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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. Meterwavelength Single-pulse Polarimetric Emission Survey. III. The Phenomenon of Nulling in Pulsars

    NASA Astrophysics Data System (ADS)

    Basu, Rahul; Mitra, Dipanjan; Melikidze, George I.

    2017-09-01

    A detailed analysis of nulling was conducted for the pulsars studied in the Meterwavelength Single-pulse Polarimetric Emission Survey. We characterized nulling in 36 pulsars including 17 pulsars where the phenomenon was reported for the first time. The most dominant nulls lasted for a short duration, less than five periods. Longer duration nulls extending to hundreds of periods were also seen in some cases. A careful analysis showed the presence of periodicities in the transition from the null to the burst states in 11 pulsars. In our earlier work, fluctuation spectrum analysis showed multiple periodicities in 6 of these 11 pulsars. We demonstrate that the longer periodicity in each case was associated with nulling. The shorter periodicities usually originate from subpulse drifting. The nulling periodicities were more aligned with the periodic amplitude modulation, indicating a possible common origin for both. The most prevalent nulls last for a single period and can be potentially explained using random variations affecting the plasma processes in the pulsar magnetosphere. On the other hand, longer-duration nulls require changes in the pair-production processes, which need an external triggering mechanism for the changes. The presence of periodic nulling puts an added constraint on the triggering mechanism, which also needs to be periodic.

  4. 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.

  5. Optical properties of the Eu(III)-La(III)-complex-doped polyolefine film and rod samples

    NASA Astrophysics Data System (ADS)

    Pogreb, Roman; Popov, Oleg; Lirtsman, Vlad; Pyshkin, Oleg; Kazachkov, Alexander; Musin, Albina; Finkelshtein, Binyamin; Shmukler, Yuri; Davidov, Dan; Bormashenko, Edward

    2005-04-01

    The work is devoted to luminescent properties of trivalent lanthanide complexes dispersed in thermoplastic host matrices. Polyethylene-based film and polypropylene-based rod both doped with these complexes were manufactured using an extrusion technique. Two kinds of dopants were used: Eu(III)-thenoyltrifluoroacetone-1,10-phenanthroline complex (Eu(III)) and Eu(III)-La(III)-1,10-phenanthroline complex (Eu(III)-La(III)). Comparison was made between these samples regarding absorption, excitation, emission and a lifetime of luminescence. Dependence of emission intensity on the excitation energy was determined. Emission spectra of the films were studied at room and helium temperatures. Optical properties of Eu(III) samples are different from Eu(III)-La(III) samples. Significant difference in spectra of these two types of samples may be attributed to the La(III) action.

  6. Luminescense properties of new complexes of Eu(III) and Tb(III) with heterotopic ligands

    NASA Astrophysics Data System (ADS)

    Patroniak, Violetta; Hnatejko, Zbigniew; Grochowska, Agnieszka M.; Stefankiewicz, Artur R.

    2006-07-01

    As a result of coordination between ligands L and L' and europium(III) and terbium(III) ions, the new architectures were formed. The formulae of the complexes have been assigned on the basis of the spectroscopic data in solution and microanalyses. The europium complexes show excellent luminescence properties with high quantum yield ( 1b-Eu 3L2) and effective intramolecular energy transfer from the ligand to the Eu(III) ions.

  7. Luminescense properties of new complexes of Eu(III) and Tb(III) with heterotopic ligands.

    PubMed

    Patroniak, Violetta; Hnatejko, Zbigniew; Grochowska, Agnieszka M; Stefankiewicz, Artur R

    2006-07-01

    As a result of coordination between ligands L and L' and europium(III) and terbium(III) ions, the new architectures were formed. The formulae of the complexes have been assigned on the basis of the spectroscopic data in solution and microanalyses. The europium complexes show excellent luminescence properties with high quantum yield (1b-Eu(3)L(2)) and effective intramolecular energy transfer from the ligand to the Eu(III) ions.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. [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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. [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.

  4. 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

  5. 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.

  6. 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.

  7. Raynaud's phenomenon.

    PubMed

    O'connor, C M

    2001-09-01

    Many persons are affected by the phenomenon known as Raynaud's. Raynaud's is classified in 2 ways-as Raynaud's disease or Raynaud's syndrome. Classification is based on the presence of associated conditions. Raynaud's is characterized by vasospasm-induced color changes of the fingers, toes, and ears. The fingers are most commonly affected. Studies involving cause, diagnosis, and treatment have been instituted with varied results. Diagnosis is primarily based on clinical symptoms involving digital color changes. Treatment is aimed at prevention of attacks and includes medication, stress reduction, and avoidance of vasoconstricting agents. Whether the phenomenon will develop into a more serious condition with which Raynaud's is associated is important. This article describes the etiology, pathophysiology, diagnosis, treatment, and nursing implications with regard to Raynaud's.

  8. 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).

  9. 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.

  10. Vacuum phenomenon.

    PubMed

    Yanagawa, Youichi; Ohsaka, Hiromichi; Jitsuiki, Kei; Yoshizawa, Toshihiko; Takeuchi, Ikuto; Omori, Kazuhiko; Oode, Yasumasa; Ishikawa, Kouhei

    2016-08-01

    This article describes the theory of the formation of the vacuum phenomenon (VP), the detection of the VP, the different medical causes, the different locations of the presentation of the VP, and the differential diagnoses. In the human body, the cavitation effect is recognized on radiological studies; it is called the VP. The mechanism responsible for the formation of the VP is as follows: if an enclosed tissue space is allowed to expand as a rebound phenomenon after an external impact, the volume within the enclosed space will increase. In the setting of expanding volume, the pressure within the space will decrease. The solubility of the gas in the enclosed space will decrease as the pressure of the space decreases. Decreased solubility allows a gas to leave a solution. Clinically, the pathologies associated with the VP have been reported to mainly include the normal joint motion, degeneration of the intervertebral discs or joints, and trauma. The frequent use of CT for trauma patients and the high spatial resolution of CT images might produce the greatest number of chances to detect the VP in trauma patients. The VP is observed at locations that experience a traumatic impact; thus, an analysis of the VP may be useful for elucidating the mechanism of an injury. When the VP is located in the abdomen, it is important to include perforation of the digestive tract in the differential diagnosis. The presence of the VP in trauma patients does not itself influence the final outcome.

  11. [Raynaud's phenomenon].

    PubMed

    Sprynger, M

    2004-06-01

    Raynaud's phenomenon (RP) is a common vascular disorder characterized by a recurrent transient vasospasm of the fingers and toes on exposure to cold or with emotional stress. Clinical criteria are used to distinguish patients with primary or idiopathic RP (formely Raynaud's disease) from those with secondary RP (formely Raynaud's syndrome). They include history, general physical examination, capillaroscopy, test for antinuclear antibody and erythrocyte sedimentation rate. More specific exams may be needed in selective cases. Excluding RP of occupational origin, the most common cause of secondary RP is a connective tissue disease (particularly scleroderma). RP may precede other clinical symptoms by several years, but most patients with RP will not progress to systemic disease. Nevertheless, primary RP may cause significant disability. We review the pathophysiology and clinical criteria of the disorder. Unfortunately, management of PR is still empirical and largely supportive.

  12. [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.

  13. 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.

  14. 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.

  15. 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

  16. Optical Properties of III-Mn-V Ferromagnetic Semiconