confirmed by (1)H NMR spectra, mass spectra, and X-ray crystal structure analysis. It is suggested that such substitution reactions of Ir complexes proceed via an ionic mechanism rather than a radical mechanism. UV-vis and luminescence spectra of the substituted Ir(III) complexes are reported. The introduction of electron-withdrawing groups such as CN and CHO groups at the 5'-position of tpy induces a blue shift of luminescence emission to about 480 nm, and the introduction of electron-donating groups such as an amino group results in a red shift to about 600 nm. A reversible change of emission for the 5'-amino derivative of Ir(tpy)(3), Ir(atpy)(3), between red and green occurs upon protonation and deprotonation.

  14. Effect of Ligand Substitution around the Dy(III) on the SMM Properties of Dual-Luminescent Zn-Dy and Zn-Dy-Zn Complexes with Large Anisotropy Energy Barriers: A Combined Theoretical and Experimental Magnetostructural Study.

    PubMed

    Costes, Jean Pierre; Titos-Padilla, Silvia; Oyarzabal, Itziar; Gupta, Tulika; Duhayon, Carine; Rajaraman, Gopalan; Colacio, Enrique

    2016-05-02

    magnetostructural data for 1-3 has allowed us to draw some conclusions about the influence of ligand substitution around the Dy(III) on the SMM properties. Finally, these SMMs exhibit metal- and ligand-centered dual emissions in the visible region, and, therefore, they can be considered as magnetoluminescent bifunctional molecular materials.

  15. Experimental investigations of the ozone zero phenomenon

    NASA Astrophysics Data System (ADS)

    Murayama, K.; Matsumura, N.; Taguchi, M.; Katoh, Y.; Teranishi, K.; Suzuki, S.; Itoh, H.

    2009-08-01

    An experimental study is carried out to clarify the mechanism of the ozone zero phenomenon. Temporal variations of both the discharge characteristics and the metallic electrode surface in the ozone generator are investigated by the Lissajous figure method and Auger electron spectroscopy (AES), respectively. The AES results suggest that a number of oxygen atoms penetrate into the stainless-steel electrode owing to the exposure to ozone. Such a surface change would result in the temporal variation of the discharge characteristics of the generator.

  16. Is iloprost effective in secondary Raynaud's phenomenon?

    PubMed

    Lustig, Nicole; Rada, Gabriel

    2015-03-09

    Patients with systemic sclerosis frequently have Raynaud's phenomenon and digital ischemic ulcers. Iloprost, a synthetic prostacyclin analogue, may be effective in these cases. Searching in Epistemonikos database, which is maintained by screening 20 databases, we identified three systematic reviews including seven randomized trials. We combined the evidence using meta-analysis and generated a summary of findings table following the GRADE approach. We concluded iloprost may lead to little or no difference in the frequency or severity of secondary Raynaud, and it is associated to adverse effects and important costs.

  17. Impact process: an important geological phenomenon.

    PubMed

    Skala, R

    1996-01-01

    The impact process was for a long period of time, even after a wider acceptance among the geological community, considered to be a marginal phenomenon in the Earth sciences. The first decade or two have showed an importance of the process itself and consequent events only too clearly. The present paper is a review describing the history and development of the impact hypothesis, structure and origin of impact craters, influence of huge impacts on the living environment and other aspects of the impact process from the point of view of geology s.l.

  18. Storage-recovery phenomenon in magnonic crystal.

    PubMed

    Chumak, A V; Vasyuchka, V I; Serga, A A; Kostylev, M P; Tiberkevich, V S; Hillebrands, B

    2012-06-22

    The phenomenon of coherent wave trapping and restoration is demonstrated experimentally in a magnonic crystal. Unlike the conventional scheme used in photonics, the trapping occurs not due to the deceleration of the incident wave when it enters the periodic structure but due to excitation of the quasinormal modes of the artificial crystal. This excitation occurs at the group velocity minima of the decelerated wave in narrow frequency regions near the edges of the band gaps of the crystal. The restoration of the traveling wave is implemented by means of phase-sensitive parametric amplification of the stored mode.

  19. Synthesis, crystal structures and magnetic properties of cyanide- and phenolate-bridged [M(III)NiII]2 tetranuclear complexes (M=Fe and Cr).

    PubMed

    Toma, Liviu; Toma, Luminita Marilena; Lescouëzec, Rodrigue; Armentano, Donatella; De Munno, Giovanni; Andruh, Marius; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2005-04-21

    The binuclear complex NiII2L(H2O)2(ClO4)2(1) and the neutral tetranuclear bimetallic compounds [{M(III)(phen)(CN)4}2{NiII2L(H2O)2}].2CH3CN with M=Fe (2) and Cr (3)[H2L=11,23-dimethyl-3,7,15,19-tetraazatricyclo[19.3.1.1(9,13)]hexacosa-2,7,9,11,13(26),14,19,21(25),22,24-decaene-25,26-diol] have been synthesized and the structures of and determined by single crystal X-ray diffraction. and are isostructural compounds whose structure is made up of centrosymmetric binuclear cations [Ni2(L)(H2O)2]2+ and two peripheral [M(phen)(CN)4]- anions [M=Fe (2) and Cr (3)] acting as monodentate ligands towards the nickel atoms through one of their four cyanide nitrogen atoms. The environment of the metal atoms in 2 and 3 is six-coordinated: two phen-nitrogen and four cyanide-carbon atoms at the iron and chromium atoms and a water molecule, one cyanide-nitrogen and two phenolate-oxygens and two imine-nitrogens from the binucleating ligand L2- at the nickel atom build distorted octahedral surroundings. The values of the FeNi and CrNi separations through the single cyanide bridge are 5.058(1) and 5.174(2)A respectively, whereas the Ni-Ni distances across the double phenolate bridge are 3.098(2)(2) and 3.101(1) A (3). The magnetic properties of have been investigated in the temperature range 1.9-290 K. The magnetic behaviour of corresponds to that of an antiferromagnetically coupled nickel(II) dimer with J=-61.0(1) cm-1, the Hamiltonian being defined as H=-J S(A).S(B). An overall antiferromagnetic behaviour is observed for and with a low-lying singlet spin state. The values of the intramolecular magnetic couplings are J(Fe-Ni)=+17.4(1) cm-1 and J(Ni-Ni(a))=-44.4(1) cm-1 for and J(Cr-Ni)=+11.8(1) cm-1 and J(Ni-Ni(a))=-44.6(1) cm-1 for [H=-J(M-Ni)(S(M).S(Ni)+S(Ma).S(Nia))-J(Ni-Nia)S(Ni)S(Nia)]. Theoretical calculations using methods based on density functional theory (DFT) have been employed on in order to analyze the efficiency of the exchange pathways involved and also to substantiate

  20. Characterization and Properties of Activated Carbon Prepared from Tamarind Seeds by KOH Activation for Fe(III) Adsorption from Aqueous Solution

    PubMed Central

    Mopoung, Sumrit; Moonsri, Phansiri; Palas, Wanwimon; Khumpai, Sataporn

    2015-01-01

    This research studies the characterization of activated carbon from tamarind seed with KOH activation. The effects of 0.5 : 1–1.5 : 1 KOH : tamarind seed charcoal ratios and 500–700°C activation temperatures were studied. FTIR, SEM-EDS, XRD, and BET were used to characterize tamarind seed and the activated carbon prepared from them. Proximate analysis, percent yield, iodine number, methylene blue number, and preliminary test of Fe(III) adsorption were also studied. Fe(III) adsorption was carried out by 30 mL column with 5–20 ppm Fe(III) initial concentrations. The percent yield of activated carbon prepared from tamarind seed with KOH activation decreased with increasing activation temperature and impregnation ratios, which were in the range from 54.09 to 82.03 wt%. The surface functional groups of activated carbon are O–H, C=O, C–O, –CO3, C–H, and Si–H. The XRD result showed high crystallinity coming from a potassium compound in the activated carbon. The main elements found in the activated carbon by EDS are C, O, Si, and K. The results of iodine and methylene blue adsorption indicate that the pore size of the activated carbon is mostly in the range of mesopore and macropore. The average BET pore size and BET surface area of activated carbon are 67.9764 Å and 2.7167 m2/g, respectively. Finally, the tamarind seed based activated carbon produced with 500°C activation temperature and 1.0 : 1 KOH : tamarind seed charcoal ratio was used for Fe(III) adsorption test. It was shown that Fe(III) was adsorbed in alkaline conditions and adsorption increased with increasing Fe(III) initial concentration from 5 to 20 ppm with capacity adsorption of 0.0069–0.019 mg/g. PMID:26689357

  1. [Fe(bipy)(CN)(4)](-) as a versatile building block for the design of heterometallic systems: synthesis, crystal structure, and magnetic properties of PPh(4)[Fe(III)(bipy)(CN)(4)] x H(2)O, [[Fe(III)(bipy)(CN)(4)](2)M(II)(H(2)O)(4)] x 4H(2)O, and [[Fe(III)(bipy)(CN)(4)](2)Zn(II)] x 2H(2)O [bipy = 2,2'-Bipyridine; M = Mn and Zn].

    PubMed

    Lescouëzec, Rodrigue; Lloret, Francesc; Julve, Miguel; Vaissermann, Jacqueline; Verdaguer, Michel

    2002-02-25

    (1) and 5.028(1), 5.076(1), and 5.176(1) A at Fe(2). The magnetic properties of 1-3 have been investigated in the temperature range 2.0-300 K. 1 is a low-spin iron(III) complex with an important orbital contribution. The magnetic properties of 3 correspond to the sum of two magnetically isolated spin triplets, the antiferromagnetic coupling between the low-spin iron(III) centers through the -CN-Zn-NC- bridging skeleton (iron-iron separation larger than 10 A) being very weak. More interestingly, 2 exhibits a significant intramolecular antiferromagnetic interaction between the central spin sextet and peripheral spin doublets, leading to a low-lying spin quartet.

  2. Association of europium(III), americium(III), and curium(III) with cellulose, chitin, and chitosan.

    PubMed

    Ozaki, Takuo; Kimura, Takaumi; Ohnuki, Toshihiko; Kirishima, Akira; Yoshida, Takahiro; Isobe, Hiroshi; Francis, Arokiasamy J

    2006-08-01

    The association of trivalent f-elements-Eu(III), Am(III), and Cm(III)--with cellulose, chitin, and chitosan was determined by batch experiments and time-resolved, laser-induced fluorescence spectroscopy (TRLFS). The properties of these biopolymers as an adsorbent were characterized based on speciation calculation of Eu(III). The adsorption study showed that an increase of the ionic strength by NaCl did not affect the adsorption kinetics of Eu(III), Am(III), and Cm(III) for all the biopolymers, but the addition of Na2CO3 significantly delayed the kinetics because of their trivalent f-element complexation with carbonate ions. It also was suggested from the speciation calculation study that all the biopolymers were degraded under alkaline conditions, leading to their masking of the adsorption of Eu(III), Am(III), and Cm(III) on the nondegraded biopolymers. The masking effect was higher for cellulose than for chitin and chitosan, indicating that of the three, cellulose was degraded most significantly in alkaline solutions. Desorption experiments suggested that some portion of the adsorbed Eu(III) penetrated deep into the matrix, being isolated in a cavity-like site. The TRLFS study showed that the coordination environment of Eu(III) is stabilized mainly by the inner spherical coordination in chitin and by the outer spherical coordination in chitosan, with less association in cellulose in comparison to chitin and chitosan. These results suggest that the association of these biopolymers with Eu(III), Am(III), and Cm(III) is governed not only by the affinity of the functional groups alone but also by other factors, such as the macromolecular steric effect. The association of degraded materials of the biopolymers also should be taken into consideration for an accurate prediction of the influence of biopolymers on the migration behavior of trivalent f-elements.

  3. NANOLEAKAGE PHENOMENON ON DEPROTEINIZED HUMAN DENTIN

    PubMed Central

    Duarte, Patrícia de Britto Pereira Garcia; da Silva, Eduardo Moreira

    2007-01-01

    Objective: The purpose of this study was to evaluate the influence of dentin deproteinization on the nanoleakage phenomenon. Material and Methods: Class V cavities were prepared in 12 human molars with cervical margins located in dentin. The cavities were assigned to 2 groups (n=6) according to dentin treatment: Group I - dentin treated in accordance with the manufacturer’s instructions and Group II - dentin treated following the manufacturer’s instructions + 10% NaOCl. Each group was sub-divided into three groups, according to the DBS (dentin bonding system) used: Scotchbond Multi Purpose (SBMP), Prime & Bond NT (PB) and Clearfil SE Bond (SE), which were applied according to manufacturer’s instructions. The cavities were restored with composite resin, and the specimens were immersed in a tracer agent (AgNO3 50%) for 24 h. The teeth were sectioned buccolingually through the center of the restorations, and nanoleakage pattern was evaluated by scanning electron microscopy (SEM) using the backscattered electron image mode. Results: SEM analysis showed different nanoleakage patterns for each DBS. Irrespective of dentin treatments, all SBMP specimens showed nanoleakage. SE did not show any nanoleakage with both dentin treatments used. PB showed nanoleakage within the hybrid layer only in Group I. Conclusions: The influence of dentin deproteinization on the nanoleakage phenomenon was dependent on dentin bonding system formulation and bonding strategies. PMID:19089146

  4. Synthesis, Crystal Structures, Magnetic Properties, and Theoretical Investigation of a New Series of Ni(II)-Ln(III)-W(V) Heterotrimetallics: Understanding the SMM Behavior of Mixed Polynuclear Complexes.

    PubMed

    Vieru, Veacheslav; Pasatoiu, Traian D; Ungur, Liviu; Suturina, Elizaveta; Madalan, Augustin M; Duhayon, Carine; Sutter, Jean-Pascal; Andruh, Marius; Chibotaru, Liviu F

    2016-12-05

    blocking in complexes with fewer axial Ln ions. Further analysis has shown that, in the absence of ZFS on Ni ion, all compounds in the two series (except those containing Y and Gd) would be SMMs. The same situation arises for perfectly axial ZFS on Ni(II) with the main anisotropy axis parallel to the main magnetic axis of Ln(III) ions. In all other cases the ZFS on Ni(II) will worsen the SMM properties. The general conclusion is that the design of efficient SMMs on the basis of such complexes should involve isotropic or weekly anisotropic metal ions, such as Mn(II), Fe(III), etc., along with strongly axial lanthanides.

  5. Room Temperature Ferromagnetic Polymer and the Correlated Anomalous Magnetoresistance Phenomenon

    NASA Astrophysics Data System (ADS)

    Huang, Jinsong; Yang, Bin; Shield, Jeffrey

    2011-03-01

    Organic magnetoresistance (OMAR) has been observed in organic semiconductor devices where resistance can change in a relatively small external magnetic field at room temperature. Since a weak magnetic field is involved, the hyperfine interaction (HFI) is employed to explain OMAR in the reported literatures. None of these issues consider the magnetic properties of the organic semiconductors themselves. However, the we recently discovered that polymer semiconductors, such as poly(3-hexylthiophene) P3HT, can have room temperature (RT) ferromagnetic properties in their crystalline phase and when mixed with phenyl-C61-butyric acid methyl ester (PCBM). Here, we will report the possible correlation between the ferromagnetic property of the P3HT:PCBM and anomalous OMAR phenomenon including the anisotropic and hysteretic OMAR behavior. The magnetic property of the polymer including the anisotropic and photo induced change of magnetism will be also discussed to explore the possible mechanism of the room temperature ferromagnetism.~ This work is partially supported by the NSF MRSEC program at University.

  6. Structural, magnetic and optical properties of an Fe(III) dimer bridged by the meridional planar divergent N,N'-bis(salicyl)hydrazide and its photo- and electro-chemistry in solution.

    PubMed

    Cheaib, Khaled; Martel, David; Clément, Nicolas; Eckes, Fabrice; Kouaho, Stéphanie; Rogez, Guillaume; Dagorne, Samuel; Kurmoo, Mohamedally; Choua, Sylvie; Welter, Richard

    2013-02-07

    {Fe(III)Cl(DMF)(2)}(2)(L) where L is N,N'-bis(salicyl)hydrazide has been synthesized as red crystals and characterized using single-crystal diffraction, infrared and UV-vis spectroscopies, and its magnetic properties studied. The dimeric unit in the structure is formed through the two meridional sets of divergent O, N, O coordinating atoms of the hexacoordinated and quadruply charged ligand. With the presence of the inversion symmetry the Fe atoms are strictly planar with the ligand. The magnetic exchange interaction is found to be antiferromagnetic with a J = -5.98(3) cm(-1) through the rare Fe-N-N-Fe pathway. Irradiation of the FeCl(3)/H(4)L red DMF solution in the visible region of the spectrum resulted in its complete discoloration and from which the unknown colorless salt [Fe(II)(DMF)(6)][Fe(II)Cl(4)] and the neutral ligand have been identified by single crystal diffraction. The UV-visible spectra of FeCl(3), H(4)L and their mixture in DMF solution indicate that the iron complex is the absorbing species and the presence of the free ligand in the irradiated solution suggests that the ligand is potentially acting as a catalyst to the photoreduction of Fe(III) to Fe(II), while electrochemistry points to a mixed-valent (Fe(II)-Fe(III)) intermediate in the process.

  7. The United States pork niche market phenomenon.

    PubMed

    Honeyman, M S; Pirog, R S; Huber, G H; Lammers, P J; Hermann, J R

    2006-08-01

    After the broad industrialization of the US pork industry, there has been a development of niche markets for export and domestic pork; that is, there is a pork niche market phenomenon. The US pork niche market phenomenon is characterized, and 2 of the major markets are explained in detail. With the Midwest's tradition of a diversified family-based agriculture and record low hog prices of the late 1990s, the conditions were conducive for this phenomenon to develop. Pork niche markets utilize various sales methods including Internet sales, local abattoir sales, direct marketing, farmer networks, and targeting to organized groups. In 2003, there were approximately 35 to 40 active pork niche marketing efforts in Iowa. The Berkshire breed is an example of a swine breed that has had a recent resurgence because of niche markets. Berkshire pork is known for tenderness and excellent quality. Berkshire registrations have increased 4-fold in the last 10 yr. One of the larger niche marketers of "natural pork" is Niman Ranch Pork, which has more than 400 farmer-producers and processes about 2,500 pigs weekly. Many US consumers of pork are interested in issues concerning the environment, food safety, pig welfare, and pig farm ownership and structure. These consumers may be willing to pay more for pork from farmers who are also concerned about these issues. Small- and medium-sized swine farmers are active in pork niche markets. Niche markets claim product differentiation by superior or unique product quality and social attributes. Quality attributes include certain swine breeds, and meat quality, freshness, taste or flavor, and tenderness. Social or credence attributes often are claimed and include freedom from antibiotics and growth promotants; local family farm production; natural, organic, outdoor, or bedded rearing; humane rearing; known origin; environmentally friendly production; and the absence of animal by-products in the feed. Niche pork markets and alternative swine

  8. Comparative study of analysis methods in biospeckle phenomenon

    NASA Astrophysics Data System (ADS)

    da Silva, Emerson Rodrigo; Muramatsu, Mikiya

    2008-04-01

    In this work we present a review of main statistical properties of speckle patterns and accomplish a comparative study of the more used methods for analysis and extraction of information from optical grainy. The first and second order space-time statistics are dicussed in an overview perspective. The biospeckle phenomenon has detailed attention, specially in its application on monitoring of activity in tissues. The main techniques used to obtain information from speckle patterns are presented, with special prominence to autocorrelation function, co-occurrence matrices, Fujii's method, Briers' contrast and spatial and temporal contrast analisys (LASCA and LASTCA). An incipient method for analysis, based on the study of sucessive correlations contrast, is introduced. Numerical simulations, using diferent probability density functions for velocities of scatterers, were made with two objectives: to test the analysis methods and to give subsidies for interpretation of in vivo results. Vegetable and animal tissues are investigated, achieving the monitoring of senescence process and vascularization maps on leaves, the accompaniment of fungi contamined fruits, the mapping of activity in flowers and the analisys of healing in rats subjected to abdominal surgery. Experiments using the biospeckle phenomenon in microscopy are carried out. At last, it is evaluated the potentiality of biospeckle as diagnosis tool in chronic vein ulcer cared with low intensity laser therapy and the better analysis methods for each kind of tissue are pointed.

  9. Focusing phenomenon and near-trapped modes of SH waves

    NASA Astrophysics Data System (ADS)

    Chen, Jeng-Tzong; Lee, Jia-Wei; Tu, Ya-Ching

    2016-09-01

    In this study, the null-field boundary integral equation method (BIEM) and the image method are used to solve the SH wave scattering problem containing semi-circular canyons and circular tunnels. To fully utilize the analytical property of circular geometry, the polar coordinates are used to expand the closed-form fundamental solution to the degenerate kernel, and the Fourier series is also introduced to represent the boundary density. By collocating boundary points to match boundary condition on the boundary, a linear algebraic system is constructed. The unknown coefficients in the algebraic system can be easily determined. In this way, a semi-analytical approach is developed. Following the experience of near-trapped modes in water wave problems of the full plane, the focusing phenomenon and near-trapped modes for the SH wave problem of the half-plane are solved, since the two problems obey the same mathematical model. In this study, it is found that the SH wave problem containing two semi-circular canyons and a circular tunnel has the near-trapped mode and the focusing phenomenon for a special incident angle and wavenumber. In this situation, the amplification factor for the amplitude of displacement is over 300.

  10. a Study of Ricochet Phenomenon for Inclined Impact of Projectile

    NASA Astrophysics Data System (ADS)

    Jo, Jong-Hyun; Lee, Young-Shin

    In this study, the numerical simulation using AUTODYN-3D program was investigated for trajectory prediction for inclined impacts of projectiles. The penetration and perforation of polycarbonate(PC) plate by 7.62 mm projectile was investigated numerically. The characteristic structure of the projectile's trajectory in the PC plates was studied. Two combined failure criteria were used in the target plate, and the target plate was modeled with the properties of polycarbonate for simulating the ricochet phenomenon. The numerical analyses were used to study the effect of the angle of inclination on the trajectory and kinetic energy of the projectile. The dynamic deformation behaviors tests of PC were compared with numerical simulation results which can be used for predictive purpose. Ricochet phenomenon for angles of inclination of 0° ≤ θ ≤ 20° in the analysis. The projectile perforated the plate for θ > 30°, thus defined a failure envelope for numerical configuration. The numerical analyses was used to study the effect under the projectile impact velocity on the depth of penetration(DOP).

  11. Dependence phenomenon analysis of the stock market

    NASA Astrophysics Data System (ADS)

    Cheng, Wuyang; Wang, Jun

    2013-04-01

    A random financial stock price model is developed by the interacting contact process, which is one of the statistical-physics systems. The contact process is a continuous-time Markov process, one interpretation of this process is as a model for the spread of an infection, where the epidemic spreading mimics the interplay of local infections and the recovery of individuals. We investigate and analyze the long-term memory, the nonlinear correlations and the multifractal phenomenon of normalized returns of the price model by statistical analysis methods, which include autocorrelation analysis, the Gaussian copula method and the multifractal analysis method. Moreover, we consider the daily returns of the Shanghai Stock Exchange Composite Index and the Shenzhen Stock Exchange Composite Index, and the comparisons of statistical behaviors of returns between the actual data and the simulation data are presented.

  12. No-reflow phenomenon: maintaining vascular integrity.

    PubMed

    Kloner, Robert A

    2011-01-01

    The no-reflow phenomenon relates to the inability to reperfuse regions of the myocardium after ischemia, despite removal of the large epicardial coronary artery occlusion. The mechanism involves microvascular obstruction. In experimental studies, using markers for flow (thioflavin S, carbon black, microspheres), perfusion defects associated with no-reflow demonstrated ultrastructural evidence of localized endothelial swelling and blebs that appeared to obstruct flow. In humans no-reflow is more complicated due to the microemboli of atherosclerotic debris and thrombi generated by percutaneous coronary intervention. The no-reflow zone expands during the first few hours of reperfusion suggesting an element of reperfusion injury. In animal models, extensive no-reflow was associated with worse infarct expansion. The phenomenon of no-reflow following reperfusion therapy for myocardial infarction in humans has been demonstrated by magnetic resonance imaging, echo contrast agents, thallium, technecium-99m-labeled albumin microspheres, Thrombolysis In Myocardial Infarction (TIMI) scores, and myocardial blush grade. Patients exhibiting no-reflow following reperfusion therapy for myocardial infarction have greater left ventricular dilation and remodeling, more congestive heart failure, shock, and reduced survival. Certain vasodilators (adenosine, nitroprusside, nicorandil, and calcium blockers) are used acutely in the catheterization laboratory and appear to improve no-reflow, but systematic studies on therapy for no-reflow are needed. There is now clinical evidence that no-reflow is a strong predictor of long-term mortality that is independent of and beyond that provided by infarct size. Identifying and treating no-reflow may have important benefits including enhancing delivery of nutrients and cells required for healing and reducing infarct expansion and ventricular remodeling, which ultimately may reduce congestive heart failure and mortality.

  13. Sorption of Pb(II), Cr(III), Cu(II), As(III) to peat, and utilization of the sorption properties in industrial waste landfill hydraulic barrier layers.

    PubMed

    Koivula, Minna P; Kujala, Kauko; Rönkkömäki, Hannu; Mäkelä, Mauri

    2009-05-15

    The low conductivity landfill barrier layers protect the groundwater and soil by limiting the water flow through the bottom layers of the landfill material. Many materials used in hydraulic barrier layers also have sorption properties which could be used to reduce environmental risks. The adsorption of lead, chromium, copper, and arsenic to peat was studied with a batch-type test and a column test for compacted peat, both without pH adjustment in acidic conditions. Peat adsorbed all the metals well, 40000mg/kg of lead, 13000mg/kg of chromium, and 8400mg/kg of copper in the column test. Arsenic was only tested in a batch-type test, and in that peat adsorbed 60mg/kg of arsenic. The column test showed heavy metals to be adsorbed on the surface layers of the compacted peat sample, on the first centimeter of the sample. The adsorption was much greater in the column test than in the batch-type test, partly due to the different pH conditions and the buffer capacity of the peat in the column test. The liquid/solid ratio of the column experiment represented a time period of approximately 40 years in a landfill, under Finnish climate conditions. The hydraulic conductivity of the peat decreased as it was compressed, but it already met the hydraulic conductivity limits set by European Union legislation for the hydraulic barrier layer (1x10(-9)m/s at a pressure of 150kPa for a 5-m layer), with a pressure of 50kPa. The results show that peat would be an excellent material to construct compacted, low hydraulic conductivity layers with adsorption properties in, e.g. industrial waste landfills.

  14. Efficacy of cilostazol for the treatment of Raynaud's phenomenon in systemic sclerosis patients.

    PubMed

    Negrini, Simone; Spanò, Francesca; Penza, Elena; Rollando, Daniela; Indiveri, Francesco; Filaci, Gilberto; Puppo, Francesco

    2016-08-01

    Cilostazol is a selective inhibitor of phosphodiesterase-III with antiplatelet, antithrombotic and vasodilating properties. The aim of our study was to evaluate the effect of the drug on vasculopathy and Raynaud's phenomenon (RP), in a series of patients with systemic sclerosis (SSc), before and after cilostazol treatment. Twenty-one consecutive SSc patients with moderate or severe RP were enrolled in an open-label study. Cilostazol was administered at the dose of 100 mg twice a day, for 12 months. Evaluations included: daily RP attack diary documenting the frequency and duration of RP episodes, Health Assessment Questionnaire-Disability Index, scleroderma visual analogue scales (VAS), flow-mediated dilation and immunological status, including endothelin 1 and interleukin 6 plasma levels. Thirteen patients completed the study. RP duration and daily number episodes recorded over a 3-week period significantly decreased after cilostazol treatment (p = 0.0049 and p = 0.0067, respectively). VAS score indicated a significant amelioration of the patients' perception of RP (p = 0.0117), and both baseline and post-ischemic brachial artery diameters were significantly increased after cilostazol treatment, as compared with basal values (p = 0.0119 and p = 0.0076, respectively). None of the patients developed digital ulcers during the study. A significant clinical improvement of RP was recorded in SSc patients undergoing cilostazol treatment. Study results indicate a potential role of cilostazol as oral maintenance therapy in SSc patients with RP.

  15. Complexation of Sn2Se6 with lanthanide(III) centers influenced by ethylene polyamines: Solvothermal syntheses, crystal structures, and optical properties of lanthanide selenidostannates

    NASA Astrophysics Data System (ADS)

    Tang, Chunying; Wang, Fang; Chen, Ruihong; Jiang, Wenqing; Zhang, Yong; Jia, Dingxian

    2013-08-01

    Lanthanide selenidostannates (H3O)n[Ce(tepa)(μ-1κ2:2κ2-Sn2Se6)]n (1), [{Yb(tepa)(μ-OH)}2(μ-1κ:2κ-Sn2Se6)]n·nH2O (2), [Htrien]2[{Ln(trien)(tren)}2(μ-1κ:2κ-Sn2Se6)][Sn2Se6] (Ln=Ce(3), Nd(4)) and [{Yb(dien)2}2(μ-OH)2]Sn2Se6 (5) were solvothermally prepared in different ethylene polyamines. The Sn2Se6 unit connects [Ce(tepa)]3+ and [{Yb(tepa)(μ-OH)}2]4+ fragments with tetradentate μ-1κ2Se1,Se2:2κ2Se5,Se6 and bidentate μ-1κSe1:2κSe5 bridging coordination modes in tepa, to form polymers 1 and 2, respectively. It joins two [Ln(trien)(tren)]3+ fragments as a μ-1κSe1:2κSe5 ligand to form binuclear complexes 3 and 4 in trien. Unlike the Sn2Se6 units in 1-4 that bind with Ln(III) centers as Se-donor ligands, the Sn2Se6 unit in 5 exists as a discrete ion. The syntheses of 1-5 show that the ethylene polyamines play an important role in the complexation of Sn2Se6 ligand with Ln(III) centers. Compounds 1-5 exhibit optical band gaps in the range of 2.09-2.42 eV, which are influenced by the complexation of Sn2Se6 with Ln(III) centers.

  16. Synthesis and luminescent properties of novel lanthanide(III) beta-diketone complexes with nitrogen p,p'-disubstituted aromatic ligands.

    PubMed

    Bellusci, Anna; Barberio, Giovanna; Crispini, Alessandra; Ghedini, Mauro; La Deda, Massimo; Pucci, Daniela

    2005-03-21

    Tris-beta-diketonate lanthanide(III) complexes (Ln = Eu, Er, Yb, Tb), of general formula [Ln(acac)3 L(m)], with chelating ligands such as 4,7-disubstituted-1,10-phenanthrolines and 4,4'-disubstituted-2,2'-bipyridines, have been synthesized and fully characterized. The inductive effects of the para-substituents on the aromatic N-donor ligands have been investigated both in the solid and in the solution states. Single-crystal X-ray structures have been determined for the diethyl 1,10-phenanthroline-4,7-dicarboxylate europium and 4,4'-dimethoxy-2,2'-bipyridine erbium derivatives, revealing a distorted square antiprismatic geometry around the lanthanide atom in both cases. The influence exerted by the p,p'-substituents with respect to the nitrogen coordinating atoms on the Ln-N bond distances is discussed comparing the geometrical parameters with those found for the crystal structures containing the fragments [Ln(III)(phen)] and [Ln(III)(bipy)] obtained from the Cambridge Structural Database. The influence exerted by the electron-attracting groups on the coordination ability of the ligands, that in some cases becomes lack of coordination of the lanthanide ions, has been also detected in solution where the loss of the ligand has been followed by UV-vis spectroscopy. Moreover, the use of relatively long alkoxy chains as substituents on the 1,10-phenanthroline ligand led to the formation of a promesogenic lanthanide complex, whose thermal behavior is encouraging for the synthesis of new lanthanide liquid-crystalline species.

  17. Dimerization, redox properties and antioxidant activity of two manganese(III) complexes of difluoro- and dichloro-substituted Schiff-base ligands.

    PubMed

    Palopoli, Claudia; Gómez, Guillermo; Foi, Ana; Doctorovich, Fabio; Mallet-Ladeira, Sonia; Hureau, Christelle; Signorella, Sandra

    2017-02-01

    Two mononuclear Mn(III) complexes [Mn(3,5-F2salpn)(H2O)2][B(C6H5)4]·2H2O (1·2H2O) and [Mn(3,5-Cl2salpn)(OAc)(H2O)]·H2O (2·H2O), where H2salpn=1,3-bis(salicylidenamino)propane, have been prepared and characterized. The crystal structure of 1·H2O shows that this complex forms μ-aqua dimers with a short Mn⋯Mn distance of 4.93Å. Under anaerobic conditions, the two complexes are stable in solution and possess trans-diaxial symmetry with the tetradentate Schiff base ligand symmetrically arranged in the equatorial plane. When left in air, these complexes slowly dimerize to yield high-valent [Mn(IV)2(3,5-X2-salpn)2(μ-O)2] in which each X2-salpn ligand wraps the two Mn ions. This process is favored in basic medium where the deprotonation of the bound water molecule is concomitant with air oxidation. The two complexes catalyze the dismutation of superoxide (superoxide dismutase (SOD) activity) and peroxide (catalase (CAT) activity) in basic medium. The phenyl-ring substituents play an important role on the CAT reaction but have little effect on SOD activity. Kinetics and spectroscopic results indicate that 1 and 2 catalyze H2O2 disproportionation through a cycle involving Mn(III)2 and Mn(IV)2 dimers, unlike related complexes with a more rigid and smaller chelate ring, which employ Mn(III)/Mn(V)O monomers.

  18. Experimental Investigations of Transport and Optical Properties of III-V Quantum Well Structures Grown Via Molecular Beam Epitaxy Under Optimal Growth Conditions

    DTIC Science & Technology

    1990-06-01

    March, 1988, Newport Beach Mariott Hotel , CA). 4. W.C Tang, Pudong Lao, and A. Madhukar, "Optical Investigation of Resonant Mixing Between Electronic...and Device Applications", (13-18 March, 1988, Newport Beach Mariott Hotel , CA). III. ST JDENTS/POST-DO CS TRAINED: 1. Mr. Nam-Min Cho (Ph.D. Oct. 1988...Semiconductors and Superconductors: Physics and Device Applications" (13-18 March, 1988, Newport Beach Mario« Hotel , CA), SPIE Vol. 946, p.150 (1988

  19. POPULATION III HYPERNOVAE

    SciTech Connect

    Smidt, Joseph; Whalen, Daniel J.; Wiggins, Brandon K.; Even, Wesley; Fryer, Chris L.; Johnson, Jarrett L.

    2014-12-20

    Population III supernovae have been of growing interest of late for their potential to directly probe the properties of the first stars, particularly the most energetic events that are visible near the edge of the observable universe. Until now, hypernovae, the unusually energetic Type Ib/c supernovae that are sometimes associated with gamma-ray bursts, have been overlooked as cosmic beacons at the highest redshifts. In this, the latest of a series of studies on Population III supernovae, we present numerical simulations of 25-50 M {sub ☉} hypernovae and their light curves done with the Los Alamos RAGE and SPECTRUM codes. We find that they will be visible at z = 10-15 to the James Webb Space Telescope and z = 4-5 to the Wide-Field Infrared Survey Telescope, tracing star formation rates in the first galaxies and at the end of cosmological reionization. If, however, the hypernova crashes into a dense shell ejected by its progenitor, it is expected that a superluminous event will occur that may be seen at z ∼ 20 in the first generation of stars.

  20. Synthesis, crystal structure and magnetic properties of trinuclear chromium(III) basic carboxylate assembly: [Cr3O(salH)7(H2O)2] (salH2=salicylic acid), a new member of [Cr3O] family

    NASA Astrophysics Data System (ADS)

    Dong, Jinlong; Liu, Bin; Yang, Binsheng

    2016-07-01

    Synthesizing a novel trinuclear chromium(III) basic carboxylate complex could give rise to new materials with interesting properties. Complex [Cr3O(salH)7(H2O)2] is formed in a one-pot, self-assembly reaction when the inert reaction mixture is exposed to dioxygen. The structural property of the complex has been acquired by single-crystal X-ray crystallography and further characterized by elemental analysis (EA), infrared (IR), UV-Visible (UV-Vis), fluorescence spectroscopy and thermo gravimetric and differential thermal analysis (TG-DTA). X-ray structural analysis shows a slightly distorted equilateral of the Cr triangle. The most important feature of the title complex is the unusual framework of the [Cr3O] family due to a terminal Ph(OH)CO2- ion of Cr(2) center, which is unique among the structurally characterized (μ3-oxo)-trichromium(III) complexes. Variable-temperature magnetic susceptibility studies indicate that the total spin value of the ground state is 1/2.

  1. Effect of sintering temperature on structural and optical properties of indium(III) oxide nanoparticles prepared with Triton X-100 by hydrothermal method.

    PubMed

    Selvakumar, D; Dharmaraj, N; Kadirvelu, K; Kumar, N S; Padaki, V C

    2014-12-10

    Indium(III) hydroxide (In(OH)3) powders prepared via Triton X-100 mediated hydrothermal method was sintered at different temperatures (400, 500 and 600°C) to yield indium(III) oxide nanoparticles (In2O3 NPs). Thermal studies of In(OH)3 confirmed complete conversion to In2O3 around 400°C. Powder X-ray diffraction (XRD) pattern of sintered In2O3 nanoparticles revealed the formation of phase pure cubic In2O3. The crystallite size of In2O3 NPs was increased from 12 to 26nm upon increasing the sintering temperature from 400°C to 600°C, while the percentage crystallinity was increased up to 90% after sintering at 600°C. A red shift in the band gap energy was observed with increasing sintering temperature due to the larger size of sintered In2O3 NPs. Room temperature photoluminescence spectra of the indium oxide nanoparticles showed both near band and excitonic emission of In2O3 due to oxygen vacancies.

  2. Effect of sintering temperature on structural and optical properties of indium(III) oxide nanoparticles prepared with Triton X-100 by hydrothermal method

    NASA Astrophysics Data System (ADS)

    Selvakumar, D.; Dharmaraj, N.; Kadirvelu, K.; Kumar, N. S.; Padaki, V. C.

    2014-12-01

    Indium(III) hydroxide (In(OH)3) powders prepared via Triton X-100 mediated hydrothermal method was sintered at different temperatures (400, 500 and 600 °C) to yield indium(III) oxide nanoparticles (In2O3 NPs). Thermal studies of In(OH)3 confirmed complete conversion to In2O3 around 400 °C. Powder X-ray diffraction (XRD) pattern of sintered In2O3 nanoparticles revealed the formation of phase pure cubic In2O3. The crystallite size of In2O3 NPs was increased from 12 to 26 nm upon increasing the sintering temperature from 400 °C to 600 °C, while the percentage crystallinity was increased up to 90% after sintering at 600 °C. A red shift in the band gap energy was observed with increasing sintering temperature due to the larger size of sintered In2O3 NPs. Room temperature photoluminescence spectra of the indium oxide nanoparticles showed both near band and excitonic emission of In2O3 due to oxygen vacancies.

  3. Epicardial halo phenomenon: a guide for pericardiocentesis?

    PubMed

    Ristić, Arsen D; Wagner, Hans-Joachim; Maksimović, Ružica; Maisch, Bernhard

    2013-05-01

    The epicardial halo delineates the heart shadow in fluoroscopy. To establish whether the sign is applicable to pericardiocentesis guidance, three investigators evaluated its intensity as absent = grade 0, indistinct = 0.5, clear = 1, intensive = 2 in posterior-anterior (PA) and lateral fluoroscopies recorded before pericardiocentesis or cardiac catheterization (Philips Integris-II BH3000). Three populations were studied: (a) 32 patients with pericardial effusion (PE group), 53.1 % males, aged 53.9 ± 13.9 years; (b) 14 patients with perimyocarditis (PM group), 64.3 % males, aged 51.6 ± 14.4 years; and (c) 46 coronary patients (CAD group), no PE, 95.6 % males, aged 67.3 ± 11.8 years. The intensity of the halo phenomenon was highest in patients with PE, lowest in patients with CAD, and intermediate in patients with PM (median sum of grades in PA/lateral view: 4/5 vs. 2/2.5 vs. 3/3, respectively) (p < 0.01). The halo phenomenon correlated well with HR and echocardiographic PE size in both angiographic views. The correlation with body mass index (BMI) and age was significant only in the lateral view and with PE volume only in the PA view. The sensitivity of the halo sign for PE was 84.1 % in PA and 92.0 % in lateral views. In 10/32 PE patients, the evaluation of the sign was repeated after PE drainage, revealing lower grades both in PA and in lateral views (p < 0.01). In conclusion, the epicardial halo sign is highly sensitive for the detection of a PE; it correlates well in at least one angiographic projection with the PE volume, HR, age, BMI, and the PE size in echocardiography and could be therefore applied as a safety guide for pericardiocentesis.

  4. Acoustic characterization of flame blowout phenomenon

    NASA Astrophysics Data System (ADS)

    Nair, Suraj

    Combustor blowout is a very serious concern in modern land-based and aircraft engine combustors. The ability to sense blowout precursors can provide significant payoffs in engine reliability and life. The objective of this work is to characterize the blowout phenomenon and develop a sensing methodology which can detect and assess the proximity of a combustor to blowout by monitoring its acoustic signature, thus providing early warning before the actual blowout of the combustor. The first part of the work examines the blowout phenomenon in a piloted jet burner. As blowout was approached, the flame detached from one side of the burner and showed increased flame tip fluctuations, resulting in an increase in low frequency acoustics. Work was then focused on swirling combustion systems. Close to blowout, localized extinction/re-ignition events were observed, which manifested as bursts in the acoustic signal. These events increased in number and duration as the combustor approached blowout, resulting an increase in low frequency acoustics. A variety of spectral, wavelet and thresholding based approaches were developed to detect precursors to blowout. The third part of the study focused on a bluff body burner. It characterized the underlying flame dynamics near blowout in greater detail and related it to the observed acoustic emissions. Vorticity was found to play a significant role in the flame dynamics. The flame passed through two distinct stages prior to blowout. The first was associated with momentary strain levels that exceed the flame's extinction strain rate, leading to flame "holes". The second was due to large scale alteration of the fluid dynamics in the bluff body wake, leading to violent flapping of the flame front and even larger straining of the flame. This led to low frequency acoustic oscillations, of the order of von Karman vortex shedding. This manifested as an abrupt increase in combustion noise spectra at 40-100 Hz very close to blowout. Finally, work

  5. [Phenomenon of polyembryony. Genetic heterogeneity of seeds].

    PubMed

    Batygina, T B; Vinogradova, G Iu

    2007-01-01

    Different concepts of polyembryony and genetic heterogeneity of seeds in flower plants have been reviewed. Different types, ways, and forms of plant reproduction appeared in the course of evolution as a consequences of the attached mode of life and autotrophy. This is ascribed to totipotency, "stemminess" of plant cells, and presence of constantly functioning meristems, which determined to a great extent the system of plant safety. There are two ways of formation of a new individual: sexual process --> gamospermy involving meiosis and gamete fusion and asexual process --> agamospermy without meiosis and gamete fusion and two types of reproduction: seed and vegetative. Both processes may take place simultaneously in one seed, as a result of which many embryos of different origins are formed: uniparental and biparental inheritance. Traditionally, this phenomenon is called polyembryony. It comprises embryoidogeny (a new category of vegetative reproduction): formation of somatic embryos (= embryoids) in the flower, seed, and on vegetative organs. Genetic heterogeneity is one of the most important characteristics of seeds, which is based on different phenomena, such as embryogeny, embryoidogeny, and gametophytic and sporophytic apomixes. When describing two types of polyembryony, sporophytic (nucellar, integumental, cleavage) and gametophytic (synergidal, antipodal), a great attention is paid to characterization of initial cells of the sexual and adventive embryos. A new concept of apogamety is developed from new positions (totipotency and "stemminess"), which is based on different genesis of cells of the egg and antipodal systems. Five possible pathways of formation of the adventive embryos have been proposed from cells of the egg apparatus. Specific features of the formation of adventive embryos in the case of gametophytic apomixis, such as androgenesis and semigamy, are discussed. Morphogenesis of the sexual and adventive embryos proceeds in the mother organism and

  6. Efficient Synthesis of Tris-Heteroleptic Iridium(III) Complexes Based on the Zn(2+)-Promoted Degradation of Tris-Cyclometalated Iridium(III) Complexes and Their Photophysical Properties.

    PubMed

    Tamura, Yuichi; Hisamatsu, Yosuke; Kumar, Sarvendra; Itoh, Taiki; Sato, Kyouhei; Kuroda, Reiko; Aoki, Shin

    2017-01-17

    We report on the efficient synthesis of tris-heteroleptic iridium (Ir) complexes based on the degradation of tris-cyclometalated Ir complexes (IrL3, L: cyclometalating ligand) in the presence of Brønsted and Lewis acids such as HCl (in 1,4-dioxane), AlCl3, TMSCl, and ZnX2 (X = Br or Cl), which affords the corresponding halogen-bridged Ir dimers (μ-complexes). Tris-cyclometalated Ir complexes containing electron-withdrawing groups such as fluorine, nitro, or CF3 moieties on the ligands were less reactive. This different reactivity was applied to the selective degradation of heteroleptic Ir complexes such as fac-Ir(tpy)2(F2ppy) (fac-12) (tpy: 2-(4'-tolyl)pyridine and F2ppy: 2-(4',6'-difluorophenyl)pyridine), mer-Ir(tpy)2(F2ppy) (mer-12), and mer-Ir(mpiq)2(F2ppy) (mer-15) (mpiq: 1-(4'-methylphenyl)isoquinoline). For example, the reaction of mer-12 with ZnBr2 gave the heteroleptic μ-complex [{Ir(tpy)(F2ppy)(μ-Br)}2] 27b as a major product, resulting from the selective elimination of the tpy ligand of mer-12, and treatment of 27b with acetylacetone (acacH) afforded the corresponding tris-heteroleptic Ir complex Ir(tpy)(F2ppy)(acac)18. In addition, another tris-heteroleptic Ir complex 35a having 8-benzenesulfonylamidoquinoline (8BSQ) ligand was synthesized. Mechanistic studies of this degradation reaction and the photochemical properties, especially a dual emission, of these newly synthesized tris-heteroleptic Ir complexes are also reported.

  7. Photodetectors using III-V nitrides

    DOEpatents

    Moustakas, T.D.; Misra, M.

    1997-10-14

    A photodetector using a III-V nitride and having predetermined electrical properties is disclosed. The photodetector includes a substrate with interdigitated electrodes formed on its surface. The substrate has a sapphire base layer, a buffer layer formed from a III-V nitride and a single crystal III-V nitride film. The three layers are formed by electron cyclotron resonance microwave plasma-assisted molecular beam epitaxy (ECR-assisted MBE). Use of the ECR-assisted MBE process allows control and predetermination of the electrical properties of the photodetector. 24 figs.

  8. Photodetectors using III-V nitrides

    DOEpatents

    Moustakas, Theodore D.; Misra, Mira

    1997-01-01

    A photodetector using a III-V nitride and having predetermined electrical properties is disclosed. The photodetector includes a substrate with interdigitated electrodes formed on its surface. The substrate has a sapphire base layer, a buffer layer formed from a III-V nitride and a single crystal III-V nitride film. The three layers are formed by electron cyclotron resonance microwave plasma-assisted molecular beam epitaxy (ECR-assisted MBE). Use of the ECR-assisted MBE process allows control and predetermination of the electrical properties of the photodetector.

  9. [Phenomenon of super-longevity in Yakutia].

    PubMed

    Tatarinova, O V; Kylbanova, E S; Neustroeva, V N; Semenova, A N; Nikitin, Iu P

    2008-01-01

    According to preliminary data of UNESCO the oldest inhabitant of a planet now lives in the Republic Sakha (Yakutia). The article presents some results of the examination of a 117-years long-liver Semennikova (Djakonova) Varvara Konstantinovna. The age of the supercentenarian is certified by the record in the metric book of Yakutsk Spiritual Consistory for the Bulunskiy Spasskiy Church. The standard methods and unified criteria of estimation applied in epidemiological researches and at examination of elderly contingent were used. The health state, lifestyle and quality of life of the supercentenarian have been studied. During physical and instrumental examination of the centenarian the following data have been obtained: asthenic type of the constitution, the lowered index of body weight; the pathology of organism's functional systems (cardiovascular, respiratory, osteomuscular), appeared in senior age. The basic biochemical parameters of the blood are registered within the limits of the norm. The centenarian almost has not suffered from serious diseases. She does not remember long-livers among her relatives. The phenomenon of supercentenarian in Yakutia is the unique example of the extremely high level of adaptation to the extreme climate with prevailing clinically slightly expressed form.

  10. Raynaud's phenomenon: from molecular pathogenesis to therapy.

    PubMed

    Prete, Marcella; Fatone, Maria Celeste; Favoino, Elvira; Perosa, Federico

    2014-06-01

    Raynaud's phenomenon (RP) is a well defined clinical syndrome characterized by recurrent episodes of digital vasospasm triggered by exposure to physical/chemical or emotional stress. RP has been classified as primary or secondary, depending on whether it occurs as an isolated condition (pRP) or is associated to an underlying disease, mainly a connective tissue disease (CTD-RP). In both cases, it manifests with unique "triple" (pallor, cyanosis and erythema), or "double" color changes. pRP is usually a benign condition, while sRP can evolve and be complicated by acral digital ulcers and gangrene, which may require surgical treatment. The pathogenesis of RP has not yet been entirely clarified, nor is it known whether autoantibodies have a role in RP. Even so, recent advances in our understanding of the pathophysiology have highlighted novel potential therapeutic targets. The aim of this review is to discuss the etiology, epidemiology, risk factors, clinical manifestations, recently disclosed pathogenic mechanisms underlying RP and their correlation with the available therapeutic options, focusing primarily on pRP and CTD-RP.

  11. Capillaroscopic pattern in paraneoplastic Raynaud's phenomenon.

    PubMed

    Lambova, S; Müller-Ladner, U

    2013-06-01

    The capillaroscopic pattern in paraneoplastic Raynaud's phenomenon (RP) has not been investigated systematically and is not well-defined. Here, we present three case reports of patients with paraneoplastic rheumatic conditions, manifested with severe secondary RP with emphasis upon capillaroscopic findings. The first patient is a 58-year-old male with known psoriasis and psoriatic arthritis, severe RP and scleroderma-like syndrome, resulting in a paraneoplastic syndrome in the context of a lung cancer. At capillaroscopic examination classic "scleroderma" pattern, an "early" type was found. The second patient is a 48-year-old woman with an abrupt onset of paraneoplastic dermatomyositis, severe RP, and a lung cancer. The capillaroscopic examination revealed frequent dilated and giant capillaries, hemorrhages and severe microvascular disarrangement-the so-called "scleroderma-like" pattern typical of the idiopathic forms of the disease. The third patient is a 56-year-old woman with paraneoplastic dermatomyositis, secondary RP, and thyroid cancer. The capillaroscopic examination showed dilated and giant capillaries, elongated capillaries, decreased mean capillary density with avascular areas, severe disarrangement, single hemorrhages, and clear evidence of neoangiogenesis. These capillaroscopic features characteristic of the "scleroderma-like" pattern are indistinguishable from those in idiopathic dermatomyositis like in the second case. Taken together, the cases illustrate the problem that capillaroscopic patterns in paraneoplastic RP in the context of scleroderma-like syndrome and dermatomyositis appear to be indistinguishable from the microvascular changes in the respective idiopathic rheumatic diseases.

  12. Priming Intelligent Behavior: An Elusive Phenomenon

    PubMed Central

    Shanks, David R.; Newell, Ben R.; Lee, Eun Hee; Balakrishnan, Divya; Ekelund, Lisa; Cenac, Zarus; Kavvadia, Fragkiski; Moore, Christopher

    2013-01-01

    Can behavior be unconsciously primed via the activation of attitudes, stereotypes, or other concepts? A number of studies have suggested that such priming effects can occur, and a prominent illustration is the claim that individuals' accuracy in answering general knowledge questions can be influenced by activating intelligence-related concepts such as professor or soccer hooligan. In 9 experiments with 475 participants we employed the procedures used in these studies, as well as a number of variants of those procedures, in an attempt to obtain this intelligence priming effect. None of the experiments obtained the effect, although financial incentives did boost performance. A Bayesian analysis reveals considerable evidential support for the null hypothesis. The results conform to the pattern typically obtained in word priming experiments in which priming is very narrow in its generalization and unconscious (subliminal) influences, if they occur at all, are extremely short-lived. We encourage others to explore the circumstances in which this phenomenon might be obtained. PMID:23637732

  13. Antimicrobial resistance: a global multifaceted phenomenon

    PubMed Central

    Prestinaci, Francesca; Pezzotti, Patrizio; Pantosti, Annalisa

    2015-01-01

    Antimicrobial resistance (AMR) is one of the most serious global public health threats in this century. The first World Health Organization (WHO) Global report on surveillance of AMR, published in April 2014, collected for the first time data from national and international surveillance networks, showing the extent of this phenomenon in many parts of the world and also the presence of large gaps in the existing surveillance. In this review, we focus on antibacterial resistance (ABR), which represents at the moment the major problem, both for the high rates of resistance observed in bacteria that cause common infections and for the complexity of the consequences of ABR. We describe the health and economic impact of ABR, the principal risk factors for its emergence and, in particular, we illustrate the highlights of four antibiotic-resistant pathogens of global concern – Staphylococcus aureus, Klebsiella pneumoniae, non-typhoidal Salmonella and Mycobacterium tuberculosis – for whom we report resistance data worldwide. Measures to control the emergence and the spread of ABR are presented. PMID:26343252

  14. Anesthesia cutoff phenomenon: Interfacial hydrogen bonding

    SciTech Connect

    Chiou, J.S.; Ma, S.M.; Kamaya, H.; Ueda, I. )

    1990-05-04

    Anesthesia cutoff refers to the phenomenon of loss of anesthetic potency in a homologous series of alkanes and their derivatives when their sizes become too large. In this study, hydrogen bonding of 1-alkanol series (ethanol to eicosanol) to dipalmitoyl-L-alpha-phosphatidylcholine (DPPC) was studied by Fourier transform infrared spectroscopy (FTIR) in DPPC-D2O-in-CCl4 reversed micelles. The alkanols formed hydrogen bonds with the phosphate moiety of DPPC and released the DPPC-bound deuterated water, evidenced by increases in the bound O-H stretching signal of the alkanol-DPPC complex and also in the free O-D stretching band of unbound D2O. These effects increased according to the elongation of the carbon chain of 1-alkanols from ethanol (C2) to 1-decanol (C10), but suddenly almost disappeared at 1-tetradecanol (C14). Anesthetic potencies of these alkanols, estimated by the activity of brine shrimps, were linearly related to hydrogen bond-breaking activities below C10 and agreed with the FTIR data in the cutoff at C10.

  15. Malonate-containing manganese(III) complexes: synthesis, crystal structure, and magnetic properties of AsPh4[Mn(mal)2(H2O)2].

    PubMed

    Delgado, Fernando S; Kerbellec, Nicolas; Ruiz-Pérez, Catalina; Cano, Joan; Lloret, Francesc; Julve, Miguel

    2006-02-06

    The novel manganese(III) complexes PPh4[Mn(mal)2(H2O)2] (1) and AsPh4[Mn(mal)2(H2O)2] (2) (PPh4+ = tetraphenylphosphonium cation, AsPh4+ = tetraphenylarsonium cation, and H2mal = malonic acid) have been prepared, and the structure of 2 was determined by X-ray diffraction analysis. 2 is a mononuclear complex whose structure is made up of trans-diaquabis(malonato)manganate(III) units and tetraphenylarsonium cations. Two crystallographically independent manganese(III) ions (Mn(1) and Mn(2)) occur in 2 that exhibit elongated octahedral surroundings with four oxygen atoms from two bidentate malonate groups in equatorial positions (Mn(1)-O = 1.923(6) and 1.9328(6) A and Mn(2)-O = 1.894(6) and 1.925(6) A) and two trans-coordinated water molecules in the axial sites (Mn(1)-Ow = 2.245(6) A and Mn(2)-Ow = 2.268(6) A). The [Mn(mal)2(H2O)2]- units are linked through hydrogen bonds involving the free malonate-oxygen atoms and the coordinated water molecules to yield a quasi-square-type anionic layer growing in the ab plane. The shortest intralayer metal-metal separations are 7.1557(7) and 7.1526(7) A (through the edges of the square). The anionic sheets are separated from each other by layers of AsPh4+ where sextuple- and double-phenyl embraces occur. The magnetic behavior of 1 and 2 in the temperature range 1.9-290 K reveals the occurrence of weak intralayer ferromagnetic interactions (J = +0.081(1) (1) and +0.072(2) cm(-1) (2)). These values are compared to those of the weak antiferromagnetic coupling [J = -0.19(1) cm(-1)], which is observed in the chain compound K2[Mn(mal)2(MeOH)2][Mn(mal)2] (3), where the exchange pathway involves the carboxyate-malonate bridge in the anti-syn conformation. The structure of 3 was reported elsewhere. Theoretical calculations on fragment models of 2 and 3 were performed to analyze and substantiate both the nature and magnitude of the magnetic couplings observed.

  16. Synthesis, complexation and water exchange properties of Gd(III)-TTDA-mono and bis(amide) derivatives and their binding affinity to human serum albumin.

    PubMed

    Ou, Ming-Hung; Chen, Yi-Ming; Chang, Ya-Hui; Lu, Wen-Kuei; Liu, Gin-Chung; Wang, Yun-Ming

    2007-07-14

    With the objective of tuning the lipophilicity of ligands and maintaining the neutrality and stability of Gd(III) chelate, we designed and synthesized two bis(amide) derivatives of TTDA, TTDA-BMA and TTDA-BBA, and a mono(amide) derivative, TTDA-N-MOBA. The ligand protonation constants and complex stability constants for various metal ions were determined in this study. The identification of the microscopic sites of protonation of the amide ligand by 1H NMR titrations show that the first protonation site occurs on the central nitrogen atom. The values of the stability constant of TTDA-mono and bis(amide) complex are significantly lower than those of TTDA and DTPA, but the selectivity constants of these ligands for Gd(III) over Zn(II) and Cu(II) are slightly higher than those of TTDA and DTPA. On the basis of the water-exchange rate values available for [Gd(TTDA-BMA)(H2O)], [Gd(TTDA-BBA)(H2O)] and [Gd(TTDA-N-MOBA)(H2O)]-, we can state that, in general, the replacement of one carboxylate group by an amide group decreases the water-exchange rate of the gadolinium(III) complexes by a factor of about three to five. The decrease in the exchange rate is explained in terms of a decreased steric crowding and charge effect around the metal ion when carboxylates are replaced by an amide group. In addition, to support the HSA protein binding studies of lipophilic [Gd(TTDA-N-MOBA)(H2O)]- and [Gd(TTDA-BBA)(H2O)] complexes, further protein-complex binding was studied by ultrafiltration and relaxivity studies. The binding constants (KA) of [Gd(TTDA-N-MOBA)(H2O)]- and [Gd(TTDA-BBA)(H2O)] are 8.6 x 10(2) and 1.0 x 10(4) dm3 mol(-1), respectively. The bound relaxivities (r1(b)) are 51.8 and 52 dm3 mmol(-1) s(-1), respectively. The KA value of [Gd(TTDA-BBA)(H2O)] is similar to that of MS-325 and indicates a stronger interaction of [Gd(TTDA-BBA)(H2O)] with HSA.

  17. Photoinduced electron and energy transfer and pH-induced modulation of the photophysical properties in homo- and heterobimetallic complexes of ruthenium(II) and rhodium(III) based on a heteroditopic phenanthroline-terpyridine bridge.

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Karmakar, Srikanta; Baitalik, Sujoy

    2013-07-15

    Homo- and heterobimetallic complexes of compositions [(bpy)2Ru(II)(phen-Hbzim-tpy)Ru(II)(tpy/tpy-PhCH3/H2pbbzim)](4+) and [(bpy)2Ru(II)(phen-Hbzim-tpy)Rh(III)(tpy-PhCH3/H2pbbzim)](5+), where phen-Hbzim-tpy = 2-[4-(2,6-dipyridin-2-ylpyridin-4-yl)phenyl]-1H-imidazole[4,5-f][1,10]phenanthroline, bpy = 2,2'-bipyridine, tpy = 2,2':6',2"-terpyridine, tpy-PhCH3 = 4'-(4-methylphenyl)-2,2':6',2"-terpyridine, and H2pbbzim = 2,6-bis(benzimidazol-2-yl)pyridine, have been synthesized and characterized by elemental analyses, electrospray ionization mass spectrometry, and (1)H NMR spectroscopy. The absorption spectra, redox behavior, and luminescence properties of these bimetallic complexes have been thoroughly investigated and compared with those of monometallic [(bpy)2Ru(II)(phen-Hbzim-tpy)](2+) and [(tpy-PhCH3)Rh(III)(tpy-Hbzim-phen)](3+) model compounds. The electrochemistry of the complexes shows a reversible Ru(II/III) oxidation in the anodic region and an irreversible Rh(III/I) reduction and several ligand-based reductions in the cathodic region. Steady-state and time-resolved luminescence data at room temperature show that an efficient intramolecular electronic energy transfer from the metal-to-ligand charge-transfer (MLCT) excited state of the [(bpy)2Ru(II)(phen-Hbzim-tpy)] chromophore to the MLCT state of the tpy-containing chromophore [(phen-Hbzim-tpy)Ru(II)(tpy/tpy-PhCH3/H2pbbzim)] occurs in all three unsymmetrical homobimetallic complexes. On the other hand, for both heterometallic dyads, an efficient intramolecular photoinduced electron transfer from the excited ruthenium moiety to the rhodium-based unit takes place. The rate constants for the energy- and electron-transfer processes have been determined by time-resolved emission spectroscopy. The influence of the pH on the absorption, steady-state, and time-resolved emission properties of complexes has been thoroughly investigated. The absorption titration data were used to determine the ground-state pK values

  18. A suspicious reason for Raynaud's phenomenon: Intrauterine device.

    PubMed

    Diken, Adem I; Yalçınkaya, Adnan; Aksoy, Eray; Yılmaz, Seyhan; Çağlı, Kerim

    2015-06-01

    Primary Raynaud's phenomenon may be insistent in patients under medical therapy, and intrauterine devices may be an unnoticed reason in these patients. Fluctuations in female sex hormone status were reported to be associated with the emergence of primary Raynaud's phenomenon symptoms. The use of intrauterine devices was not reported to be associated with Raynaud's phenomenon previously. Intrauterine device may stimulate vascular hyperactivity regarding hormonal or unknown mechanisms that result in Raynaud's phenomenon. We present a postmenopausal patient who complained of primary Raynaud's phenomenon symptoms and had recovery after the removal of her copper intrauterine device.

  19. Influence of thickness and annealing on linear and nonlinear optical properties of manganese (III) chloride tetraphenyl porphine (MnTPPCl) organic thin films

    NASA Astrophysics Data System (ADS)

    Alharbi, S. R.; Darwish, A. A. A.; Al Garni, S. E.; ElSaeedy, H. I.; Abd El-Rahman, K. F.

    2016-09-01

    Thin films of manganese (III) chloride 5,10,15,20-tetraphenyl-21H,23H-porphine (MnTPPCl) with different film thickness were deposited by an evaporation technique. Some optical constants were calculated for these films at a thickness of 110, 220 and 330 nm and annealing temperature of 373 and 437 K. IR spectrum demonstrating that the thermal evaporation method is a good one to acquire undissociated and stoichiometric MnTPPCl films. Our perceptions demonstrate that the mechanism of the optical absorption obeys with the indirect transition. It was found that the energy gap, Eg, affected by the film thickness and annealing. Dispersion of the refractive index is described using single oscillator model. Dispersion parameters are calculated as a function of the film thickness and annealing temperature. In addition, the third-order nonlinear susceptibility, χ(3), and the nonlinear refractive index, n2, were calculated.

  20. Synthesis and luminescent properties of Tb(III) complex with a novel pyrazolone ligand and its interaction with bovine serum albumin

    NASA Astrophysics Data System (ADS)

    Yang, Zhengfa; Tang, Ruiren; Zhang, Zhenfeng

    2012-12-01

    A novel aromatic pyrazolone ligand, methyl 6-(3-methyl-1-phenyl-5-pyrazolone-4-carbonyl) pyridine-2-carboxylic acid (L), and its corresponding Tb(III) complexes, Tb(L)3·2H2O, was successfully prepared. L and its complex were characterized by means of mass spectrum (MS), elemental analysis, infrared spectroscopy (IR), 1HNMR and thermogravimetric analysis (TGA). The luminescence spectra showed that L was an efficient sensitizer for Tb(III) luminescence. The interaction of Tb(L)3·2H2O with bovine serum albumin (BSA) has been investigated through fluorescence spectroscopy under physiological conditions. The Stern-Volmer analysis indicated that the fluorescence quenching of BSA by Tb(L)3·2H2O was resulted from static mechanism, and the binding constants (Ka) were 2.36 × 104, 1.54 × 104 and 1.12 × 104 at 288 K, 298 K and 310 K, respectively. The binding sites (n) and the corresponding thermodynamic parameters ΔH, ΔS, and ΔG were calculated at different temperatures. According to the theoretical and experimental results, van der Waals interactions and hydrogen bonds were found to play major roles in the binding reaction. Furthermore, synchronous fluorescence spectra and circular dichroism (CD) spectra indicated that the conformation of BSA was changed. The results obtained in the work can help understand the action mode between rare earth complexes with BSA, and they are also expected to provide important information of designs of new inspired drugs based on rare earth compounds.

  1. Dinuclear and 1D iron(III) Schiff base complexes bridged by 4-salicylideneamino-1,2,4-triazolate: X-ray structures and magnetic properties.

    PubMed

    Herchel, Radovan; Pavelek, Lubomír; Trávníček, Zdeněk

    2011-11-28

    Four new iron(III) complexes were obtained by the reaction of 4-salicylideneamino-1,2,4-triazole (Hsaltrz) and selected dinuclear μ-oxo-bridged iron(III) Schiff base complexes [{FeL(4)}(2)(μ-O)], where L(4) represents a terminal tetradentate dianionic Schiff-base ligand. X-ray structural analysis revealed a novel bridging mode of κN,κO of the saltrz ligand to form dinuclear complexes [{Fe(salen)(μ-saltrz)}(2)]·CH(3)OH (1) (H(2)salen = N,N'-ethylenebis(salicylimine)) and [{Fe(salpn)(μ-saltrz)}(2)] (2) (H(2)salpn = N,N'-1,2-propylenbis(salicylimine)), whereas one-dimensional (1D) zig-zag chains were formed in the case of [{Fe(salch)(μ-saltrz)}·0.5CH(3)OH](n) (3) (H(2)salch = N,N'-cyclohexanebis(salicylimine)) and [Fe(salophen)(μ-saltrz)](n) (4) (H(2)salophen = N,N'-o-phenylenebis(salicylimine)). It was also shown that the rigidity of the terminal ligand L(4) can be considered as the key factor for the molecular dimensionality of the products. The thorough magnetic analysis based on SQUID experiments, including the isotropic exchange and the zero-field splitting of both temperature and field dependent data, was performed for dimeric (1 and 2) and also for polymeric compounds (3 and 4) and revealed weak antiferromagnetic exchange mediated by the saltrz anions with much larger D-parameter (|D|≫|J|).

  2. Structure property relationships in polymer blends and composites. Part I. Polymer/POSS composites. Part II. Poly(ethylene terephthalate) ionomer/polyamide 6 blends. Part III. Elastomer/boron nitride composites

    NASA Astrophysics Data System (ADS)

    Iyer, Subramanian

    Multiphase polymer systems are an increasingly important technical area of polymer science. By definition, a multiphase system is one that has two or more distinct phases. From the standpoint of commercial applications and developments, polymer blending represents one of the easiest ways to achieve properties not available in individual materials. This work discusses the structure property relationships in polymer certain blends and composites. Polymer/polyhedral oligomeric silsesquioxanes (POSSRTM) blends and copolymers have gained significant attention in the last decade due the unique properties of the inorganic-organic hybrid structure of POSS. The majority of the research in polymer/POSS has been in the form of copolymers and thermosets. The criteria for the reinforcement of polymers using POSS as a filler material is not been discussed in literature. Part I of the thesis will highlight the effect of blending POSS with different polymers and discuss the rules for reinforcement of polymers when using POSS as a filler material. Part II of the thesis will discuss the structure property relationships in poly(ethylene terephthalate) ionomer/polyamide 6 blends. Part III will discuss the control of coefficient of thermal expansion of elastomers using boron nitride as a filler material.

  3. Animal Rights as a Mainstream Phenomenon

    PubMed Central

    Rollin, Bernard E.

    2011-01-01

    Simple Summary The twentieth century has witnessed a bewildering array of ethical revolutions, from civil rights to environmentalism to feminism. Often ignored is the rise of massive societal concern across the world regarding animal treatment. Regulation of animal research exists in virtually all western countries, and reform of “factory farming” is regnant in Europe and rapidly emerging in the United States. Opponents of concern for animals often dismiss the phenomenon as rooted in emotion and extremist lack of appreciation of how unrestricted animal use has improved human life. Such a view totally ignores the rational ethical basis for elevating legal protection for animals, as explained in this essay. Abstract Businesses and professions must stay in accord with social ethics, or risk losing their autonomy. A major social ethical issue that has emerged in the past four decades is the treatment of animals in various areas of human use. Society's moral concern has outgrown the traditional ethic of animal cruelty that began in biblical times and is encoded in the laws of all civilized societies. There are five major reasons for this new social concern, most importantly, the replacement of husbandry-based agriculture with industrial agriculture. This loss of husbandry to industry has threatened the traditional fair contract between humans and animals, and resulted in significant amounts of animal suffering arising on four different fronts. Because such suffering is not occasioned by cruelty, a new ethic for animals was required to express social concerns. Since ethics proceed from preexisting ethics rather than ex nihilo, society has looked to its ethic for humans, appropriately modified, to find moral categories applicable to animals. This concept of legally encoded rights for animals has emerged as a plausible vehicle for reform. PMID:26486217

  4. Binary 193nm photomasks aging phenomenon study

    NASA Astrophysics Data System (ADS)

    Dufaye, Félix; Sartelli, Luca; Pogliani, Carlo; Gough, Stuart; Sundermann, Frank; Miyashita, Hiroyuki; Hidenori, Yoshioka; Charras, Nathalie; Brochard, Christophe; Thivolle, Nicolas

    2011-05-01

    193nm binary photomasks are still used in the semiconductor industry for the lithography of some critical layers for the nodes 90nm and 65nm, with high volumes and over long period. These 193nm binary masks seem to be well-known but recent studies have shown surprising degrading effects, like Electric Field induced chromium Migration (EFM) [1] or chromium migration [2] [3] . Phase shift Masks (PSM) or Opaque MoSi On Glass (OMOG) might not be concerned by these effects [4] [6] under certain conditions. In this paper, we will focus our study on two layers gate and metal lines. We will detail the effects of mask aging, with SEM top view pictures revealing a degraded chromium edge profile and TEM chemical analyses demonstrating the growth of a chromium oxide on the sidewall. SEMCD measurements after volume production indicated a modified CD with respect to initial CD data after manufacture. A regression analysis of these CD measurements shows a radial effect, a die effect and an isolated-dense effect. Mask cleaning effectiveness has also been investigated, with sulphate or ozone cleans, to recover the mask quality in terms of CD. In complement, wafer intrafield CD measurements have been performed on the most sensitive structure to monitor the evolution of the aging effect on mask CD uniformity. Mask CD drift have been correlated with exposure dose drift and isolated-dense bias CD drift on wafers. In the end, we will try to propose a physical explanation of this aging phenomenon and a solution to prevent from it occurring.

  5. Electron string phenomenon: physics and use

    NASA Astrophysics Data System (ADS)

    Donets, Evgeny D.

    2004-01-01

    Electron string phenomenon arises as a result of phase transition of a state of multiply reflected electron beam to this new discovered state of one component electron plasma and can be easily observed in the reflex mode of EBIS operation. The transition goes via a strong instability, which causes considerable electron energy spread, which in its turn suppresses the instability. Electron string state is a stationary state of hot pure electron plasma, which is heated by injected electron beam and cooled because of electron loses. Electron string is quiet in broad regions of experimental parameters, so that it is used for confinement and ionization of positive ions by electron impact to highly charge states similar to electron beams in EBIS. Application of electron strings instead of electron beams for ion production allows to save about 99% of electric power of electron beam and simultaneously to improve reliability of an ion source considerably. The JINR EBIS `Krion-2' in the string mode of operation is used for production of N7+, Ar16+ and Fe24+ ion beams and their acceleration to relativistic energies on the facility of the JINR super conducting one turn injection synchrotron `Nuklotron'. The tubular electron string possibly can exist and it is under study now theoretically and experiments are prepared now. Estimations show that a Tubular Electron String Ion Source (TESIS) could have up to three orders of magnitude higher ion output then a Linear one (LESIS). In frames of nuclear astrophysics electron strings can be used for research of fusion nuclear reactions at low energies in conditions when both beam and target nuclei do not carry orbital electrons. The project NARITA — Nuclear Astrophysics Researches in an Ion Trap Apparatus is proposed. Polarization effects also can be studied.

  6. Characterization of ribonuclease III from Brucella.

    PubMed

    Wu, Chang-Xian; Xu, Xian-Jin; Zheng, Ke; Liu, Fang; Yang, Xu-Dong; Chen, Chuang-Fu; Chen, Huan-Chun; Liu, Zheng-Fei

    2016-04-01

    Bacterial ribonuclease III (RNase III) is a highly conserved endonuclease, which plays pivotal roles in RNA maturation and decay pathways by cleaving double-stranded structure of RNAs. Here we cloned rncS gene from the genomic DNA of Brucella melitensis, and analyzed the cleavage properties of RNase III from Brucella. We identified Brucella-encoding small RNA (sRNA) by high-throughput sequencing and northern blot, and found that sRNA of Brucella and Homo miRNA precursor (pre-miRNA) can be bound and cleaved by B.melitensis ribonuclease III (Bm-RNase III). Cleavage activity of Bm-RNase III is bivalent metal cations- and alkaline buffer-dependent. We constructed several point mutations in Bm-RNase III, whose cleavage activity indicated that the 133th Glutamic acid residue was required for catalytic activity. Western blot revealed that Bm-RNase III was differently expressed in Brucella virulence strain 027 and vaccine strain M5-90. Collectively, our data suggest that Brucella RNase III can efficiently bind and cleave stem-loop structure of small RNA, and might participate in regulation of virulence in Brucella.

  7. Time-Dependent Rate Phenomenon in Viruses

    PubMed Central

    Aiewsakun, Pakorn

    2016-01-01

    ABSTRACT Among the most fundamental questions in viral evolutionary biology are how fast viruses evolve and how evolutionary rates differ among viruses and fluctuate through time. Traditionally, viruses are loosely classed into two groups: slow-evolving DNA viruses and fast-evolving RNA viruses. As viral evolutionary rate estimates become more available, it appears that the rates are negatively correlated with the measurement timescales and that the boundary between the rates of DNA and RNA viruses might not be as clear as previously thought. In this study, we collected 396 viral evolutionary rate estimates across almost all viral genome types and replication strategies, and we examined their rate dynamics. We showed that the time-dependent rate phenomenon exists across multiple levels of viral taxonomy, from the Baltimore classification viral groups to genera. We also showed that, by taking the rate decay dynamics into account, a clear division between the rates of DNA and RNA viruses as well as reverse-transcribing viruses could be recovered. Surprisingly, despite large differences in their biology, our analyses suggested that the rate decay speed is independent of viral types and thus might be useful for better estimation of the evolutionary time scale of any virus. To illustrate this, we used our model to reestimate the evolutionary timescales of extant lentiviruses, which were previously suggested to be very young by standard phylogenetic analyses. Our analyses suggested that these viruses are millions of years old, in agreement with paleovirological evidence, and therefore, for the first time, reconciled molecular analyses of ancient and extant viruses. IMPORTANCE This work provides direct evidence that viral evolutionary rate estimates decay with their measurement timescales and that the rate decay speeds do not differ significantly among viruses despite the vast differences in their molecular features. After adjustment for the rate decay dynamics, the

  8. Elementary and Secondary Education Property Accounting. A Handbook of Standard Terminology and a Guide for Classifying Information About Education Property. State Educational Records and Reports Series: Handbook III, Revised 1977.

    ERIC Educational Resources Information Center

    Davis (Robert) Associates, Inc., Atlanta, GA.

    The purposes of this handbook are to provide a comprehensive guide to standard terminology relating to property (sites, buildings, and equipment) used in education, a list of suggested data items useful in describing property, general data items useful in describing property, and general guidelines that can assist the reader in understanding and…

  9. Combination of Metal Coordination Tetrahedra and Asymmetric Coordination Geometries of Sb(III) in the Organically Directed Chalcogenidometalates: Structural Diversity and Ion-exchange Properties.

    PubMed

    Feng, Mei-Ling; Wang, Kai-Yao; Huang, Xiao-Ying

    2016-04-01

    Chalcogenidometalates exhibit rich and diverse structures and properties applicable to ion exchange, thermoelectrics, photocatalysis, nonlinear optics, and so on. This personal account summarizes our recent progress in constructing chalcogenidometalates by combining metal coordination tetrahedra and the asymmetric coordination geometries of Sb(3+) in the presence of organic species (typically organic amines and metal-organic amine complexes), which has been demonstrated as an effective strategy for synthesizing chalcogenidometalates with diversified structures and interesting properties. The linkage modes of asymmetric SbQn (n = 3, 4) geometries and group 13 (or 14) metal coordination tetrahedra are analyzed, and the secondary building units (SBUs), with different compositions and architectures, are clarified. The crucial role and function of organic species in the formation of chalcogenidometalates are explored, with an emphasis on their powerful structure-directing features. In particular, some chalcogenidometalates in this family exhibit excellent ion-exchange properties for Cs(+) and/or Sr(2+) ions; the factors affecting ion-exchange properties are discussed to understand the underlying ion-exchange mechanism.

  10. DFT/TD-DFT study on the electronic structures and optoelectronic properties of several blue-emitting iridium(III) complexes.

    PubMed

    Shi, Lili; Hong, Bo; Guan, Wei; Wu, Zhijian; Su, Zhongmin

    2010-06-24

    The electronic structures and optoelectronic properties of several blue-emitting phosphors (dfppy)(2)Ir(pyN2), (dfppy)Ir(pyN2)(2), and (fpmb)(2)Ir(pyN3) [dfppyH: 2-(2,4-difluorophenyl)pyridine; pyN2H: 5-(2-pyridyl)-3-trifluoromethylpyrazole; Hfpmb: 1-(4-fluorophenyl)-2,3-dihydro-3-methyl-1H-benzo[d]imidazole; and pyN3H: 2-(5-(trifluoromethyl)-2H-1,2,4-triazol-3-yl)pyridine] are investigated with density functional theory. The injection abilities of holes and electrons are estimated by evaluating the ionization potentials and electron affinities. It is found that the properties of the ligands have great influence on the photophysical properties, such as energy gap, absorption spectra, emission spectra, etc. The assumed complex (dfppy)(2)Ir(pyN2) is found to be a good candidate for blue-emitting material. We suggest that the luminescent properties of this class of materials can be tuned by modifications of the corresponding ligands.

  11. Synthesis, Photochemical, and Redox Properties of Gold(I) and Gold(III) Pincer Complexes Incorporating a 2,2':6',2"-Terpyridine Ligand Framework.

    PubMed

    Gimeno, M Concepción; López-de-Luzuriaga, José M; Manso, Elena; Monge, Miguel; Olmos, M Elena; Rodríguez-Castillo, María; Tena, María-Teresa; Day, David P; Lawrence, Elliot J; Wildgoose, Gregory G

    2015-11-16

    Reaction of [Au(C6F5)(tht)] (tht = tetrahydrothiophene) with 2,2':6',2"-terpyridine (terpy) leads to complex [Au(C6F5)(η(1)-terpy)] (1). The chemical oxidation of complex (1) with 2 equiv of [N(C6H4Br-4)3](PF6) or using electrosynthetic techniques affords the Au(III) complex [Au(C6F5)(η(3)-terpy)](PF6)2 (2). The X-ray diffraction study of complex 2 reveals that the terpyridine acts as tridentate chelate ligand, which leads to a slightly distorted square-planar geometry. Complex 1 displays fluorescence in the solid state at 77 K due to a metal (gold) to ligand (terpy) charge transfer transition, whereas complex 2 displays fluorescence in acetonitrile due to excimer or exciplex formation. Time-dependent density functional theory calculations match the experimental absorption spectra of the synthesized complexes. In order to further probe the frontier orbitals of both complexes and study their redox behavior, each compound was separately characterized using cyclic voltammetry. The bulk electrolysis of a solution of complex 1 was analyzed by spectroscopic methods confirming the electrochemical synthesis of complex 2.

  12. Structural and functional properties of CiNTH, an endonuclease III homologue of the ascidian Ciona intestinalis: critical role of N-terminal region.

    PubMed

    Kato, Seiji; Hashiguchi, Kazunari; Igarashi, Kento; Moriwaki, Takahito; Yonekura, Shin-Ichiro; Zhang-Akiyama, Qiu-Mei

    2012-01-01

    Oxidatively damaged bases in DNA can cause cell death, mutation and/or cancer induction. To overcome such deleterious effects of DNA base oxidation, cells are equipped with base excision repair (BER) initiated by DNA glycosylases. Endonuclease III (Nth), a major DNA glycosylase, mainly excises oxidatively damaged pyrimidines from DNA. The aims of this study were to obtain an overview of the repair mechanism of oxidatively damaged bases and to elucidate the function of BER in maintaining genome stability during embryogenesis and development. In this study, we used the ascidian Ciona intestinalis because at every developmental stage it is possible to observe the phenotype of individuals with DNA damage or mutations. Sequence alignment analysis revealed that the amino acid sequence of Ciona intestinalis Nth homologue (CiNTH) had high homology with those of Escherichia coli, Saccharomyces cerevisiae, Schizosaccharomyces pombe, Caenorhabditis elegans and human Nth homologues. It was evident that two domains, the Helix-hairpin-Helix and 4Fe-4S cluster domains that are critical regions for the Nth activity, are well conserved in CiNTH. CiNTH efficiently complemented the sensitivity of E. coli nth nei mutant to H(2)O(2). CiNTH was bifunctional, with DNA glycosylase and AP lyase activities. It removed thymine glycol, 5-formyluracil and 8-oxoguanine paired with G from DNA via a β-elimination reaction. Interestingly, the N-terminal 44 amino acids were essential for the DNA glycosylase activity of CiNTH.

  13. Cyclometalated Iminophosphorane Gold(III) and Platinum(II) Complexes. A Highly Permeable Cationic Platinum(II) Compound with Promising Anticancer Properties.

    PubMed

    Frik, Malgorzata; Fernández-Gallardo, Jacob; Gonzalo, Oscar; Mangas-Sanjuan, Víctor; González-Alvarez, Marta; Serrano del Valle, Alfonso; Hu, Chunhua; González-Alvarez, Isabel; Bermejo, Marival; Marzo, Isabel; Contel, María

    2015-08-13

    New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are described. Most of them are more cytotoxic to a number of human cancer cell lines than cisplatin. Cationic Pt(II) derivatives 4 and 5, which differ only in the anion, Hg2Cl6(2-) or PF6(-) respectively, display almost identical IC50 values in the sub-micromolar range (25-335-fold more active than cisplatin on these cell lines). The gold compounds induced mainly caspase-independent cell death, as previously reported for related cycloaurated compounds containing IM ligands. Cycloplatinated compounds 3, 4, and 5 can also activate alternative caspase-independent mechanisms of death. However, at short incubation times cell death seems to be mainly caspase dependent, suggesting that the main mechanism of cell death for these compounds is apoptosis. Mercury-free compound 5 does not interact with plasmid (pBR322) DNA or with calf thymus DNA. Permeability studies of 5 by two different assays, in vitro Caco-2 monolayers and a rat perfusion model, have revealed a high permeability profile for this compound (comparable to that of metoprolol or caffeine) and an estimated oral fraction absorbed of 100%, which potentially makes it a good candidate for oral administration.

  14. Synthesis, structure and magnetic properties of Na 9Co 2O 7, a new mixed-valent sodium cobaltate(II,III)

    NASA Astrophysics Data System (ADS)

    Sofin, M.; Peters, E.-M.; Jansen, M.

    2004-04-01

    Na 9Co 2O 7 was prepared via the azide/nitrate route. Stoichiometric mixtures of the precursors (Co 3O 4, NaN 3 and NaNO 3) were heated in a special regime up to 450 °C and annealed at this temperature for 100 h in specially designed silver containers. Single crystals have been grown by annealing a Na 2O/Na 9Co 2O 7 mixture (molar ratio 1:2) at 500 °C for 2000 h in silver crucibles, which were sealed in glass ampoules under dried Ar. According to the X-ray analysis of the crystal structure ( Pca2 1, Z=4, a=9.5477(6) Å, b=9.9040(6) Å, c=10.1919(7) Å, 4103 independent reflections, R1=5.23% (all data)) there are isolated Co IIIO 4 tetrahedra and Co IIO 3 triangles. Na 9Co 2O 7 is isostructural to Na 9Fe 2O 7, and shows Curie-Weiss behaviour down to ˜25 K. The best fit (for Co II ( S=3/2) and Co III ( S=2)) yields an average value of the magnetic moment (per cobalt) μ=3.23 μB ( g=2.07) and Θ=-6 K. At 20 K one observes an onset of ferromagnetic order.

  15. Synthesis, Characterization, Properties and DFT Calculations of 2-(Benzo[b]thiophen-2-yl)pyridine-based Iridium(III) Complexes with Different Ancillary Ligands.

    PubMed

    Li, Gao-Nan; Zeng, Yong-Pi; Li, Kai-Xiu; Chen, Hao-Hua; Xie, Hui; Zhang, Fu-Lin; Chen, Guang-Ying; Niu, Zhi-Gang

    2016-01-01

    A series of new cyclometalated btp-based iridium(III) complexes with three different ancillary ligands, Ir(btp)2(bozp) (3a), Ir(btp)2(btzp) (3b) and Ir(btp)2(izp) (3c) (btp = 2-(benzo[b]thiophen-2-yl)pyridine, bozp =2-(benzo[d]oxazol-2-yl)phenol, btzp =2-(benzo[d]thiazol-2-yl)phenol, izp = 2-(2 H-indazol-2-yl)phenol), have been synthesized and fully characterized. The crystal structure of 3b has been determined by single crystal X-ray diffraction analysis. A comparative study has been carried out for complexes 3a - 3c by UV-vis absorption spectroscopy, photoluminescence spectroscopy, cyclic voltammetry and DFT calculations. This observation illustrates that the substitution of N or S in ancillary ligand can lead to a marked bathochromic shift of absorption and emission wavelengths. The spectroscopic characterisation of these complexes has been complemented by DFT and TD-DFT calculations, supporting the assignment of (3)MLCT/(3)LC to the lowest energy excited state.

  16. Cyclometalated Iminophosphorane Gold(III) and Platinum(II) Complexes. A Highly Permeable Cationic Platinum(II) Compound with Promising Anticancer Properties

    PubMed Central

    2015-01-01

    New organometallic gold(III) and platinum(II) complexes containing iminophosphorane ligands are described. Most of them are more cytotoxic to a number of human cancer cell lines than cisplatin. Cationic Pt(II) derivatives 4 and 5, which differ only in the anion, Hg2Cl62– or PF6– respectively, display almost identical IC50 values in the sub-micromolar range (25–335-fold more active than cisplatin on these cell lines). The gold compounds induced mainly caspase-independent cell death, as previously reported for related cycloaurated compounds containing IM ligands. Cycloplatinated compounds 3, 4, and 5 can also activate alternative caspase-independent mechanisms of death. However, at short incubation times cell death seems to be mainly caspase dependent, suggesting that the main mechanism of cell death for these compounds is apoptosis. Mercury-free compound 5 does not interact with plasmid (pBR322) DNA or with calf thymus DNA. Permeability studies of 5 by two different assays, in vitro Caco-2 monolayers and a rat perfusion model, have revealed a high permeability profile for this compound (comparable to that of metoprolol or caffeine) and an estimated oral fraction absorbed of 100%, which potentially makes it a good candidate for oral administration. PMID:26147404

  17. Anomalous dielectric behaviour in centrosymmetric organic–inorganic hybrid chlorobismuthate(III) containing functional N,N-dimethylethylammonium ligand. Crystal structure and properties

    SciTech Connect

    Piecha, A.; Gągor, A.; Węcławik, M.; Jakubas, R.; Medycki, W.

    2013-01-15

    Graphical abstract: Display Omitted Highlights: ► Novel organic–inorganic hybrid chlorobismuthate(III). ► Unprecedented dielectric response in non-polar material. ► Dielectric relaxation characterized by an exceptionally large dielectric increment. ► The NMR measurements confirmed dynamic disorder of cations. -- Abstract: The structure of [C{sub 2}H{sub 5}NH(CH{sub 3}){sub 2}{sup +}]{sub 3}[BiCl{sub 6}{sup −}] (abbreviated as DCB) was determined by a single-crystal X-ray diffraction at 115 K. The compound adopts tetragonal symmetry with the space group I4{sub 1}/acd; a = 23.35 Å, c = 17.60 Å, V = 9598 Å{sup 3} and Z = 16. The crystal structure of DCB is built up of isolated [BiCl{sub 6}]{sup 3−} units and N,N-dimethylethylammonium counterions that are accommodated in the large voids. At ambient temperature two-thirds of the counterions appear to be dynamically disordered. Dynamics of this type of cations contributes to the enhanced dielectric permittivity of DCB. A low frequency dielectric relaxation process that takes place between 200 and 300 K is characterized by an exceptionally large dielectric increment, Δε > 100, which is unprecedented in nonferroelectric materials. The molecular motions of the N,N-dimethylethylammonium cations were studied by means of {sup 1}H NMR spin-lattice relaxation time measurements.

  18. Synthesis, X-ray diffraction structures, spectroscopic properties, and in vitro antitumor activity of isomeric (1H-1,2,4-triazole)Ru(III) complexes.

    PubMed

    Arion, Vladimir B; Reisner, Erwin; Fremuth, Madeleine; Jakupec, Michael A; Keppler, Bernhard K; Kukushkin, Vadim Yu; Pombeiro, Armando J L

    2003-09-22

    Three ruthenium(III) complexes containing 1H-1,2,4-triazole (Htrz), viz., (H(2)trz)[cis-RuCl(4)(Htrz)(2)], 1, (H(2)trz)[trans-RuCl(4)(Htrz)(2)], 2, and (Ph(3)PCH(2)Ph)[trans-RuCl(4)(Htrz)(2)], 3, have been synthesized by reaction between RuCl(3) and excess of the triazole in 2.38 M HCl (1 and 2), while 3 was obtained by metathesis of 2 and [Ph(3)PCH(2)Ph]Cl in water. The products were characterized by IR, UV-vis, electrospray mass spectrometry, cyclic voltammetry, and X-ray crystallography (1 and 3). X-ray diffraction study revealed cis and trans arrangements of the triazole ligands in 1 and 3, correspondingly, and unprecedented monodentate coordination of the triazole through N2 and stabilization of its 4H tautomeric form, which is the disfavored one for the free triazole. The cytotoxicity of 1 and 2 has been assayed in three human carcinoma cell lines SW480, HT29 (colon carcinoma), and SK-BR-3 (mammary carcinoma). Both compounds exhibit antiproliferative activity in vitro. Time-dependent response of all three lines to 1 and 2 and a structure-activity relationship, i.e., higher activity of the trans-isomer 2 than that of cis-species 1, have been observed.

  19. Optical and physical properties of stratospheric aerosols from balloon measurements in the visible and near-infrared domains. III. Presence of aerosols in the middle stratosphere.

    PubMed

    Renard, Jean-Baptiste; Ovarlez, Joëlle; Berthet, Gwenaël; Fussen, Didier; Vanhellemont, Filip; Brogniez, Colette; Hadamcik, Edith; Chartier, Michel; Ovarlez, Henri

    2005-07-01

    The aerosol extinction measurements in the ultraviolet and visible wavelengths by the balloonborne spectrometer Spectroscopie d'Absorption Lunaire pour l'Observation des Minoritaires Ozone et NOx (SALOMON) show that aerosols are present in the middle stratosphere, above 25-km altitude. These observations are confirmed by the extinction measurements performed by a solar occultation radiometer. The balloonborne Laboratoire de Météorologie Dynamique (LMD) counter instrument also confirms the presence of aerosol around 30-km altitude, with an unrealistic excess of micronic particles assuming that only liquid sulfate aerosols are present. An unexpected spectral structure around 640-nm observed by SALOMON is also detectable in extinction measurements by the satellite instrument Stratospheric Aerosols and Gas Experiment III. This set of measurements could indicate that solid aerosols were detected at these altitude ranges. The amount of soot detected up to now in the lower stratosphere is too low to explain these measurements. Thus, the presence of interplanetary dust grains and micrometeorites may need to be invoked. Moreover, it seems that these grains fill the stratosphere in stratified layers.

  20. Optical and physical properties of stratospheric aerosols from balloon measurements in the visible and near-infrared domains. III. Presence of aerosols in the middle stratosphere

    NASA Astrophysics Data System (ADS)

    Renard, Jean-Baptiste; Ovarlez, Joëlle; Berthet, Gwenaël; Fussen, Didier; Vanhellemont, Filip; Brogniez, Colette; Hadamcik, Edith; Chartier, Michel; Ovarlez, Henri

    2005-07-01

    The aerosol extinction measurements in the ultraviolet and visible wavelengths by the balloonborne spectrometer Spectroscopie d'Absorption Lunaire pour l'Observation des Minoritaires Ozone et NO_x (SALOMON) show that aerosols are present in the middle stratosphere, above 25-km altitude. These observations are confirmed by the extinction measurements performed by a solar occultation radiometer. The balloonborne Laboratoire de Météorologie Dynamique (LMD) counter instrument also confirms the presence of aerosol around 30-km altitude, with an unrealistic excess of micronic particles assuming that only liquid sulfate aerosols are present. An unexpected spectral structure around 640-nm observed by SALOMON is also detectable in extinction measurements by the satellite instrument Stratospheric Aerosols and Gas Experiment III. This set of measurements could indicate that solid aerosols were detected at these altitude ranges. The amount of soot detected up to now in the lower stratosphere is too low to explain these measurements. Thus, the presence of interplanetary dust grains and micrometeorites may need to be invoked. Moreover, it seems that these grains fill the stratosphere in stratified layers.

  1. A newly developed chromium(III) gel technology

    SciTech Connect

    Sydansk, R.D. . Research Div.)

    1990-08-01

    Laboratory testing of a recently developed chromium(III) (Cr(III)) gel technology is reported. The gels can be used in conjunction with a number of oilfield treatments. The single-fluid acrylamide-polymer/Cr(III)-carboxylate aqueous gels are formed by crosslinking acrylamide polymer with a Cr(III)-carboxylate-complex crosslinking agent. Representative gel compositions and associated gel properties are discussed.

  2. The Structure of Bis(phthalocyaninato)neodymium(III).

    DTIC Science & Technology

    1980-06-01

    synthesis of lanthanide (III) phthalocyanine complexes 1 was established by Kirin and Moskalev, many studies on their composi- 2 tions and properties have...been reported. For instance, intense attention has been directed toward electrochromism of bis(phthalocyaninato) lanthanide (III) complexes , Pc2Ln(III)H...The structural analysis of bis(phthalocyaninato) lanthanide (III) complexes would provide useful information to investigate their electo- chromuism, and

  3. Global Positioning System III (GPS III)

    DTIC Science & Technology

    2015-12-01

    from the SV Bus, specifically the Scalable Power Regulation Unit and is being amplified by the solar arrays which act as highly efficient antennas. To...Military Operations in Urban Terrain; Defense-Wide Mission Support; Air Mobility; and Space Launch Orbital Support. For military users, the GPS III...Service: The GPS III program will provide O&S for on- orbit support through the Launch and On- Orbit Support contract. For Space Vehicle (SV)01 and

  4. Powerful Radio Burst Indicates New Astronomical Phenomenon

    NASA Astrophysics Data System (ADS)

    2007-09-01

    Astronomers studying archival data from an Australian radio telescope have discovered a powerful, short-lived burst of radio waves that they say indicates an entirely new type of astronomical phenomenon. Region of Strong Radio Burst Visible-light (negative greyscale) and radio (contours) image of Small Magellanic Cloud and area where burst originated. CREDIT: Lorimer et al., NRAO/AUI/NSF Click on image for high-resolution file ( 114 KB) "This burst appears to have originated from the distant Universe and may have been produced by an exotic event such as the collision of two neutron stars or the death throes of an evaporating black hole," said Duncan Lorimer, Assistant Professor of Physics at West Virginia University (WVU) and the National Radio Astronomy Observatory (NRAO). The research team led by Lorimer consists of Matthew Bailes of Swinburne University in Australia, Maura McLaughlin of WVU and NRAO, David Narkevic of WVU, and Fronefield Crawford of Franklin and Marshall College in Lancaster, Pennsylvania. The astronomers announced their findings in the September 27 issue of the online journal Science Express. The startling discovery came as WVU undergraduate student David Narkevic re-analyzed data from observations of the Small Magellanic Cloud made by the 210-foot Parkes radio telescope in Australia. The data came from a survey of the Magellanic Clouds that included 480 hours of observations. "This survey had sought to discover new pulsars, and the data already had been searched for the type of pulsating signals they produce," Lorimer said. "We re-examined the data, looking for bursts that, unlike the usual ones from pulsars, are not periodic," he added. The survey had covered the Magellanic Clouds, a pair of small galaxies in orbit around our own Milky Way Galaxy. Some 200,000 light-years from Earth, the Magellanic Clouds are prominent features in the Southern sky. Ironically, the new discovery is not part of these galaxies, but rather is much more distant

  5. Variations on a theme - the evolution of hydrocarbon solids. III. Size-dependent properties - the optEC(s)(a) model

    NASA Astrophysics Data System (ADS)

    Jones, A. P.

    2012-06-01

    Context. The properties of hydrogenated amorphous carbon (a-C:H) dust evolve in response to the local radiation field in the interstellar medium (ISM) and the evolution of these properties is particularly dependent upon the particle size. Aims: A model for finite-sized, low-temperature amorphous hydrocarbon particles, based on the microphysical properties of random and defected networks of carbon and hydrogen atoms, with surfaces passivated by hydrogen atoms, has been developed. Methods: The eRCN/DG and the optEC(s) models have been combined, adapted and extended into a new optEC(s)(a) model that is used to calculate the optical properties of hydrocarbon grain materials down into the sub-nanometre size regime, where the particles contain only a few tens of carbon atoms. Results: The optEC(s)(a) model predicts a continuity in properties from large to small (sub-nm) carbonaceous grains. Tabulated data of the size-dependent optical constants (from EUV to cm wavelengths) for a-C:H (nano-)particles as a function of the bulk material band gap [Eg(bulk)], or equivalently the hydrogen content, are provided. The effective band gap [Eg(eff.)] is found to be significantly larger than Eg(bulk) for hydrogen-poor a-C(:H) nano-particles and their predicted long-wavelength (λ > 30 μm) optical properties differ from those derived for interstellar polycyclic aromatic hydrocarbons (PAHs). Conclusions: The optEC(s)(a) model is used to investigate the size-dependent structural and spectral evolution of a-C(:H) materials under ISM conditions, including: the IR-FUV extinction, the 217 nm bump and the infrared emission bands. The model makes several predictions that can be tested against observations. Appendices A-E are available in electronic from at http://www.aanda.orgData files are only available form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/542/A98

  6. Recent achievements in the management of Raynaud's phenomenon.

    PubMed

    Baumhäkel, Magnus; Böhm, Michael

    2010-04-15

    Raynaud's phenomenon is a clinical disorder with episodic digital ischemic vasospasm triggered by cold- or emotional-stress. It was first mentioned by Maurice Raynaud in 1862 describing "a local asphyxia of the extremities" and was further divided into primary Raynaud's disease and secondary Raynaud's phenomenon, which is often related to connective tissue diseases, but also physical or chemical strain. Though pathophysiology of Raynaud's phenomenon is still poorly understood, systemic and local vascular effects are most likely to be involved in primary Raynaud's disease. In secondary Raynaud's phenomenon additional abnormalities in vascular structure and function may play the major role. Thus, medical treatment of Raynaud's phenomenon remains unsatisfactory, due to limited understanding of pathophysiological mechanisms. This review addresses current evidence for medical treatment of primary and secondary Raynaud's phenomenon with regard to pathophysiological mechanisms as well as future perspectives.

  7. Raynaud's phenomenon of the nipple associated with labetalol use.

    PubMed

    McGuinness, Naomi; Cording, Vicky

    2013-02-01

    Raynaud's phenomenon of the nipple is an unusual cause of severe nipple pain. Precipitants for Raynaud's phenomenon of the nipple are known to be cold temperatures, caffeine, and emotional stress. Nipple pain is quoted as the most common cause of cessation of breastfeeding. It is important that lactation consultants and other health care professionals are aware of Raynaud's phenomenon of the nipple and the treatment options available. This is a case of a 37-year-old woman, Gravida 2, Para 1, who was first seen in the antenatal clinic at 34 weeks gestation. A diagnosis of Raynaud's phenomenon of the nipple was made after she began taking labetalol for pregnancy-induced hypertension. The phenomenon had occurred in both of her previous pregnancies on commencing labetalol and resolved postnatally on cessation of the drug. We aim to raise awareness of both the condition itself and the potential role of labetalol in the development of Raynaud's phenomenon of the nipple.

  8. PX Andromedae and the SW Sextantis phenomenon

    NASA Technical Reports Server (NTRS)

    Hellier, Coel; Robinson, E. L.

    1994-01-01

    We show that the emission-line peculiarities of PX And and other SW Sex stars can be explained by an accretion stream which overflows the initial impact with the accretion disk and continues to a later reimpact. The overflowing stream is seen projected against a brighter disk and produces the 'phase 0.5 absorption' features. Emission from the reimpact site produces the high-velocity line wings which alternate from red to blue on the orbital cycle. We conclude that substantial disk overflow is the property distinguishing SW Sex stars from other cataclysmic variables.

  9. Assessment of Technologies for the Space Shuttle External Tank Thermal Protection System and Recommendations for Technology Improvement - Part III: Material Property Characterization, Analysis, and Test Methods

    NASA Technical Reports Server (NTRS)

    Gates, Thomas S.; Johnson, Theodore F.; Whitley, Karen S.

    2005-01-01

    The objective of this report is to contribute to the independent assessment of the Space Shuttle External Tank Foam Material. This report specifically addresses material modeling, characterization testing, data reduction methods, and data pedigree. A brief description of the External Tank foam materials, locations, and standard failure modes is provided to develop suitable background information. A review of mechanics based analysis methods from the open literature is used to provide an assessment of the state-of-the-art in material modeling of closed cell foams. Further, this report assesses the existing material property database and investigates sources of material property variability. The report presents identified deficiencies in testing methods and procedures, recommendations for additional testing as required, identification of near-term improvements that should be pursued, and long-term capabilities or enhancements that should be developed.

  10. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.

    Several court cases involving acquisition, use, and disposal of property by institutions of higher education are briefly summarized in this chapter. Cases discussed touch on such topics as municipal annexation of university property; repurchase of properties temporarily allocated to faculty members; implications of zoning laws and zoning board…

  11. Percolation phenomenon in mixed reverse micelles: the effect of additives.

    PubMed

    Paul, Bidyut K; Mitra, Rajib K

    2006-03-01

    The conductivity of AOT/IPM/water reverse micellar systems as a function of temperature, has been found to be non-percolating at three different concentrations (100, 175 and 250 mM), while the addition of nonionic surfactants [polyoxyethylene(10) cetyl ether (Brij-56) and polyoxyethylene(20) cetyl ether (Brij-58)] to these systems exhibits temperature-induced percolation in conductance in non-percolating AOT/isopropyl myristate (IPM)/water system at constant compositions (i.e., at fixed total surfactant concentration, omega and X(nonionic)). The influence of total surfactant concentration (micellar concentration) on the temperature-induced percolation behaviors of these systems has been investigated. The effect of Brij-58 is more pronounced than that of Brij-56 in inducing percolation. The threshold percolation temperature, Tp has been determined for these systems in presence of additives of different molecular structures, physical parameters and/or interfacial properties. The additives have shown both assisting and resisting effects on the percolation threshold. The additives, bile salt (sodium cholate), urea, formamide, cholesteryl acetate, cholesteryl benzoate, toluene, a triblock copolymer [(EO)13(PO)30(EO)13, Pluronic, PL64], polybutadiene, sucrose esters (sucrose dodecanoates, L-1695 and sucrose monostearate S-1670), formamide distinctively fall in the former category, whereas sodium chloride, cholesteryl palmitate, crown ether, ethylene glycol constitute the latter for both systems. Sucrose dodecanoates (L-595) had almost marginal effect on the process. The observed behavior of these additives on the percolation phenomenon has been explained in terms of critical packing parameter and/or other factors, which influence the texture of the interface and solution properties of the mixed reverse micellar systems. The activation energy, Ep for the percolation process has been evaluated. Ep values for the AOT/Brij-56 systems have been found to be lower than those of

  12. Tuning the surface properties of novel ternary iron(III) fluoride-based catalysts using the template effect of the matrix.

    PubMed

    Guo, Ying; Lippitz, Andreas; Saftien, Paul; Unger, Wolfgang E S; Kemnitz, Erhard

    2015-03-21

    Sol-gel prepared ternary FeF3-MgF2 materials have become promising heterogeneous catalysts due to their porosity and surface Lewis/Brønsted acidity (bi-acidity). Despite the good catalytic performance, nanoscopic characterisations of this type of material are still missing and the key factors controlling the surface properties have not yet been identified, impeding both a better understanding and further development of ternary fluoride catalysts. In this study, we characterised the interaction between the bi-acidic component (FeF3) and the matrix (MgF2) on the nano-scale. For the first time, the formation pathway of FeF3-MgF2 was profiled and the template effect of MgF2 during the synthesis process was discovered. Based on these new insights two novel materials, FeF3-CaF2 and FeF3-SrF2, were established, revealing that with decreasing the atomic numbers (from Sr to Mg), the ternary fluorides exhibited increasing surface acidity and surface area but decreasing pore size. These systematic changes gave rise to a panel of catalysts with tuneable surface and bulk properties either by changing the matrix alkaline earth metal fluoride or by adjusting their ratios to Fe or both. The template effect of the alkaline earth metal fluoride matrix was identified as the most probable key factor determining the surface properties and further influencing the catalytic performance in ternary fluoride based catalysts, and paves the way to targeted design of next-generation catalysts with tunable properties.

  13. Chloride derivatives of lanthanoid(III) ortho-oxidotungstates(VI) with the formula LnCl[WO4] (Ln=Gd-Lu): Syntheses, crystal structures and spectroscopic properties

    NASA Astrophysics Data System (ADS)

    Schustereit, Tanja; Schleid, Thomas; Höppe, Henning A.; Kazmierczak, Karolina; Hartenbach, Ingo

    2015-03-01

    The lanthanoid(III) chloride ortho-oxidotungstates(VI) with the formula LnCl[WO4] crystallize monoclinically in space group C2/m (a=1019-1032, b=721-733, c=682-689 pm and β=107-108°, Z=4) for Ln=Gd-Er and triclinically in space group P1¯ (a=593-596, b=719-721, c=684-686 pm, α=93-94, β≈103 and γ≈122°, Z=2) for Ln=Tm-Lu. The monoclinic structure contains crystallographically unique Ln3+ cations, which are surrounded by two Cl- and six O2- anions forming distorted trigonal dodecahedra. Their fusion via common edges leads to anionic layers ∞ 2 {[ LnCl2/2eO4/2eO2/1t ] 6 - }. The polyhedra around the Ln3+ cations in the triclinic crystal structure are also built up by two Cl-, but only five O2- anions to form distorted monocapped trigonal prisms. Their linkage through edges constitutes anionic strands ∞ 1 {[ LnCl2/2eO2/2eO3/1t ] 6 - } along [100]. The complex anionic entities of both LnCl[WO4] arrangements become interconnected by W6+ cations to complete the structures by generating discrete [WO4]2- tetrahedra. Since the title compounds emerge as pure phases according to X-ray powder diffractometry, spectroscopic measurements such as single crystal Raman as well as diffuse reflectance spectroscopy (DRS) were performed. Furthermore, GdCl[WO4] and LuCl[WO4] are suitable host materials for doping with Eu3+, which leads to materials with a red luminescence upon excitation with UV light for both structures. Moreover, TbCl[WO4] exhibits a Tb3+-typical yellow-green bulk luminescence upon UV excitation, which could be analyzed by luminescence spectroscopy.

  14. Solid state and solution properties of lanthanide(III) complexes of a tetraiminodiphenolate macrocyclic ligand. X-ray structure, 1H NMR and luminescence spectral studies

    NASA Astrophysics Data System (ADS)

    Bag, Pradip; Dutta, Supriya; Flörke, Ulrich; Nag, Kamalaksha

    2008-11-01

    The lanthanide(III) complexes of composition [Ln(LH 2)(H 2O) 3Cl]Cl 2 (Ln = La-Lu and Y, 1- 15) derived from the tetraiminodiphenolate macrocyclic ligand L 2- have been prepared and characterized. In these compounds, the two uncoordinated imine nitrogens of the macrocycle are protonated and hydrogen-bonded with the metal-bound phenolate oxygens and thereby provide a zwitterionic structure to the ligand. The X-ray crystal structure of the compounds of La and Nd have been determined and they are found to be isostructural. The coordination polyhedra for the eight-coordinated metal centre in the complex cation [Ln(N 2O 2)(O 3Cl)] 2+ can be described as distorted square antiprism. Intermolecular hydrogen-bondings involving the three coordinated water molecules and the two uncoordinated chloride ions give rise to the 2-D network in which the chlorides are triply hydrogen-bridged and the water molecules are doubly hydrogen-bridged. Moreover, the aromatic rings in this network are involved in π-π interaction in two different ways. 1H NMR spectra of the complexes in (CD 3) 2SO have been studied. The spectral assignments for the paramagnetic complexes of Ce-Eu have been made from { 1H- 1H} COSY spectra and longitudinal relaxation time ( T1) measurements. It is inferred that the complex species [Ln(LH 2){(CD 3) 2SO} 4] 3+ that exist in solution are isostructural for the compounds of La-Eu. The contact and pseudo-contact contribution to the isotropic paramagnetic shifts in the complexes of Ce-Eu have been estimated. The luminescence spectra of the complexes of La, Sm, Eu and Tb have been studied in methanol-ethanol (1:4) glassy matrix and in the solid state at 77 K, and the quantum yields have been estimated.

  15. Luminescent xerogels obtained through embedding Tb(III) and Eu(III) complexes in silica matrix

    NASA Astrophysics Data System (ADS)

    Stan, Corneliu S.; Marcotte, Nathalie; Secula, Marius S.; Popa, Marcel

    2013-07-01

    The paper reports the preparation of two luminescent xerogels through embedding in a silica matrix of Tb(III) and Eu(III) complexes using succinimide (SI) and N-hydroxysuccinimide (NHSI) as ligands. In the first stage, Tb(III) and Eu(III) complexes with N-hydroxysuccinimide and succinimide were prepared at 1:3 metal to ligand ratio. Strong luminescent emission was observed only in case of Eu(III)-SI and Tb(III)-NHSI complexes while the Eu(III)-NHSI and Tb(III)-SI complexes exhibited none or weak photoluminescent properties. In the second stage, the selected highly luminescent complexes were embedded in silica matrices via a sol-gel procedure leading to the formation of xerogels with transparent-glassy aspect which keep the remarkable photoluminescence properties of the free complexes. The selected, highly luminescent free complexes and their correspondent silica xerogels were investigated through thermal analysis, powder XRD, SEM, FT-IR and fluorescence spectroscopy. Their excellent photoluminescent properties and excitation spectra, conveniently located in UV-A region, might recommend these materials for applications in optoelectronic devices where photonic conversion layers are required.

  16. The Galactic Census of High- and Medium-mass Protostars. III. 12CO Maps and Physical Properties of Dense Clump Envelopes and Their Embedding GMCs

    NASA Astrophysics Data System (ADS)

    Barnes, Peter J.; Hernandez, Audra K.; O'Dougherty, Stefan N.; Schap, William J., III; Muller, Erik

    2016-11-01

    We report the second complete molecular line data release from the Census of High- and Medium-mass Protostars (CHaMP), a large-scale, unbiased, uniform mapping survey at sub-parsec resolution, of millimeter-wave line emission from 303 massive, dense molecular clumps in the Milky Way. This release is for all 12CO J = 1 \\to 0 emission associated with the dense gas, the first from Phase II of the survey, which includes 12CO, 13CO, and C18O. The observed clump emission traced by both 12CO and HCO+ (from Phase I) shows very similar morphology, indicating that, for dense molecular clouds and complexes of all sizes, parsec-scale clumps contain Ξ ˜ 75% of the mass, while only 25% of the mass lies in extended (≳10 pc) or “low density” components in these same areas. The mass fraction of all gas above a density of 109 m-3 is {ξ }9 ≳ 50%. This suggests that parsec-scale clumps may be the basic building blocks of the molecular interstellar medium, rather than the standard GMC concept. Using 12CO emission, we derive physical properties of these clumps in their entirety, and compare them to properties from HCO+, tracing their denser interiors. We compare the standard X-factor converting {I}{12{CO}} to {N}{{{H}}2} with alternative conversions, and show that only the latter give whole-clump properties that are physically consistent with those of their interiors. We infer that the clump population is systematically closer to virial equilibrium than when considering only their interiors, with perhaps half being long-lived (10s of Myr), pressure-confined entities that only terminally engage in vigorous massive star formation, supporting other evidence along these lines that was previously published.

  17. Synthesis, spectroscopic and antimicrobial studies of La(III), Ce(III), Sm(III) and Y(III) Metformin HCl chelates.

    PubMed

    Refat, Moamen S; Al-Azab, Fathi M; Al-Maydama, Hussein M A; Amin, Ragab R; Jamil, Yasmin M S; Kobeasy, Mohamed I

    2015-05-05

    Metal complexes of Metformin hydrochloride were prepared using La(III), Ce(III), Sm(III) and Y(III). The resulting complexes were discussed and synthesized to serve as potential insulin-mimetic. Some physical properties and analytical data of the four complexes were checked. The elemental analysis shows that La(III), Ce(III) Sm(III) and Y(III) formed complexes with Metformin in 1:3 (metal:MF) molar ratio. All the synthesized complexes are white and possess high melting points. These complexes are soluble in dimethylsulfoxide and dimethylformamide, partially soluble in hot methanol and insoluble in water and some other organic solvents. From the spectroscopic (infrared, UV-vis and florescence), effective magnetic moment and elemental analyses data, the formula structures are suggested. The results obtained suggested that Metformin reacted with metal ions as a bidentate ligand through its two imino groups. The molar conductance measurements proved that the Metformin complexes are slightly electrolytic in nature. The kinetic thermodynamic parameters such as: E(∗), ΔH(∗), ΔS(∗) and ΔG(∗) were estimated from the DTG curves. The antibacterial evaluations of the Metformin and their complexes were also performed against some gram positive, negative bacteria as well as fungi.

  18. Synthesis and in vitro microbial evaluation of La(III), Ce(III), Sm(III) and Y(III) metal complexes of vitamin B6 drug

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Al-Azab, Fathi M.; Al-Maydama, Hussein M. A.; Amin, Ragab R.; Jamil, Yasmin M. S.

    2014-06-01

    Metal complexes of pyridoxine mono hydrochloride (vitamin B6) are prepared using La(III), Ce(III), Sm(III) and Y(III). The resulting complexes are investigated. Some physical properties, conductivity, analytical data and the composition of the four pyridoxine complexes are discussed. The elemental analysis shows that the formed complexes of La(III), Ce(III), Sm(III) and Y(III) with pyridoxine are of 1:2 (metal:PN) molar ratio. All the synthesized complexes are brown in color and possess high melting points. These complexes are partially soluble in hot methanol, dimethylsulfoxide and dimethylformamide and insoluble in water and some other organic solvents. Elemental analysis data, spectroscopic (IR, UV-vis. and florescence), effective magnetic moment in Bohr magnetons and the proton NMR suggest the structures. However, definite particle size is determined by invoking the X-ray powder diffraction and scanning electron microscopy data. The results obtained suggested that pyridoxine reacted with metal ions as a bidentate ligand through its phenolate oxygen and the oxygen of the adjacent group at the 4‧-position. The molar conductance measurements proved that the pyridoxine complexes are electrolytic in nature. The kinetic and thermodynamic parameters such as: Ea, ΔH*, ΔS* and ΔG* were estimated from the DTG curves. The antibacterial evaluation of the pyridoxine and their complexes were also performed against some gram positive, negative bacteria as well as fungi.

  19. Synthesis, spectroscopic and antimicrobial studies of La(III), Ce(III), Sm(III) and Y(III) Metformin HCl chelates

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Al-Azab, Fathi M.; Al-Maydama, Hussein M. A.; Amin, Ragab R.; Jamil, Yasmin M. S.; Kobeasy, Mohamed I.

    2015-05-01

    Metal complexes of Metformin hydrochloride were prepared using La(III), Ce(III), Sm(III) and Y(III). The resulting complexes were discussed and synthesized to serve as potential insulin-mimetic. Some physical properties and analytical data of the four complexes were checked. The elemental analysis shows that La(III), Ce(III) Sm(III) and Y(III) formed complexes with Metformin in 1:3 (metal:MF) molar ratio. All the synthesized complexes are white and possess high melting points. These complexes are soluble in dimethylsulfoxide and dimethylformamide, partially soluble in hot methanol and insoluble in water and some other organic solvents. From the spectroscopic (infrared, UV-vis and florescence), effective magnetic moment and elemental analyses data, the formula structures are suggested. The results obtained suggested that Metformin reacted with metal ions as a bidentate ligand through its two imino groups. The molar conductance measurements proved that the Metformin complexes are slightly electrolytic in nature. The kinetic thermodynamic parameters such as: E∗, ΔH∗, ΔS∗ and ΔG∗ were estimated from the DTG curves. The antibacterial evaluations of the Metformin and their complexes were also performed against some gram positive, negative bacteria as well as fungi.

  20. Proof phenomenon as a function of the phenomenology of proving.

    PubMed

    Hipólito, Inês

    2015-12-01

    Kurt Gödel wrote (1964, p. 272), after he had read Husserl, that the notion of objectivity raises a question: "the question of the objective existence of the objects of mathematical intuition (which, incidentally, is an exact replica of the question of the objective existence of the outer world)". This "exact replica" brings to mind the close analogy Husserl saw between our intuition of essences in Wesensschau and of physical objects in perception. What is it like to experience a mathematical proving process? What is the ontological status of a mathematical proof? Can computer assisted provers output a proof? Taking a naturalized world account, I will assess the relationship between mathematics, the physical world and consciousness by introducing a significant conceptual distinction between proving and proof. I will propose that proving is a phenomenological conscious experience. This experience involves a combination of what Kurt Gödel called intuition, and what Husserl called intentionality. In contrast, proof is a function of that process - the mathematical phenomenon - that objectively self-presents a property in the world, and that results from a spatiotemporal unity being subject to the exact laws of nature. In this essay, I apply phenomenology to mathematical proving as a performance of consciousness, that is, a lived experience expressed and formalized in language, in which there is the possibility of formulating intersubjectively shareable meanings.

  1. Vacuum surface flashover: A high-pressure phenomenon

    SciTech Connect

    Gray, E.W.

    1985-07-01

    Desorbed gases from insulator surfaces may be much more important in flashover initiation than properties of the dielectric surface. Ambient neutral densities, immediately above the insulator surface, in the initial stages of flashover have been calculated to lie in the range from 2 x 10/sup 17//cm/sup 3/ to 2 x 10/sup 21//cm/sup 3/ with a mean of about 1 x 10/sup 19//cm/sup 3/, whether flashover occurred on surfaces in air at atmospheric pressure or in vacuum as low as 10/sup -6/ Torr. The evidence presented indicates that, for dc and microsecond pulse voltages, surface flashover is a local, relatively high-pressure phenomenon. Comparison of field strengths of surface flashover for various insulating materials perpendicular to the electrodes, operating pressures, and voltage waveforms appears to indicate that flashover values range well within an order of magnitude (approx.18--80kV/cm). A filamentary nature of the flashover discharge is shown and is consistent with gas breakdown phenomena. Ionization wave front velocities are examined and these compare favorably with those obtained from gaseous breakdown studies.

  2. Cyclic swelling as a phenomenon inherent to biodegradable polyesters.

    PubMed

    Dittrich, Milan; Snejdrova, Eva

    2014-11-01

    The aim of this study is to evaluate and describe the phenomenon and mechanism of the spontaneous cyclic swelling and deswelling of linear and branched aliphatic polyesters in the aqueous medium. The fluctuation of gel volume in one or several cycles as an inherent property of biodegradable and bioerodible materials has not yet been described. We have observed the process at linear and branched polyesters of aliphatic α-hydroxy acids. The period of duration of cycles was in order of hours to days, as influenced by the size of the bodies ranging from 25 to 1000 mg, the temperature in the range of 7°C-42°C, ionic strength, and pH value. The results demonstrated that swelling is accompanied by hydrolysis of ester bonds with the development of small water-soluble osmotically active molecules. After reaching a higher degree of swelling, the obstruction effect of the gel decreases and the diffusion of soluble degradation products from the body to the environment prevails. A decrease in osmotic pressure inside the body and a decrease in the hydrophilic character of the gel matrix result in deswelling by a collapse of the structure, probably due to hydrophobic interactions of nonpolar polyester chains.

  3. Raynaud's phenomenon with oral manifestation in systemic lupus erythematosus.

    PubMed

    da Cunha Bang, F; Lange Wantzin, G; Dahl Christensen, J

    1985-01-01

    A 24-year-old woman with discoid lupus erythematosus developed systemic lupus erythematosus after 6 years. One of the clinical features was Raynaud's phenomenon in the fingers and toes, and furthermore Raynaud's phenomenon appeared in the tongue when exposed to cold and windy weather.

  4. Fluorescence: An Interdisciplinary Phenomenon for Different Education Levels

    ERIC Educational Resources Information Center

    García, J. A.; Moreno, J. M.; Perales, F. J.; Romero, J.; Sánchez, P.; Gómez-Robledo, L.

    2012-01-01

    This paper shows the scientific foundations of a natural phenomenon of undoubted interest and applicability in our day, fluorescence, and its possibilities for teaching at three educational levels: primary, secondary and university. It begins by describing the nature of the phenomenon and continues by explaining how we work with students of the…

  5. The Grey Nomad Phenomenon: Changing the Script of Aging

    ERIC Educational Resources Information Center

    Onyx, Jenny; Leonard, Rosemary

    2007-01-01

    This article explores a relatively new and little understood phenomenon, that of the Australian Grey Nomads. Every year increasing numbers of older Australians take to the road. This article explores the phenomenon both empirically and theoretically. A grounded approach is used by which the experience is explored from an ethnographic account…

  6. Raynaud's phenomenon of the nipples: an elusive diagnosis.

    PubMed

    Morino, Carolyn; Winn, Susan M

    2007-05-01

    Pain and throbbing of the nipples associated with Raynaud's phenomenon often mimics yeast or fungal infections. Breastfeeding mothers with Raynaud's of the nipples are often treated inappropriately for organisms such as Candida Albicans with topical or systemic antifungal agents. This case report describes the eventual diagnosis of Raynaud's phenomenon of the nipples in a breastfeeding mother who was initially treated for yeast.

  7. STUDIES ON THE MECHANISM OF THE SHWARTZMAN PHENOMENON

    PubMed Central

    Stetson, Chandler A.; Good, Robert A.

    1951-01-01

    The inhibition of the Shwartzman phenomenon by nitrogen mustard and benzene has been confirmed and investigated further. This inhibition can be correlated with the leucopenia induced by these agents. Evidence is presented indicating that polymorphonuclear leucocytes play an essential role in the preparation of the skin for the Shwartzman phenomenon. PMID:14803631

  8. Theoretical insights into the separation of Am(III) over Eu(III) with PhenBHPPA.

    PubMed

    Wu, Han; Wu, Qun-Yan; Wang, Cong-Zhi; Lan, Jian-Hui; Liu, Zhi-Rong; Chai, Zhi-Fang; Shi, Wei-Qun

    2015-10-14

    Due to the similar chemical properties of actinides An(iii) and lanthanides Ln(iii), their separation in spent nuclear fuel reprocessing is extremely challenging. A 1,10-phenanthroline dipicolinamide-based ligand (PhenBHPPA) has been identified to possess a selectivity for Am(iii) over Eu(iii) and could potentially be used for group actinide extraction. In this study, quasi-relativistic density functional theoretical calculations have been used to disclose the interaction mechanisms of Am(iii) and Eu(iii) complexes with PhenBHPPA. The electronic structures, bonding nature, QTAIM (Quantum Theory of Atoms in Molecules) analyses and thermodynamic behaviors of the Am(iii) and Eu(iii) complexes with PhenBHPPA have been explored in detail. According to the Wiberg bond indices (WBIs) and QTAIM analyses, interactions between the ligand and metal cations (Am(iii) and Eu(iii)) exhibit a weakly covalent character. Thermodynamic analyses show that the charged complexes [ML(NO3)2](+) appear to be the most stable species in the complexation processes. Moreover, it is more energetically favorable for PhenBHPPA to bind to Am(iii) compared to Eu(iii). Our study could render new insights into understanding the selectivity of the ligand towards minor actinides and the separation of An(iii) from Ln(iii) via liquid-liquid extraction.

  9. Synthesis and photophysical properties of peripherally and non-peripherally mercaptopyridine substituted metal free, Mg(II) and Al(III) phthalocyanines

    NASA Astrophysics Data System (ADS)

    Arslanoğlu, Yasin; Idowu, Mopelola; Nyokong, Tebello

    The syntheses and photophysical properties of metallophthalocyanines containing Mg2+ and Al3+ as central metal ions and their unmetallated derivative (complexes 3-8) tetra- substituted at the non-peripheral (α) and peripheral (β) positions with 2-mercaptopyridine are reported. The trends in triplet and fluorescence quantum yields are described for these compounds. The complexes exhibited relatively high triplet quantum yields (ΦT) ranging from 0.33 to 0.54 and fluorescence quantum yields (ΦF) ranging from 0.02 to 0.29. Triplet state lifetimes of the complexes were long ranging from 120 to 460 μs, indicating a potential use of these complexes as photosensitizers.

  10. On the evolution of accretion disc flow in cataclysmic variables. III - Outburst properties of constant and uniform-alpha model discs

    NASA Technical Reports Server (NTRS)

    Lin, D. N. C.; Faulkner, J.; Papaloizou, J.

    1985-01-01

    Attention is given to the stability and evolution of some simple accretion disk models in which the viscosity is prescribed by an ad hoc, uniform-alpha model. Emphasis is placed on systems in which the mass input rate from the secondary to the disk around the primary is assumed to be constant, although initial calculations with variable mass input rates are also performed. Time-dependent visual magnitude light curves constructed for cataclysmic binaries with a range of disk size, primary mass and mass input rate, and viscosity magnitude, are compared with the observed properties of various cataclysmic variable subclasses. The results obtained indicate that the observational differences between novae and dwarf novae may be due to mass input rate differences. The present models can reproduce the gross observational features of U-Gem-type dwarf nova outbursts.

  11. [Study on whorl swarming growth phenomenon of Proteus mirabilis].

    PubMed

    He, Xianyuan; Liao, Sixiang; Liu, Junkang; Li, Kun; Liu, Yanxia; Yu, Lurong

    2015-02-01

    The present paper is aimed to explore the origins of Proteus mirabilis (PM) whorl swarming growth phenomenon. The whorl swarming growth phenomenon of PM was observed by changed bacterial culture inoculation time, humidity, vaccination practices, cultured flat placement, magnetic field, pH and other factors. Bacterial ring spiral direction of rotation is counterclockwise and the volatile growth process of PM was whorl swarming growth phenomenon. Spiro fluctuation phenomenon was of high frequency in the sealing tanks by cultured anytime inoculation, wherever inoculation technique applied or not, the presence or absence of the magnetic field, and wherever the dish position was. The experimental results showed that the whorl swarming growth phenomenon of PM requires specific pH environment, in which the facts may be relative to its genetic characteristics and the Earths rotation.

  12. Correction of the Pulfrich phenomenon by surgery and laser.

    PubMed

    Diaper, Charles J M; Heron, Gordon; MacMillan, Ewen S

    2002-02-01

    We describe 2 patients who presented with asymmetrical media changes and a spontaneous Pulfrich phenomenon. In the first case, the phenomenon was due to cataract formation and an interocular latency difference of 1.49 ms +/-0.07 (SD) was found. After cataract surgery, the symptoms resolved and no interocular latency difference could be measured. In the second case, the phenomenon was caused by posterior capsule opacification and an interocular latency difference of 1.16 +/- 0.08 ms was found. The symptoms were alleviated and no interocular latency difference could be measured after a neodymium:YAG laser capsulotomy was performed. The symptomatology of the Pulfrich phenomenon is often difficult for patients to explain. Clinicians should be aware of the phenomenon with cataract patients.

  13. Property.

    ERIC Educational Resources Information Center

    Goldblatt, Steven M.; Piele, Philip K.

    This chapter reviews 1982 cases related to school property. Cases involving citizen efforts to overturn school board decisions to close schools dominate the property chapter, and courts continue to uphold school board authority to close schools, transfer students, and sell or lease the buildings. Ten cases involving detachment and attachment of…

  14. Property.

    ERIC Educational Resources Information Center

    Bickel, Robert D.; Zeller, Trisha A.

    A number of cases related to property issues involving institutions of higher education are examined in this chapter. Cases discussed touch on such topics as funding for property and equipment acquisition; opposition to building construction or demolition; zoning issues; building construction and equipment contracts; and lease agreements. Current…

  15. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.; Johnson, Margaret M.

    This chapter deals with 1981 cases involving disputes over property. Cases involving the detachment and attachment of land continue to dominate the property chapter with 11 cases reported, the same number summarized in last year's chapter. One case involving school board referenda raised the interesting question of whether or not a state could…

  16. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.

    Chapter 7 of a book on school law, this chapter deals with 1979 cases involving disputes over property. Cases involving taxpayer attempts to prevent the construction of school buildings dominate this year's property chapter, as they did last year's. Yet, paradoxically, there is also a significant increase in cases in which taxpayers tried to…

  17. Photochemical Properties of Red-Emitting Tris(cyclometalated) Iridium(III) Complexes Having Basic and Nitro Groups and Application to pH Sensing and Photoinduced Cell Death.

    PubMed

    Kando, Aya; Hisamatsu, Yosuke; Ohwada, Hiroki; Itoh, Taiki; Moromizato, Shinsuke; Kohno, Masahiro; Aoki, Shin

    2015-06-01

    Cyclometalated iridium(III) complexes, because of their photophysical properties, have the potential for use as luminescent probes for cellular imaging. We previously reported on a pH-activatable iridium complex that contains three N,N-diethylamino groups, namely, fac-Ir(deatpy)3 5, which was synthesized via a regioselective aromatic substitution reaction at the 5'-position with tolylpyridine groups of fac-Ir(tpy)3 2. It was found that 5 shows a considerable enhancement in emission intensity in the pH range from neutral to slightly acidic (pH 6.5-7.4) in aqueous solution and selectively stains lysosome in HeLa-S3 cells, due to the protonation of the diethylamino groups. In addition, 5 functions as a pH-dependent singlet oxygen ((1)O2) generator and induces necrosis-like cell death. However, observing the green emission of 5 is often hampered by autofluorescence emanating from nearby tissues. To overcome this problem, we designed and synthesized a series of new pH-activatable Ir(III) complexes that contain diethylamino, guanidyl, and iminoimidazolidinyl groups on the mpiq ligand of Ir(mpiq)3 7 and the tfpiq ligand of Ir(tfpiq)3 8, which exhibit a red emission, namely, Ir(deampiq)3 13, Ir(gmpiq)3 14, Ir(imzmpiq)3 15, and Ir(imztfpiq)3 16. The emission intensity of these Ir complexes is enhanced substantially by protonation of their basic groups, and they induce the necrosis-like cell death of HeLa-S3 cells by photoirradiation at 465 nm. A strong orange-red emission of Ir(mpiq-NO2)3 9 and Ir(tfpiq-NO2)3 10 is also reported.

  18. Synthesis, structural characterization, solution behavior, and in vitro antiproliferative properties of a series of gold complexes with 2-(2'-pyridyl)benzimidazole as ligand: comparisons of gold(III) versus gold(I) and mononuclear versus binuclear derivatives.

    PubMed

    Serratrice, Maria; Cinellu, Maria A; Maiore, Laura; Pilo, Maria; Zucca, Antonio; Gabbiani, Chiara; Guerri, Annalisa; Landini, Ida; Nobili, Stefania; Mini, Enrico; Messori, Luigi

    2012-03-05

    A variety of gold(III) and gold(I) derivatives of 2-(2'-pyridyl)benzimidazole (pbiH) were synthesized and fully characterized and their antiproliferative properties evaluated in a representative ovarian cancer cell line. The complexes include the mononuclear species [(pbi)AuX(2)] (X = Cl, 1; OAc, 2), [(pbiH)AuCl] (3), [(pbiH)Au(PPh(3))][PF(6)] (4-PF(6)), and [(pbi)Au(L)] (L = PPh(3), 5; TPA, 6), and the binuclear gold(I)/gold(I) and gold(I)/gold(III) derivatives [(PPh(3))(2)Au(2)(μ(2)-pbi)][PF(6)] (10-PF(6)), [ClAu(μ(3)-pbi)AuCl(2)] (7),and [(PPh(3))Au(μ(3)-pbi)AuX(2)][PF(6)] (X = Cl, 8-PF(6); OAc, 9-PF(6)). The molecular structures of 6, 7, and 10-PF(6) were determined by X-ray diffraction analysis. The chemical behavior of these compounds in solution was analyzed both by cyclic voltammetry in DMF and absorption UV-vis spectroscopy in an aqueous buffer. Overall, the stability of these gold compounds was found to be acceptable for the cellular studies. For all complexes, relevant antiproliferative activities in vitro were documented against A2780 human ovarian carcinoma cells, either resistant or sensitive to cisplatin, with IC(50) values falling in the low micromolar or even in the nanomolar range. The investigated gold compounds were found to overcome resistance to cisplatin to a large degree. Results are interpreted and discussed in the frame of current knowledge on cytotoxic and antitumor gold compounds.

  19. Reinforcement of acrylic resins for provisional fixed restorations. Part III: effects of addition of titania and zirconia mixtures on some mechanical and physical properties.

    PubMed

    Panyayong, W; Oshida, Y; Andres, C J; Barco, T M; Brown, D T; Hovijitra, S

    2002-01-01

    Acrylic resins have been used in many different applications in dentistry, especially in the fabrication of provisional fixed partial dentures. Ideally, a provisional crown and bridge material should be easy to handle and should protect teeth against physical, chemical, and thermal injuries. Some of the problems associated with this use are related to the material's poor mechanical properties. It has been demonstrated that acrylic resin can be strengthened through the addition of structural component of different size distributed in the acrylic matrix, thus forming a composite structure. The purpose of this study was to investigate the addition effects of mixtures of titania (titanium dioxide, TiO(2)) powder and zirconia (zirconium dioxide, ZrO(2)) powder being incorporated with pre-polymerized beads mixed in monomer liquid, on some mechanical and physical properties of PMMA resin. The pre-polymerized powder poly(methyl methacrylate) resin was admixed with titania and zirconia powder. A mixing ratio was controlled by volume % of 0, 1.0, 2.0, and 3.0 (samples with 0 v/o served as control groups). For using mixture of titania and zirconia, total amount of the mixture was controlled by volume % of 1.0, 2.0, and 3.0, in which titania and zirconia were mixed at the ratio 1 :1, 1 :2 and 2 :1. Prior to mechanical tests, all rectangular-shaped samples (25 mm x 2 mm x 5 mm) were stored in 37 degrees C distilled water for 7 days after polishing all six sides of samples. Samples were then subjected to the three-point bending flexion test to evaluate the bending strength as well as the modulus of elasticity. Weight gain and exothermic reaction survey were investigated as well. All data were collected and analyzed with one-way analysis of variance (ANOVA) and Sidak method (p=0.05). It was found that the addition of particles generally decreased the water absorbed by the composite system. Only 1 percent by volume concentration of 1 :1 ratio and 2 percent by volume concentration

  20. New 1,2,4-triazole-based azo-azomethine dye. Part III: Synthesis, characterization, thermal property, spectrophotometric and computational studies

    NASA Astrophysics Data System (ADS)

    Erfantalab, Malihe; Khanmohammadi, Hamid

    A new 1,2,4-triazole-based azo-azomethine compound, H2L, has been prepared by condensation reaction of 1-(3-formyl-4-hydroxyphenylazo)-4-ethylbenzene with prepared triazole-based diamine. The structure of H2L was characterized by using FT-IR, UV-Vis and 1H NMR spectroscopic methods as well as elemental analysis. Hard model chemometrics method has been used to determine the formation constants of zinc(II), copper(II), nickel(II) and cobalt(II) complexes of H2L in DMSO by UV-Vis spectrophotometric method. Solvatochromic behavior of the dye has been also investigated in some organic solvents with different polarities. Thermal properties of the prepared dye was examined by thermogravimetric analysis. Results indicated that the framework of the dye was stable up to 245 °C. Furthermore,1H chemical shifts and UV-Vis of H2L were studied by the gauge independent atomic orbital (GIAO), continuous set of gauge transformations (CSGT) and time-dependent density functional theory (TD-DFT) methods respectively at the level of density functional theory using B3LYP/6-311+G(d) basis sets in DMSO. The computational data are in reasonably good agreement with the experimental data.

  1. Synthesis, radii dependent self-assembly crystal structures and luminescent properties of rare earth (III) complexes with a tripodal salicylic derivative.

    PubMed

    Wang, Ya-Wen; Zhang, Yan-Ling; Dou, Wei; Zhang, Ai-Jiang; Qin, Wen-Wu; Liu, Wei-Sheng

    2010-10-14

    Five new rare earth complexes with a new flexible tripodal salicylic ligand (H(3)L), 2,2'-(2-((2-carboxyphenoxy)methyl)-2-(4-methylphenylsulfonamido)propane-1,3-diyl)bis(oxy)dibenzoic acid, of formulae [La(2)L(2)(DMF)(4)]·4DMF·4EtOH·2H(2)O (1), [Eu(2)L(2)(DMF)(4)]·2DMF (2), {[GdL(DMF)(H(2)O)(2)]·DMF}(∞) (3), {[TbL(DMF)(H(2)O)(2)]·DMF}(∞) (4) and {[YL(DMF)(H(2)O)(2)]·DMF}(∞) (5) (DMF = N,N-dimethylformamide) have been prepared. The single-crystal X-ray diffraction analysis revealed that complexes 1 and 2 present a cage-like homodinuclear species, while 3-5 show a helical one-dimensional coordination polymer. All these complexes are further connected by hydrogen bonds or π-π interactions, resulting in 3D supramolecular structures. The photophysical properties of the Eu and Tb complexes are investigated in the solid state at room temperature.

  2. Polyaryl ether dendrimer with a 4-phenylacetyl-5-pyrazolone-based terbium(III) complex as core: synthesis and photophysical properties.

    PubMed

    Shen, Li; Shi, Mei; Li, Fuyou; Zhang, Dengqing; Li, Xianghong; Shi, Enxian; Yi, Tao; Du, Yukou; Huang, Chunhui

    2006-08-07

    A series of novel dendritic beta-diketone ligands, 1-phenyl-3-[G-n]-4-phenylacetyl-5-pyrazolone (n = 0-3, G stands for polyaryl ether), were synthesized by introducing Fréchet-type dendritic branches. The corresponding Tb3+-cored dendritic complexes were characterized by X-ray crystallography, elemental analysis, ESI mass spectra, and FT-IR spectra. These dendritic complexes, prepared from aqueous solution, exhibit high stability. Interestingly, the study of photophysical properties shows that the luminescence quantum yields of the dendritic Tb-complexes increase from 0.1 to 2.26% with an increase of the dendritic generation from 0 to 3. Importantly, an "energy-reservoir effect" was observed in the dendritic system using the method based on the resonance energy transfer from these complexes to rhodamine 6G. With the increase of the dendritic generation, the metal-centered luminescence quantum yield was almost the same, and the energy transfer (phi(transfer)) from the ligand to Tb(3+) increased. Further measurements of the triplet state and oxygen quenching of these dendritic complexes verify that this enhancement of the energy transfer (phi(transfer)) is attributed to both an "antenna effect" and a "shell effect".

  3. Evaluation of the grand-canonical partition function using expanded Wang-Landau simulations. III. Impact of combining rules on mixtures properties

    SciTech Connect

    Desgranges, Caroline; Delhommelle, Jerome

    2014-03-14

    Combining rules, such as the Lorentz-Berthelot rules, are routinely used to calculate the thermodynamic properties of mixtures using molecular simulations. Here we extend the expanded Wang-Landau simulation approach to determine the impact of the combining rules on the value of the partition function of binary systems, and, in turn, on the phase coexistence and thermodynamics of these mixtures. We study various types of mixtures, ranging from systems of rare gases to biologically and technologically relevant mixtures, such as water-urea and water-carbon dioxide. Comparing the simulation results to the experimental data on mixtures of rare gases allows us to rank the performance of combining rules. We find that the widely used Lorentz-Berthelot rules exhibit the largest deviations from the experimental data, both for the bulk and at coexistence, while the Kong and Waldman-Hagler provide much better alternatives. In particular, in the case of aqueous solutions of urea, we show that the use of the Lorentz-Berthelot rules has a strong impact on the Gibbs free energy of the solute, overshooting the value predicted by the Waldman-Hagler rules by 7%. This result emphasizes the importance of the combining rule for the determination of hydration free energies using molecular simulations.

  4. STELLAR KINEMATICS AND STRUCTURAL PROPERTIES OF VIRGO CLUSTER DWARF EARLY-TYPE GALAXIES FROM THE SMAKCED PROJECT. III. ANGULAR MOMENTUM AND CONSTRAINTS ON FORMATION SCENARIOS

    SciTech Connect

    Toloba, E.; Guhathakurta, P.; Peletier, R. F.; Emsellem, E.; Lisker, T.; Van de Ven, G.; Simon, J. D.; Adams, J. J.; Benson, A. J.; Falcón-Barroso, J.; Ryś, A.; Gorgas, J.; Hensler, G.; Janz, J.; Laurikainen, E.; Salo, H.; Paudel, S.

    2015-02-01

    We analyze the stellar kinematics of 39 dwarf early-type galaxies (dEs) in the Virgo Cluster. Based on the specific stellar angular momentum λ{sub Re} and the ellipticity, we find 11 slow rotators and 28 fast rotators. The fast rotators in the outer parts of the Virgo Cluster rotate significantly faster than fast rotators in the inner parts of the cluster. Moreover, 10 out of the 11 slow rotators are located in the inner 3° (D < 1 Mpc) of the cluster. The fast rotators contain subtle disk-like structures that are visible in high-pass filtered optical images, while the slow rotators do not exhibit these structures. In addition, two of the dEs have kinematically decoupled cores and four more have emission partially filling in the Balmer absorption lines. These properties suggest that Virgo Cluster dEs may have originated from late-type star-forming galaxies that were transformed by the environment after their infall into the cluster. The correlation between λ{sub Re} and the clustercentric distance can be explained by a scenario where low luminosity star-forming galaxies fall into the cluster, their gas is rapidly removed by ram-pressure stripping, although some of it can be retained in their core, their star formation is quenched but their stellar kinematics are preserved. After a long time in the cluster and several passes through its center, the galaxies are heated up and transformed into slow rotating dEs.

  5. SUPERSTARS III: K-2.

    ERIC Educational Resources Information Center

    North Carolina State Dept. of Public Education, Raleigh.

    SUPERSTARS III is a K-8 program designed as an enrichment opportunity for self-directed learners in mathematics. The basic purpose of SUPERSTARS III is to provide the extra challenge that self-motivated students need in mathematics and to do so in a structured, long-term program that does not impinge on the normal classroom routine or the…

  6. PROPERTIES OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE NORTHWEST PHOTON DOMINATED REGION OF NGC 7023. III. QUANTIFYING THE TRADITIONAL PROXY FOR PAH CHARGE AND ASSESSING ITS ROLE

    SciTech Connect

    Boersma, C.; Bregman, J.; Allamandola, L. J.

    2015-06-10

    Polycyclic aromatic hydrocarbon (PAH) emission in the Spitzer/IRS spectral map of the northwest photon dominated region (PDR) in NGC 7023 is analyzed. Here, results from fitting the 5.2–14.5 μm spectrum at each pixel using exclusively PAH spectra from the NASA Ames PAH IR Spectroscopic Database (www.astrochem.org/pahdb/) and observed PAH band strength ratios, determined after isolating the PAH bands, are combined. This enables the first quantitative and spectrally consistent calibration of PAH charge proxies. Calibration is straightforward because the 6.2/11.2 μm PAH band strength ratio varies linearly with the ionized fraction (PAH ionization parameter) as determined from the intrinsic properties of the individual PAHs comprising the database. This, in turn, can be related to the local radiation field, electron density, and temperature. From these relations diagnostic templates are developed to deduce the PAH ionization fraction and astronomical environment in other objects. The commonly used 7.7/11.2 μm PAH band strength ratio fails as a charge proxy over a significant fraction of the nebula. The 11.2/12.7 μm PAH band strength ratio, commonly used as a PAH erosion indicator, is revealed to be a better tracer for PAH charge across NGC 7023. Attempting to calibrate the 12.7/11.2 μm PAH band strength ratio against the PAH hydrogen adjacency ratio (duo+trio)/solo is, unexpectedly, anti-correlated. This work both validates and extends the results from Paper I and Paper II.

  7. Design, synthesis, characterization, and OFET properties of amphiphilic heteroleptic tris(phthalocyaninato) europium(III) complexes. The effect of crown ether hydrophilic substituents.

    PubMed

    Gao, Yingning; Ma, Pan; Chen, Yanli; Zhang, Ying; Bian, Yongzhong; Li, Xiyou; Jiang, Jianzhuang; Ma, Changqin

    2009-01-05

    Two amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic crown ether heads and hydrophobic octyloxy tails [Pc(mCn)(4)]Eu[Pc(mCn)(4)]Eu[Pc(OC(8)H(17))(8)] [m = 12, n = 4, H(2)Pc(12C4)(4) = 2,3,9,10,16,17,23,24-tetrakis(12-crown-4)phthalocyanine; m = 18, n = 6, H(2)Pc(18C6)(4) = 2,3,9,10,16,17,23,24-tetrakis(18-crown-6)phthalocyanine; H(2)Pc(OC(8)H(17))(8) = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] (1, 2) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound [Pc(mCn)(4)]Eu[Pc(mCn)(4)] (m = 12, n = 4; m = 18, n = 6) and metal-free H(2)Pc(OC(8)H(17))(8) in the presence of Eu(acac)(3).H(2)O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene. These novel sandwich triple-decker complexes were characterized by a wide range of spectroscopic methods and electrochemically studied. With the help of the Langmuir-Blodgett technique, these typical amphiphilic triple-decker complexes were fabricated into organic field effect transistors (OFET) with top contact configuration on bare SiO(2)/Si substrate, hexamethyldisilazane-treated SiO(2)/Si substrate, and octadecyltrichlorosilane (OTS)-treated SiO(2)/Si substrate, respectively. The device performance is revealed to be dependent on the species of crown ether substituents and substrate surface treatment. OFETs fabricated from the triple decker with 12-crown-4 hydrophilic substituents, 1, allow the hole transfer in the direction parallel to the aromatic phthalocyanine rings. In contrast, the devices of a triple-decker compound containing 18-crown-6 as hydrophilic heads, 2, transfer holes in a direction along the long axis of the assembly composed of face-to-face aggregated triple-decker molecules, revealing the effect of molecular structure, specifically the crown ether substituents on the film structure and OFET functional properties. The carrier mobility for hole as high as 0.33 cm(2) V(-1) s(-1) and current modulation of 7.91 x 10

  8. THE BOLOCAM GALACTIC PLANE SURVEY. III. CHARACTERIZING PHYSICAL PROPERTIES OF MASSIVE STAR-FORMING REGIONS IN THE GEMINI OB1 MOLECULAR CLOUD

    SciTech Connect

    Dunham, Miranda K.; Evans, Neal J.; Harvey, Paul; Merello, Manuel; Rosolowsky, Erik; Cyganowski, Claudia J.; Aguirre, James; Bally, John; Battersby, Cara; Ginsburg, Adam; Glenn, Jason; Stringfellow, Guy S.; Bradley, Eric Todd; Dowell, Darren; Drosback, Meredith; Schlingman, Wayne; Shirley, Yancy L.; Walawender, Josh; Williams, Jonathan P.

    2010-07-10

    We present the 1.1 mm Bolocam Galactic Plane Survey (BGPS) observations of the Gemini OB1 molecular cloud complex, and targeted NH{sub 3} observations of the BGPS sources. When paired with molecular spectroscopy of a dense gas tracer, millimeter observations yield physical properties such as masses, radii, mean densities, kinetic temperatures, and line widths. We detect 34 distinct BGPS sources above 5{sigma} = 0.37 Jy beam{sup -1} with corresponding 5{sigma} detections in the NH{sub 3}(1,1) transition. Eight of the objects show water maser emission (20%). We find a mean millimeter source FWHM of 1.12 pc and a mean gas kinetic temperature of 20 K for the sample of 34 BGPS sources with detections in the NH{sub 3}(1,1) line. The observed NH{sub 3} line widths are dominated by non-thermal motions, typically found to be a few times the thermal sound speed expected for the derived kinetic temperature. We calculate the mass for each source from the millimeter flux assuming the sources are isothermal and find a mean isothermal mass within a 120'' aperture of 230 {+-} 180 M{sub sun}. We find a total mass of 8400 M{sub sun} for all BGPS sources in the Gemini OB1 molecular cloud, representing 6.5% of the cloud mass. By comparing the millimeter isothermal mass to the virial mass calculated from the NH{sub 3} line widths within a radius equal to the millimeter source size, we find a mean virial parameter (M{sub vir}/M {sub iso}) of 1.0 {+-} 0.9 for the sample. We find mean values for the distributions of column densities of 1.0 x 10{sup 22} cm{sup -2} for H{sub 2}, and 3.0 x 10{sup 14} cm{sup -2} for NH{sub 3}, giving a mean NH{sub 3} abundance of 3.0 x 10{sup -8} relative to H{sub 2}. We find volume-averaged densities on the order of 10{sup 3}-10{sup 4} cm{sup -3}. The sizes and densities suggest that in the Gem OB1 region the BGPS is detecting the clumps from which stellar clusters form, rather than smaller, higher density cores where single stars or small multiple systems

  9. Uhthoff's phenomenon in multiple sclerosis and neuromyelitis optica.

    PubMed

    Park, Kwiyoung; Tanaka, Keiko; Tanaka, Masami

    2014-01-01

    To evaluate and compare the incidence and clinical features of Uhthoff's phenomenon in Japanese patients with neuromyelitis optica (NMO) and those with multiple sclerosis (MS), we asked 135 consecutive patients with MS and an NMO-related disorder (NMOrd) whether they experienced worse neurological symptoms after an increase in body temperature. Responses were obtained from 54 MS and 37 NMOrd patients. Uhthoff's phenomenon was observed in 26 MS (48.1%) and 20 NMOrd patients (54.1%). Motor and sensory symptoms were more frequent than visual symptoms in both diseases. The incidence of Uhthoff's phenomenon was similar in MS and NMOrd.

  10. The Page kidney phenomenon secondary to a traumatic fall.

    PubMed

    Babel, Nitin; Sakpal, Sujit Vijay; Chamberlain, Ronald Scott

    2010-02-01

    Page kidney is a rare phenomenon of hyperreninemic hypertension caused by compression of the renal parenchyma. It has been reported in healthy individuals after blunt abdominal or flank trauma, and in patients after invasive nephrological interventions. We present a case of acute on chronic renal failure and Page kidney phenomenon in an elderly male after a traumatic fall, who underwent effective medical management until spontaneous recovery to baseline was observed. A brief discussion on the Page kidney phenomenon is provided with a suggested algorithmic approach towards the management of this process.

  11. Lucio's phenomenon: exuberant case report and review of Brazilian cases*

    PubMed Central

    Rocha, Rafael Henrique; Emerich, Paulo Sergio; Diniz, Lucia Martins; de Oliveira, Marcela Bahia Barretto; Cabral, Aline Neves Freitas; do Amaral, Ana Cristina Vervloet

    2016-01-01

    Lucio’s phenomenon is an uncommon reaction characterized by severe necrotizing cutaneous lesions that occurs in patients with Lucio’s leprosy and lepromatous leprosy. It is considered by some authors as a variant of type 2 or 3 reaction. Death can occur because of blood dyscrasia or sepsis. Precipitating factors include infections, drugs and pregnancy. We report a 31-year-old female patient exhibiting both clinical and histopathological features of lepromatous leprosy and Lucio’s phenomenon presenting favorable response to treatment. We complement our report with a literature review of the Brazilian cases of Lucio’s phenomenon published in Portuguese and English. PMID:28300896

  12. Severe Raynaud's phenomenon-A streamlined approach to acute management.

    PubMed

    Lee, Regent; Lomas, Oliver; Handa, Ashok

    2011-01-01

    Raynaud's phenomenon is an exaggerated vasospastic response to cold or emotional stress which not only may cause the patient severe pain but also critical ischaemia and necrosis of the digits. We report the case of a 69-year-old woman who presented with rest pain, impending ulceration and necrosis of finger tips due to an episode of left-sided Raynaud's phenomenon. Intravenous prostacyclin was administered successfully as a bridge to endoscopic thoracic sympathectomy. Vascular surgery units are ideally positioned for the acute management of severe Raynaud's phenomenon to provide continuity of care to patients with profound digital ischaemia and impending tissue loss.

  13. The ''hot spleen'' phenomenon in metastatic malignant melanoma: its incidence and relationship with the immune system

    SciTech Connect

    Wagstaff, J.; Phadke, K.; Adam, N.; Thatcher, N.; Crowther, D.

    1982-02-01

    Of patients with Stage II and III malignant melanoma, 34.7% display reversal of the liver-spleen ratio on technetium-99m-sulfhur colloid isotope scans. Such an occurrence does not suggest a greater likelihood of relapse or a worse survival. The phenomenom is more common in female patients and there is a significant relationship between the presence of a ''hot spleen'' and a high IgM level. Patients with Stage II disease and high IgM levels have relapses more quickly than do those with normal IgM levels. Lymphopenia is common in patients with Stage II and III disease and the survival of these patients is worse than that of those with normal lymphocyte counts. In this report, the data are discussed together with results from other investigations, and a unifying hypothesis is presented which explains the phenomenon and relates it to increased activity of macrophages as a result of the presence of the tumor. The usefulness of isotope liver scanning in stage III malignant melanoma is also discussed.

  14. Exploring wind-driving dust species in cool luminous giants. III. Wind models for M-type AGB stars: dynamic and photometric properties

    NASA Astrophysics Data System (ADS)

    Bladh, S.; Höfner, S.; Aringer, B.; Eriksson, K.

    2015-03-01

    Context. Stellar winds observed in asymptotic giant branch (AGB) stars are usually attributed to a combination of stellar pulsations and radiation pressure on dust. Shock waves triggered by pulsations propagate through the atmosphere, compressing the gas and lifting it to cooler regions which creates favourable conditions for grain growth. If sufficient radiative acceleration is exerted on the newly formed grains through absorption or scattering of stellar photons, an outflow can be triggered. Strong candidates for wind-driving dust species in M-type AGB stars are magnesium silicates (Mg2SiO4 and MgSiO3). Such grains can form close to the stellar surface, they consist of abundant materials and, if they grow to sizes comparable to the wavelength of the stellar flux maximum, they experience strong acceleration by photon scattering. Aims: The purpose of this study is to investigate if photon scattering on Mg2SiO4 grains can produce realistic outflows for a wide range of stellar parameters in M-type AGB stars. Methods: We use a frequency-dependent radiation-hydrodynamics code with a detailed description for the growth of Mg2SiO4 grains to calculate the first extensive set of time-dependent wind models for M-type AGB stars. This set includes 139 solar-mass models, with three different luminosities (5000 L⊙, 7000 L⊙, and 10 000 L⊙) and effective temperatures ranging from 2600 K to 3200 K. The resulting wind properties, visual and near-IR photometry and mid-IR spectra are compared with observations. Results: We show that the models can produce outflows for a wide range of stellar parameters. We also demonstrate that they reproduce observed mass-loss rates and wind velocities, as well as visual and near-IR photometry. However, the current models do not show the characteristic silicate features at 10 and 18 μm as a result of the cool temperature of Mg2SiO4 grains in the wind. Including a small amount of Fe in the grains further out in the circumstellar envelope will

  15. The mass-loss return from evolved stars to the Large Magellanic Cloud. III. Dust properties for carbon-rich asymptotic giant branch stars

    NASA Astrophysics Data System (ADS)

    Srinivasan, S.; Sargent, B. A.; Matsuura, M.; Meixner, M.; Kemper, F.; Tielens, A. G. G. M.; Volk, K.; Speck, A. K.; Woods, P. M.; Gordon, K.; Marengo, M.; Sloan, G. C.

    2010-12-01

    We present a radiative transfer model for the circumstellar dust shell around a Large Magellanic Cloud (LMC) long-period variable (LPV) previously studied as part of the Optical Gravitational Lensing Experiment (OGLE) survey of the LMC. OGLE LMC LPV 28579 (SAGE J051306.40-690946.3) is a carbon-rich asymptotic giant branch (AGB) star for which we have Spitzer broadband photometry and spectra from the SAGE and SAGE-Spec programs along with broadband UBVIJHKs photometry. By modeling this source, we obtain a baseline set of dust properties to be used in the construction of a grid of models for carbon stars. We reproduce the spectral energy distribution of the source using a mixture of amorphous carbon and silicon carbide with 15% SiC by mass. The grain sizes are distributed according to the KMH model, with γ = 3.5, amin = 0.01 μm and a0 = 1.0 μm. The best-fit model produces an optical depth of 0.28 for the dust shell at the peak of the SiC feature (11.3 μm), with an inner radius of about 1430 R_⊙ or 4.4 times the stellar radius. The temperature at this inner radius is 1310 K. Assuming an expansion velocity of 10 km s-1, we obtain a dust mass-loss rate of 2.5 × 10-9 M_⊙ yr-1. We calculate a 15% variation in this mass-loss rate by testing the sensitivity of the fit to variation in the input parameters. We also present a simple model for the molecular gas in the extended atmosphere that could give rise to the 13.7 μm feature seen in the spectrum. We find that a combination of CO and C2H2 gas at an excitation temperature of about 1000 K and column densities of 3 × 1021 cm-2 and 1019 cm-2 respectively are able to reproduce the observations. Given that the excitation temperature is close to the temperature of the dust at the inner radius, most of the molecular contribution probably arises from this region. The luminosity corresponding to the first epoch of SAGE observations is 6580 L_⊙. For an effective temperature of about 3000 K, this implies a stellar mass of

  16. Parametrization of the magnetic behavior of the triangular spin ladder chains organically templated: (C2N2H10)[M(HPO3)F3] (M(III) = Fe, Cr, and V). Crystal structure and thermal and spectroscopic properties of the iron(III) phase.

    PubMed

    Fernández-Armas, Sergio; Mesa, José L; Pizarro, José L; Clemente-Juan, Juan Modesto; Coronado, Eugenio; Arriortua, María I; Rojo, Teófilo

    2006-04-17

    A new iron(III) phosphite templated by ethylenediamine has been synthesized using solvothermal conditions under autogenous pressure. The (C2N2H10)[Fe(HPO3)F3] compound has been characterized by single-crystal X-ray diffraction data and spectroscopic and magnetic techniques. The crystal structure is formed by chains extended along the c axis and surrounded by ethylenediammonium cations. A study by diffuse-reflectance spectroscopy has been performed, and the calculated Dq, B, and C parameters for the Fe(III) cations are 1030, 720, and 3080 cm(-1), respectively. The Mössbauer spectrum at room temperature is characteristic of Fe(III) ions. The electron spin resonance (ESR) spectra carried out at different temperatures show isotropic signals with a g value of 2.00(1). The thermal evolution of the intensity of the ESR signals indicates the existence of antiferromagnetic interactions for the Fe(III) phase. The magnetic susceptibility data of the Cr(III) and V(III) compounds show antiferromagnetic couplings. The J-exchange parameters of the Fe(III) and Cr(III) compounds have been calculated by using a model for a triangular spin ladder chain. The values are J1 = -1.63(1) K and J2 = -0.87(2) K with g = 2.02 for the Fe(III) phase and J(1) = -0.56(2) K and J2 = -0.40(2) K with g = 1.99 for the Cr(III) compound. In the case of the V(III) phase, the fit has been performed considering a linear chain with the magnetic parameters D = 2.5 cm(-1) and J = -1.15(1) K.

  17. Glow phenomenon surrounding the vertical stabilizer and OMS pods

    NASA Technical Reports Server (NTRS)

    1994-01-01

    This 35mm frame, photographed as the Space Shuttle Columbia was orbiting Earth during a 'night' pass, documents the glow phenomenon surrounding the vertical stabilizer and the Orbital Maneuvering System (OMS) pods of the spacecraft.

  18. Spontaneous Involution of Congenital Melanocytic Nevus With Halo Phenomenon.

    PubMed

    Lee, Noo Ri; Chung, Hee-Chul; Hong, Hannah; Lee, Jin Wook; Ahn, Sung Ku

    2015-12-01

    Congenital melanocytic nevus (CMN) is a neural crest-derived hamartoma, which appear at or soon after birth. CMN has a dynamic course and may show variable changes over time, including spontaneous involution. Spontaneous involution of CMN is a rare phenomenon and is often reported in association with halo phenomenon or vitiligo. The mechanism of halo phenomenon is yet to be investigated but is suggested to be a destruction of melanocytes by immune responses of cytotoxic T cells or IgM autoantibodies. Here, the authors report an interesting case of spontaneously regressed medium-sized CMN with halo phenomenon and without vitiligo, which provides evidence that cytotoxic T cells account for the halo formation and pigmentary regression of CMN.

  19. Rumpel-Leede phenomenon presenting as a hypertensive urgency.

    PubMed

    Varela, Daniel; Tran, Dat; Ngamdu, Kyari Sumayin; Trullender, Brett; Mukherjee, Debabrata; Abbas, Aamer

    2016-04-01

    Rumpel-Leede (R-L) phenomenon is the rare event in which the small dermal capillaries of an extremity rupture in response to application of a compressive device to that extremity, such as when inflating a cuff during noninvasive blood pressure monitoring or when applying a tourniquet to draw blood. This capillary rupture results in formation of a petechial rash distal to the compressive device. R-L phenomenon is believed to occur most often in patients with underlying vascular disease, such as diabetes mellitus or thrombocytopenia. R-L phenomenon is most often benign, though it may rarely be associated with pain and discomfort. There is no treatment for this condition apart from treatment of the underlying vascular disease or thrombocytopenia. We report a 57-year-old woman who presented with hypertensive urgency and experienced R-L phenomenon during blood pressure cuff inflation.

  20. Prevalence of Raynaud's phenomenon in young Greek males.

    PubMed

    Tzilalis, Vassilios; Panagiotopoulos, Nikolaos; Papatheodorou, George; Rallis, Efstathios; Kassimos, Dimitrios

    2011-01-01

    The aim of this paper is to study the prevalence of Raynaud's phenomenon in young males. Young males were examined prospectively in a district hospital, and laboratory tests were performed on the basis of the clinical history. Young males (3.912), age 18-28 years old, were examined. Raynaud's phenomenon was present in seven men (1,79 per 1.000, 95% CI 0.72-3.68). Three of them had at least one member in their family diagnosed with Raynaud's phenomenon. Three were smokers. All had negative immunological test. Five patients reported having severe attacks and two had only mild ischemic attacks. The treatment was conservative for all patients, two of them necessitated vasodilators. Very low prevalence of Raynaud's phenomenon was observed in this young male group compared with the previous studies.

  1. Post-traumatic Raynaud's phenomenon following volar plate injury.

    PubMed

    Chodakiewitz, Yosef G; Daniels, Alan H; Kamal, Robin N; Weiss, Arnold-Peter C

    2014-04-01

    Post-traumatic Raynaud's phenomenon following non-penetrating or non-repetitive injury is rare. We report a case of Raynaud's phenomenon occurring in a single digit 3 months following volar plate avulsion injury. Daily episodes of painless pallor of the digit occurred for 1 month upon any exposure to cold, resolving with warm water therapy. Symptoms resolved after the initiation of hand therapy, splinting, and range-of- motion exercises.

  2. Synthesis of iron(II,III) oxide/zinc oxide/copper(II) oxide (Fe3O4/ZnO/CuO) nanocomposites and their photosonocatalytic property for organic dye removal.

    PubMed

    Taufik, Ardiansyah; Saleh, Rosari

    2017-04-01

    A facile sol-gel method was adopted to synthesize iron(II,III) oxide/zinc oxide/copper(II) oxide (Fe3O4/ZnO/CuO) nanocomposites with various CuO loadings at a low temperature. The prepared nanocomposites were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, UV-Vis spectroscopy, vibrating sample magnetometry, and Brunauer-Emmett-Teller (BET) surface area analyses. The photosonocatalytic properties of the nanocomposites were tested by methylene blue removal in aqueous solutions under the combination of UV or visible light and ultrasound. The catalyst with the lowest CuO loading exhibited the highest photosonocatalytic performance under UV light, while the fastest degradation under visible light was achieved at the highest CuO loading. Overall, the photosonocatalytic process with light and ultrasound irradiation led to more complete degradation compared to using light alone. According to the experiments performed with radical scavengers, the holes and OH radicals are the dominant oxidative species. The nanocomposites can be easily separated from the treated solution using an external magnetic field, and the samples remain very stable after 4 cycles. These results indicate that these materials have great potential for treating organic pollutants in wastewaters.

  3. Influences of group-III source preflow on the polarity, optical, and structural properties of GaN grown on nitridated sapphire substrates by metal-organic chemical vapor deposition

    SciTech Connect

    Li, Chengguo; Liu, Hongfei; Chua, Soo Jin

    2015-03-28

    We report the influences of group-III source preflow, which were introduced prior to the growth of the low temperature GaN on the polarity, photoluminescence (PL), and crystallographic properties of GaN epilayers grown on nitridated c-plane sapphire substrates by metal-organic chemical vapor deposition. By studying the surface morphology evolutions under chemical etching in KOH, we found that with increasing the trimethyl-gallium (TMGa) preflow duration (t), the polarity of the GaN film can be changed from a complete N-polarity to a mixture of N- and Ga-polarity and further to a complete Ga-polarity. PL and high-resolution X-ray diffraction studies revealed that the impurity incorporation and the edge- and screw-type threading dislocations are strongly polarity dependent. A further study at the optimized t (i.e., 30 s for TMGa) shows that the polarity inversion of GaN can be realized not only by TMGa preflow but also by trimethyl-aluminium preflow and by trimethyl-indium preflow. A two-monolayer model was employed to explain the polarity inversion mechanism.

  4. Synthesis and magnetic properties of Co1-xZnxFe2O4 (x=0÷1) nanopowders by thermal decomposition of Co(II), Zn(II) and Fe(III) carboxylates

    NASA Astrophysics Data System (ADS)

    Stefanescu, Mircea; Bozdog, Marius; Muntean, Cornelia; Stefanescu, Oana; Vlase, Titus

    2015-11-01

    Nanoparticles of cobalt-zinc ferrite Co1-xZnxFe2O4 with x varying from 0 to 1.0 were prepared by a new method, the thermal decomposition of carboxylates of Fe(III), Co(II) and Zn(II). The obtained carboxylate precursor was characterized by thermal analysis and FT-IR spectroscopy. The precursor was annealed at 350, 600 and 1000 °C. It was found that the spinel cobalt-zinc ferrite was formed starting at 350 °C, but in mixture with simple oxides γ-Fe2O3, Co3O4 and ZnO. At 1000 °C Co1-xZnxFe2O4 was formed quantitatively as a single, well-crystallized phase. The saturation magnetization of the samples annealed at 1000 °C decreased significantly with increasing Zn2+ content from 83.93 emu/g (x=0) to 4.92 emu/g (x=1.0). At 350 and 600 °C the saturation magnetization had the same trend, even if there were contributions of other magnetic phases. Obtaining of spinel ferrite was evidenced by X-ray diffractometry and FT-IR spectrometry. Powder morphology was determined by scanning electron microscopy. Magnetic properties of the synthesized ferrites were investigated employing a conventional induction method.

  5. Preparation, crystal structure, spectrographic characterization, thermal and third-order nonlinear optical properties of benzyltriethylammonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate(III) for all-optical switching applications

    NASA Astrophysics Data System (ADS)

    Wang, X. Q.; Ren, Q.; Chen, J. W.; Yu, W. T.; Fang, H. L.; Li, T. B.; Cong, H. J.; Liu, X. T.; Zhu, L. Y.; Zhang, G. H.; Xu, D.

    2011-05-01

    The preparation and crystal structure of a novel nonlinear optical organometallic crystal, benzyltriethylammonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)aurate(III) (BTEAADT), are described. The crystal was characterized by elemental analyses, infrared and X-ray powder diffraction spectroscopy, thermal analysis and optical absorption. A typical highly optical quality single crystal with dimensions of about 30 × 3 × 3 mm 3 has been grown from an acetone solution by the solvent evaporation method. The specific heat of the crystal was measured to be 692.0 J mol -1 K -1 at 300 K. The thin film of BTEAADT doped into poly(methyl methacrylate) (PMMA) with a concentration of 1 wt% was prepared using spin-coating method. The linear properties of the thin film were investigated by a prism coupler. The third-order nonlinear optical properties of BTEAADT doped PMMA film was investigated by using the laser Z-scan technique with 20 ps pulses at 1064 nm. A large negative nonlinear refraction and no nonlinear absorption have been observed. The refractive index and the thickness of the film are 1.4682 and 1.15 μm, respectively. The nonlinear refractive index is calculated to be -3.978 × 10 -15m 2/W for the film. At the same time, the nonlinear absorption coefficient is 0. Two figures of merit, W and T of the film, were calculated to be |W| = 1.07 > 1, |T| = 0 << 1. All results show that BTEAADT crystal has very potential applications on all-optical switching.

  6. White Light Emissive Dy(III) Single-Molecule Magnets Sensitized by Diamagnetic [Co(III) (CN)6 ](3-) Linkers.

    PubMed

    Chorazy, Szymon; Rams, Michał; Nakabayashi, Koji; Sieklucka, Barbara; Ohkoshi, Shin-Ichi

    2016-05-23

    The self-assembly of Dy(III) -3-hydroxypyridine (3-OHpy) complexes with hexacyanidocobaltate(III) anions in water produces cyanido-bridged {[Dy(III) (3-OHpy)2 (H2 O)4 ] [Co(III) (CN)6 ]}⋅H2 O (1) chains. They reveal a single-molecule magnet (SMM) behavior with a large zero direct current (dc) field energy barrier, ΔE=266(12) cm(-1) (≈385 K), originating from the single-ion property of eight-coordinated Dy(III) of an elongated dodecahedral geometry, which are embedded with diamagnetic [Co(III) (CN)6 ](3-) ions into zig-zag coordination chains. The SMM character is enhanced by the external dc magnetic field, which results in the ΔE of 320(23) cm(-1) (≈460 K) at Hdc =1 kOe, and the opening of a butterfly hysteresis loop below 6 K. Complex 1 exhibits white Dy(III) -based emission realized by energy transfer from Co(III) and 3-OHpy to Dy(III) . Low temperature emission spectra were correlated with SMM property giving the estimation of the zero field ΔE. 1 is a unique example of bifunctional magneto-luminescent material combining white emission and slow magnetic relaxation with a large energy barrier, both controlled by rich structural and electronic interplay between Dy(III) , 3-OHpy, and [Co(III) (CN)6 ](3-) .

  7. [Raynaud's phenomenon - first sign of malignancy: case report].

    PubMed

    Sutić, Anamarija; Gračanin, Gudelj; Morović-Vergles, Jadranka

    2014-06-01

    Raynaud's phenomenon is a common phenomenon in the general population. It most commonly occurs in healthy individuals, in whom there is no associated illness or any other cause of Raynaud's phenomenon (primary or idiopathic Raynaud's phenomenon). Secondary Raynaud's phenomenon is common with rheumatic diseases (systemic sclerosis, systemic lupus erythematosus, primary Sjögren's syndrome, mixed connective tissue disease, etc.), occlusive vascular diseases, hematologic disorders, use of vibrating tools and use of some medications, and rarely with malignancy. We report on a patient who presented with a three-week history of painful Raynaud's attacks, which was the reason for seeking assistance of internists in emergency clinic. Upon admission to the hospital and diagnostic work-up, adenocarcinoma of the lung was found. Antinuclear antibodies (ANA), anti-dsDNA antibodies, anticardiolipin IgM and IgG antibodies were present in a lower titer. It is known that rheumatoid factor or ANA characteristic of rheumatic disease are often present in patients with paraneoplastic rheumatic syndromes, which can lead to wrong conclusions about the possible systemic connective tissue diseases and ultimately delay the correct diagnosis. The first appearance of Raynaud's phenomenon as an isolated symptom in people older than 50, with painful signs of ischemia, as in our patient, or the occurrence of asymmetric grasping fingers, especially in men, regardless of the presence of RF, ANA, anti-dsDNA or other autoantibodies, requires broader diagnostic evaluation for malignancy.

  8. Abnormal platelet aggregation in patients with Raynaud's phenomenon.

    PubMed Central

    Biondi, M L; Marasini, B

    1989-01-01

    Platelet aggregation in vitro to several aggregating agents (serotonin (5-HT), adenosine diphosphate, adrenaline and collagen) was studied in 16 patients with primary and secondary Raynaud's phenomenon and compared with that in 13 normal volunteers. Platelets from patients with Raynaud's phenomenon had significantly greater responses to all the 5-HT concentrations tested (p less than 0.001 for 10 microM; p less than 0.01 for 1 microM; p less than 0.05 for 0.1 microM; p less than 0.02 for 0.025 microM) and to low doses of adenosine diphosphate (p less than 0.01 for 1 microM; p less than 0.02 for 0.5 microM) but normal responses to collagen, adrenaline, and high doses of adenosine diphosphate. Patients with secondary Raynaud's phenomenon were significantly more hypersensitive to 0.5 microM adenosine diphosphate than patients with primary Raynaud's phenomenon. In patients with secondary Raynaud's phenomenon there was a significant correlation between the extent of 5-HT aggregation and the duration of the disease. The finding that platelets from patients with Raynaud's phenomenon have enhanced responses to 5-HT and adenosine diphosphate, but normal responses to adrenaline and collagen, is consistent with a role for 5-HT in this disease. PMID:2760232

  9. In situ hydrothermal syntheses, structures and photoluminescent properties of four novel metal-organic frameworks constructed by lanthanide (Ln=Ce(III), Pr(III), Eu(III)) and Cu(I) metals with flexible dicarboxylate acids and piperazine-based ligands

    SciTech Connect

    Ay, Burak; Karaca, Serkan; Yildiz, Emel; Lopez, Valerie; Nanao, Max H.; Zubieta, Jon

    2016-01-15

    Four novel metal-organic frameworks,[Cu{sub 2}Cl{sub 2}(pyrz)]{sub n} (1) and (H{sub 2}pip){sub n}[Ln{sub 2}(pydc){sub 4}(H{sub 2}O){sub 2}]{sub n} (Ln=Ce (2), Pr (3) and Eu (4), H{sub 2}pzdc=2,3-pyrazinedicarboxylic acid, pyrz=pyrazine, H{sub 2}pydc=2,6-pyridinedicarboxylic acid, H{sub 2}pip=piperazine) have been synthesized under hydrothermal conditions and characterized by the elemental analysis, ICP, Far IR (FIR), FT-IR spectra, TGA, single crystal X-ray diffraction analysis and powder X-ray diffraction (PXRD). Compound 1 is two-dimensional containing Cl-Cu-Cl sites, while the lanthanide complexes contain one-dimensional infinite Ln–O-Ln chains. All the complexes show high thermal stability. The complexes 1–3 exhibit luminescence emission bands at 584, 598 and 614 nm at room temperature when excited at 300 nm. Complex 4 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four novel metal-organic frameworks have been synthesized under hydrothermal conditions. Thermal and luminescent properties of the compounds have been investigated.

  10. Clumping in Massive Star Winds and Its Possible Connection to the B[e] Phenomenon

    NASA Astrophysics Data System (ADS)

    Kubátová, B.; Kubát, J.; Hamann, W.-R.; Oskinova, L.

    2017-02-01

    It has been observationally established that winds of hot massive stars have highly variable characteristics. The variability evident in the winds is believed to be caused by structures on a broad range of spatial scales. Small-scale structures (clumping) in stellar winds of hot stars are possible consequence of an instability appearing in their radiation hydrodynamics. To understand how clumping may influence calculation of theoretical spectra, different clumping properties and their 3D nature have to be taken into account. Properties of clumping have been examined using our 3D radiative transfer calculations. Effects of clumping for the case of the B[e] phenomenon are discussed.

  11. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.

    Numerous cases in this year's chapter dealt with the same topics of previous years--contracts and bids for building construction, and detachment and annexation of a portion of a school district. The courts continued to attribute board discretionary authority to school boards in school property matters. Intergovernmental disputes over ownership or…

  12. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.; Forsberg, James R.

    This chapter summarizes and analyze all state supreme court and federal court decisions as well as other significant court decisions involving school property. The cases discussed are generally limited to those decided during 1974 and reported in the General Digest on or before March 1, 1975. In their discussion, the authors attempt to integrate…

  13. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.

    A review of cases involving higher education property matters shows that many are concerned with building construction, equipment installation, or repair contracts. A number of other cases involve routine conflicts between colleges or universities and other governmental entities over matters such as requests for special exceptions to zoning…

  14. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.; Forsberg, James R.

    This chapter summarizes recent state supreme court and federal court decisions involving school property. The cases discussed are generally limited to those decided during 1975 and reported in the General Digest as of March 1976. In their discussion, the authors attempt to integrate related cases and to illuminate any unifying legal principles…

  15. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.

    Reflecting widespread unhappiness with the growing tax burdens in this country, the most active area of litigation reported in the property chapter this year involves various attempts by taxpayers to prevent the construction or remodeling of public school facilities. While some taxpayers fought to keep schools from being built, others in New York…

  16. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.

    The author notes that controversies over construction bids and contracts continue to represent the largest number of property cases reported in this year's chapter. Most of these cases are routine disputes between colleges or universities and contractors over such issues as the return of bid bonds, recovery of additional costs for construction…

  17. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.; Johnson, Margaret M.

    While the number of cases dealing with school property issues was significantly lower than in previous years, a significant number of cases involving the detachment and attachment of land to school districts arose. Eight of the eleven cases dealing with land detachment come from Illinois. The cases concerned requests from parents that their…

  18. Property.

    ERIC Educational Resources Information Center

    Piele, Philip K.; Forsberg, James R.

    While the types of cases reported in this year's chapter are essentially the same as those reported in last year's, the number of certain types of cases have changed--in some instances significantly. For example, the number of cases raising constitutional issues in the areas of school construction, location, and property use have declined. On the…

  19. Antithrombin III blood test

    MedlinePlus

    ... AT III) is a protein that helps control blood clotting. A blood test can determine the amount of ... may mean you have an increased risk of blood clotting. This can occur when there is not enough ...

  20. Tuning the cytotoxic properties of new ruthenium(III) and ruthenium(II) complexes with a modified bis(arylimino)pyridine Schiff base ligand using bidentate pyridine-based ligands.

    PubMed

    Garza-Ortiz, Ariadna; Maheswari, Palanisamy Uma; Lutz, Martin; Siegler, Maxime A; Reedijk, Jan

    2014-06-01

    Synthesis, spectroscopy, characterization, structures, and cytotoxicity studies of 2,6-bis(2,6-diisopropylphenyliminomethyl)pyridine (LLL) ruthenium compounds are described. The starting compound [RuCl3(LLL)] has been fully characterized using IR spectroscopy, UV-vis spectroscopy, electrospray ionization mass spectrometry, and NMR spectroscopy. In addition, the crystal structure of the ligand LLL has been determined using single-crystal X-ray diffraction. With the ruthenium(III) trichloride compound as starting material, a new family of Ru(II) complexes with a number of neutral and charged bidentate co-ligands have been synthesized and used for characterization and cytotoxicity studies. The synthesis of the corresponding [Ru(II)LLL(LL)Cl](+/0) complexes with co-ligands- LL is 1,10-phenanthroline, 2,2'-bipyridyl, 2-(phenylazo)pyridine, 2-(phenylazo)-3-methylpyridine, 2-(tolylazo)pyridine, or the anionic 2-picolinate-is reported. Analytical, spectroscopic (IR spectroscopy, UV-vis spectroscopy, (1)H NMR spectroscopy, and electrospray ionization mass spectrometry), and structural characterization of the new compounds is described. Crystal structure analyses of two Ru(II) compounds show a slightly distorted octahedral Ru(II) geometry with tridentate LLL coordinated in a planar meridional fashion, and the chelating co-ligand (LL) and a chloride ion complete the octahedron. The co-ligand plays a significant role in modulating the physicochemical and cytotoxic properties of these new ruthenium complexes. The in vitro cytotoxicity of these new Ru(II) complexes (half-maximal inhibitory concentration, IC50, of 0.5-1.5 μM), in comparison with the parent Ru(III) compound (half-maximal inhibitory concentration of 3.9-4.3 μM) is higher for several of the human cancer cell lines tested. The cytotoxic activity of some of the new ruthenium compounds is even higher than that of cisplatin in the same cancer cell lines. The cytotoxicity of these new anticancer compounds is

  1. Iridium(III) Mediated Reductive Transformation of Closed-Shell Azo-Oxime to Open-Shell Azo-Imine Radical Anion: Molecular and Electronic Structure, Electron Transfer, and Optoelectronic Properties.

    PubMed

    Pramanik, Shuvam; Roy, Sima; Ghorui, Tapas; Ganguly, Sanjib; Pramanik, Kausikisankar

    2016-02-15

    The hydrogen bonded bis azo-oximato [IrCl2(L(NOH))(L(NO))] 2 and its deprotonated form (Et3NH)[IrCl2(L(NO))2] (Et3NH)(+)3(-) have been isolated in the crystalline state by a facile synthetic method. The azo-oxime frameworks in 3(-) have been conveniently transformed to the azo-imine by reduction with NaBH4 or ascorbic acid. Notably, the coordinated azo-imines accept an extra electron thereby furnishing the azo-imine radical anion complex 4. The underlying reductive transformation can be best described by proton-coupled electron transfer (PCET) process. Both the coordinated ligands (azo-oxime) in 3(-) are typically closed-shell monoanion (L(NO-)), but their reduced form (azo-imine) can behave as open-shell monoanion (L(NH•-)) owing to the presence of highly stabilized virtual orbitals. Remarkable enhancement of the π-acidity in azo-imine relative to the precursor azo-oxime has also been reflected from the electrochemical study. The irido complexes display rich optoelectronic properties, and the origin of the transitions has been scrutinized by the TD-DFT method. The molecular geometries of the complexes 2 and 3(-) reveal that the syn orientation of the azo-oximes frameworks is favored because of strong noncovalent H-bonding and π-π stacking interactions. In the course of the reduction of 3(-), the sterically encumbered disposition of the azo-oximes is converted to the relaxed anti form in the transformed azo-imines. Diffraction study reveals the electronic structure of 4 as [Ir(III)Cl2{(L(NH))2(•-)}]. The superior stabilization of the unpaired spin on the ligand array rather than metal has also been substantiated from EPR and DFT studies. Theoretical analysis reveals that the odd electron delocalizes primarily over both the azo-imine moieties ([IrCl2(L(NH•-))(L(NH))] ↔ ([IrCl2(L(NH))(L(NH•-))]) with no apparent contribution from metal, and this type of ligand-centered mixed valency (LCMV) can be best expressed as Robin-Day class III (fully delocalized

  2. Photodetectors using III-V nitrides

    DOEpatents

    Moustakas, T.D.

    1998-12-08

    A bandpass photodetector using a III-V nitride and having predetermined electrical properties is disclosed. The bandpass photodetector detects electromagnetic radiation between a lower transition wavelength and an upper transition wavelength. That detector comprises two low pass photodetectors. The response of the two low pass photodetectors is subtracted to yield a response signal. 24 figs.

  3. Photodetectors using III-V nitrides

    DOEpatents

    Moustakas, Theodore D.

    1998-01-01

    A bandpass photodetector using a III-V nitride and having predetermined electrical properties. The bandpass photodetector detects electromagnetic radiation between a lower transition wavelength and an upper transition wavelength. That detector comprises two low pass photodetectors. The response of the two low pass photodetectors is subtracted to yield a response signal.

  4. The post-mortem pink teeth phenomenon: a case report.

    PubMed

    Soriano, Evelyne-Pessoa; Carvalho, Marcus-Vitor-Diniz de; Santos, Francisco-Bernardo Dos; Mendoza, Clóvis-César de; Araújo, Maria-do Socorro-Dantas de; Campello, Reginaldo-Inojosa-Carneiro

    2009-07-01

    This study presents the case of the post-mortem pink teeth phenomenon observed during an autopsy procedure performed on the body of a man who was kidnapped and murdered approximately 30 days before the examination. The corpse was in an advanced stage of decomposition and putrefaction. Both maxillary and jaw bones were intact, as well as the permanent teeth which presented the "pink teeth phenomenon", probably due to a haemorrhage in the pulp chambers. The pink discolouration was most pronounced at the neck of the teeth. The cause of death was asphyxia. Although the examiners stressed that post-mortem pink teeth must not be considered as a reliable odontological parameter for determining the cause of death, the results of other studies have shown that the pink teeth phenomenon is a common finding related to cases of asphyxia such as strangulation, drowning or suffocation. Thus, the pink teeth phenomenon must be studied in order to determine its role as a post-mortem finding. As of now, an exact relationship between the cause of death and this phenomenon remains unknown.

  5. Analysis of rewarming curves in Raynaud's phenomenon of various aetiologies.

    PubMed

    Salem, K M; Baker, M; Hilliam, R M; Davies, S; Deighton, C; Bainbridge, L C; Manning, G

    2009-10-01

    This study investigated whether a modified Cold Provocation Test could distinguish between 86 normal subjects and 31 patients with Raynaud's phenomenon or 59 with hand arm vibration syndrome (HAVS). Of the HAVS subjects, 56 were seen for medical reports as they were involved in litigation. Their assessments were done in a different location but the same protocol was used. A standardised cold stress was used to reduce the finger temperature to 15 degrees C or less without inducing reflex hyperaemia. This test had acceptable repeatability for subjects without HAVS with an intra-class correlation of 0.7. Baseline temperature, temperature rise in the first 30 seconds and the time taken to rewarm by 5 degrees C were measured. Patients with Raynaud's phenomenon and HAVS had cooler hands than controls. HAVS patients rewarmed most in the first 30 seconds. Patients with Raynaud's phenomenon take longer to rewarm by 5 degrees C than controls or those with HAVS (P<0.001). A baseline difference of >7.5 degrees C between the temperature of the digit and that of the room is unlikely to occur in patients with Raynaud's phenomenon or HAVS. A temperature gain of > or =2.2 degrees C in the first 30 seconds on rewarming combined with a low baseline temperature strongly suggests HAVS. This modified cold provocation test may differentiate between patients with Raynaud's phenomenon, HAVS and controls but this observation requires independent verification in subjects not involved in litigation and tested in the same facility.

  6. Public information for the assessment of quality: a widespread social phenomenon.

    PubMed Central

    Valone, Thomas J; Templeton, Jennifer J

    2002-01-01

    We propose that the use of public information about the quality of environmental resources, obtained by monitoring the sampling behaviour of others, may be a widespread social phenomenon allowing individuals to make faster, more accurate assessments of their environment. To demonstrate this (i) we define public information and distinguish it from other kinds of social information; (ii) we review empirical work demonstrating the benefits and costs of using public information to estimate food patch quality; (iii) we examine recent work showing that individuals may also be using public information to improve their estimates of the quality of such disparate environmental parameters as breeding patches, opponents and mates; and finally (iv) we suggest avenues of future work to better understand the nature of public information use and when it might be used or ignored. Such work should lead to a more complete understanding of the behaviour of individuals in social aggregations. PMID:12495512

  7. Scaling in non-stationary time series. (II). Teen birth phenomenon

    NASA Astrophysics Data System (ADS)

    Ignaccolo, M.; Allegrini, P.; Grigolini, P.; Hamilton, P.; West, B. J.

    2004-05-01

    This paper is devoted to the problem of statistical mechanics raised by the analysis of an issue of sociological interest: the teen birth phenomenon. It is expected that these data are characterized by correlated fluctuations, reflecting the cooperative properties of the process. However, the assessment of the anomalous scaling generated by these correlations is made difficult, and ambiguous as well, by the non-stationary nature of the data that shows a clear dependence on seasonal periodicity (periodic component) and an average changing slowly in time (slow component) as well. We use the detrending techniques described in the companion paper [The earlier companion paper], to safely remove all the biases and to derive the genuine scaling of the teen birth phenomenon.

  8. A New Demonstration of the Illusory Letters Phenomenon: Graphemic Restoration in Arabic Word Perception.

    PubMed

    Jordan, Timothy R; Sheen, Mercedes; AlJassmi, Maryam A; Paterson, Kevin B

    2015-02-01

    The illusory letters phenomenon (ILP) is a unique demonstration that words can be perceived as complete even when letters are physically absent. However, the ILP has only ever been reported for a Latinate language (English), and it is unknown whether the illusion occurs for alphabetic languages with fundamentally different visual properties. Here we report a demonstration of the ILP for Arabic in which stimuli containing only the exterior letters of three-letter Arabic words and a nonsense pattern in the interior position were presented to fluent Arabic readers. Despite being incomplete, participants perceived these stimuli as complete Arabic words with all letters visible in their appropriate positions, and were unable to distinguish between illusory and normal displays. This finding provides an important extension of the original ILP and suggests that alphabetic languages may be widely susceptible to the phenomenon and reading generally may occur as a process augmented by illusory percepts.

  9. Type III burst pair

    NASA Astrophysics Data System (ADS)

    Ning, Zongjun; Fu, Qijun; Lu, Quankang

    2000-05-01

    We present a special solar radio burst detected on 5 January 1994 using the multi-channel (50) spectrometer (1.0-2.0 GHz) of the Beijing Astronomical Observatory (BAO). Sadly, the whole event could not be recorded since it had a broader bandwidth than the limit range of the instrument. The important part was obtained, however. The event is composed of a normal drift type III burst on the lower frequency side and a reverse drift type III burst appearing almost simultaneously on the high side. We call the burst type III a burst pair. It is a typical characteristic of two type III bursts that they are morphologically symmetric about some frequency from 1.64 GHz to 1.78 GHz on the dynamic spectra records, which indicates that there are two different electron beams from the same acceleration region travelling simultaneously in opposite directions (upward and downward). A magnetic reconnection mode is a nice interpretation of type III burst pair since the plasma beta β~=0.01 is much less than 1 and the beams have velocity of about 1.07×10^8 cm s^-1 after leaving the reconnection region if we assume that the ambient magnetic field strength is about 100 G.

  10. Type III burst pair.

    NASA Astrophysics Data System (ADS)

    Zongjun, Ning; Fu, Qijun; Quankang, Lu

    2000-05-01

    Presents a special solar radio burst detected on 5 January 1994 using the multi-channel (50) spectrometer (1.0 - 2.0 GHz) of the Beijing Astronomical Observatory. Sadly, the whole event could not be recorded since it had a broader bandwidth than the limit range of the instrument. The important part was obtained, however. The event is composed of a normal drift type III burst on the lower frequency side and a reverse drift type III burst appearing almost simultaneously on the high side. The authors call the burst type III a burst pair. It is a typical characteristic of two type III bursts that they are morphologically symmetric about some frequency from 1.64 GHz to 1.78 GHz on the dynamic spectra records, which indicates that there are two different electron beams from the same acceleration region travelling simultaneously in opposite directions (upward and downward). A magnetic reconnection mode is an interpretation of type III burst pair.

  11. New route to the mixed valence semiquinone-catecholate based mononuclear FeIII and catecholate based dinuclear MnIII complexes: first experimental evidence of valence tautomerism in an iron complex.

    PubMed

    Shaikh, Nizamuddin; Goswami, Sanchita; Panja, Anangamohan; Wang, Xin-Yi; Gao, Song; Butcher, Ray J; Banerjee, Pradyot

    2004-09-20

    The semiquinone-catecholate based mixed valence complex, [FeIII(bispicen)(Cl4Cat)(Cl4SQ)] x DMF (1), and catecholate based (H2bispictn)[Mn2III(Cl4Cat)4(DMF)2] (2) (bispicen = N,N'-bis(2-pyridylmethyl)-1,2-ethanediamine, bispictn = N,N'-bis(2-pyridylmethyl)-1,3-propanediamine, Cl4Cat = tetrachlorocatecholate dianion, and Cl4SQ = tetrachlorosemiquinone radical anion) were synthesized directly utilizing a facile route. Both the complexes have been characterized by single crystal X-ray diffraction study. The electronic structures have been elucidated by UV-vis-NIR absorption spectroscopy, cyclic voltammetry, EPR, and magnetic properties. The structural as well as spectroscopic features support the mixed valence tetrachlorosemiquinone-tetrachlorocatecholate charge distribution in 1. The ligand based mixed valence state was further confirmed by the presence of an intervalence charge transfer (IVCT) band in the 1900 nm region both in solution and in the solid. The intramolecular electron transfer, a phenomenon known as valence tautomerism (VT), has been followed by electronic absorption spectroscopy. For 1, the isomeric form [FeIII(bispicen)(Cl4Cat)(Cl4SQ)] is favored at low temperature, while at an elevated temperature, the [FeII(bispicen)(Cl4SQ)2] redox isomer dominates. Infrared as well as UV-vis-NIR spectral characterization for 2 suggest that the MnIII(Cat)2- moiety is admixed with its mixed valence semiquinone-catecholate isomer MnII(SQ)(Cat)-, and the electronic absorption spectrum is dominated by the mixed charged species. The origin of the intervalence charge transfer band in the 1900 nm range is associated with the mixed valence form, MnII(Cl4Cat)(Cl4SQ)-. The observation of VT in complex 1 is the first example where a mixed valence semiquinone-catecholate iron(III) complex undergoes intramolecular electron transfer similar to manganese and cobalt complexes.

  12. The role of ocean phenomenon in music compositions

    NASA Astrophysics Data System (ADS)

    Liu, Chi-Min

    2016-04-01

    This is a preliminarily interdisciplinary study for exploring the elements of ocean phenomenon appearing in some compositions of classical music. The so-called ocean phenomenon contain wave conditions, climate change, coastal landform, and other natural events around or over the sea. In some music compositions, it is apparent that natural phenomenon over the sea influence the composers' moods and the music pieces they composed. In this poster, some music compositions in the 19th and the early 20th centuries will be introduced to demonstrate the relation between ocean and music works. These works include Meeresstille by Schubert, Étude Op.25 No.12 by Chopin, Fingal's Cave Overture by Mendelssohn, Der Fliegende Holländer by Wagner and La Mer by Debussy. In addition, present idea may give a novel way for music teachers to elucidate the knowledge of ocean science in classes.

  13. Ringing phenomenon based whispering-gallery-mode sensing

    PubMed Central

    Ye, Ming-Yong; Shen, Mei-Xia; Lin, Xiu-Min

    2016-01-01

    Highly sensitive sensing is one of the most important applications of whispering-gallery-mode (WGM) microresonators, which is usually accomplished through a tunable continuous-wave laser sweeping over a whispering-gallery mode with the help of a fiber taper in a relative slow speed. It is known that if a tunable continuous-wave laser sweeps over a high quality whispering-gallery mode in a fast speed, a ringing phenomenon will be observed. The ringing phenomenon in WGM microresonators is mainly used to measure the Q factors and mode-coupling strengths. Here we experimentally demonstrate that the WGM sensing can be achieved based on the ringing phenomenon. This kind of sensing is accomplished in a much shorter time and is immune to the noise caused by the laser wavelength drift. PMID:26796871

  14. Statistical Agent Based Modelization of the Phenomenon of Drug Abuse

    NASA Astrophysics Data System (ADS)

    di Clemente, Riccardo; Pietronero, Luciano

    2012-07-01

    We introduce a statistical agent based model to describe the phenomenon of drug abuse and its dynamical evolution at the individual and global level. The agents are heterogeneous with respect to their intrinsic inclination to drugs, to their budget attitude and social environment. The various levels of drug use were inspired by the professional description of the phenomenon and this permits a direct comparison with all available data. We show that certain elements have a great importance to start the use of drugs, for example the rare events in the personal experiences which permit to overcame the barrier of drug use occasionally. The analysis of how the system reacts to perturbations is very important to understand its key elements and it provides strategies for effective policy making. The present model represents the first step of a realistic description of this phenomenon and can be easily generalized in various directions.

  15. The coronary slow flow phenomenon: a new cardiac "Y" syndrome?

    PubMed

    Leone, Maria Cristina; Gori, Tommaso; Fineschi, Massimo

    2008-01-01

    The coronary slow flow phenomenon (CSFP) is an angiographic finding that is characterised by delayed progression of the contrast medium during coronary angiography. The mechanism of this phenomenon remains unknown. In the present paper, we revise the current evidence regarding this phenomenon and discuss recent findings from our group reporting increased resting resistances in patients with the CSFP. We report that these patients had preserved blood flow responses to the intracoronary infusion of the vasodilator papaverine, demonstrating that the CSFP is not necessarily associated with an abnormal coronary flow reserve. Based on these findings and on the review of the current literature, we concur with the concept proposed by Beltrame et al. that the CSFP should be considered a separate clinical entity. Further studies are necessary to describe the clinical characteristics, including the prognosis, of these patients and to identify potential treatments.

  16. Ringing phenomenon based whispering-gallery-mode sensing

    NASA Astrophysics Data System (ADS)

    Ye, Ming-Yong; Shen, Mei-Xia; Lin, Xiu-Min

    2016-01-01

    Highly sensitive sensing is one of the most important applications of whispering-gallery-mode (WGM) microresonators, which is usually accomplished through a tunable continuous-wave laser sweeping over a whispering-gallery mode with the help of a fiber taper in a relative slow speed. It is known that if a tunable continuous-wave laser sweeps over a high quality whispering-gallery mode in a fast speed, a ringing phenomenon will be observed. The ringing phenomenon in WGM microresonators is mainly used to measure the Q factors and mode-coupling strengths. Here we experimentally demonstrate that the WGM sensing can be achieved based on the ringing phenomenon. This kind of sensing is accomplished in a much shorter time and is immune to the noise caused by the laser wavelength drift.

  17. High prevalence of isolated sleep paralysis: kanashibari phenomenon in Japan.

    PubMed

    Fukuda, K; Miyasita, A; Inugami, M; Ishihara, K

    1987-06-01

    In Japan, a set of experiences called kanashibari is considered identical with isolated sleep paralysis. We investigated this phenomenon by means of a questionnaire administered to 635 college students (390 men and 245 women). Of all subjects, about 40% had experienced at least one episode of kanashibari [subjects of K(+)]. Therefore, isolated sleep paralysis is apparently a more common phenomenon than is usually appreciated. About half of the subjects of K(+) reported that they had been under "physical or psychological stress" or in a "disturbed sleep and wakefulness cycle" immediately before the episode. Many subjects of K(+) experienced the first episode in adolescence. In the distribution of age of first attack, the peak occurred at an earlier age in women subjects than in men subjects. These findings suggest that two factors influence the occurrence of the phenomenon. One is exogenous physical or psychological load and the other is endogenous biological development.

  18. Kernohan's phenomenon associated with left ruptured occipital arteriovenous malformation.

    PubMed

    Fujimoto, A; Sato, H; Katayama, W; Nakai, K; Tsunoda, T; Kobayashi, E; Nose, T

    2004-05-01

    A 23-year-old woman presented with ipsilateral hemiparesia due to rupture of a left occipital arteriovenous malformation (AVM). Emergency decompression (the onset-operation interval was 46 minutes,) was carried out and the patient could leave the hospital upon recovery without neurological deficits. In general, Kernohan's phenomenon is caused by the gradual displacement of the cerebral peduncle against the tentorial edge caused by compression by the contralateral mass. This phenomenon is very rare among the cases with spontaneous intracranial hemorrhage and only three cases including the present one have been reported in the literature. In all cases the onset-operation intervals of were very short. Kernohan's phenomenon associated with a ruptured AVM is a rare condition and emergency decompression is required.

  19. Tears of wine: new insights on an old phenomenon

    PubMed Central

    Venerus, David C.; Nieto Simavilla, David

    2015-01-01

    Anyone who has enjoyed a glass of wine has undoubtedly noticed the regular pattern of liquid beads that fall along the inside of the glass, or ‘tears of wine.’ The phenomenon is the result of a flow against gravity along the liquid film on the glass, which is induced by an interfacial tension gradient. It is generally accepted that the interfacial tension gradient is due to a composition gradient resulting from the evaporation of ethanol. We re-examine the tears of wine phenomenon and investigate the importance of thermal effects, which previously have been ignored. Using a novel experiment and simple model we find that evaporative cooling contributes significantly to the flow responsible for wine tears, and that this phenomenon occurs primarily because of the thermodynamic behavior of ethanol-water mixtures. Also, the regular pattern of tear formation is identified as a well-known hydrodynamic instability. PMID:26548566

  20. Tears of wine: new insights on an old phenomenon

    NASA Astrophysics Data System (ADS)

    Venerus, David C.; Nieto Simavilla, David

    2015-11-01

    Anyone who has enjoyed a glass of wine has undoubtedly noticed the regular pattern of liquid beads that fall along the inside of the glass, or ‘tears of wine.’ The phenomenon is the result of a flow against gravity along the liquid film on the glass, which is induced by an interfacial tension gradient. It is generally accepted that the interfacial tension gradient is due to a composition gradient resulting from the evaporation of ethanol. We re-examine the tears of wine phenomenon and investigate the importance of thermal effects, which previously have been ignored. Using a novel experiment and simple model we find that evaporative cooling contributes significantly to the flow responsible for wine tears, and that this phenomenon occurs primarily because of the thermodynamic behavior of ethanol-water mixtures. Also, the regular pattern of tear formation is identified as a well-known hydrodynamic instability.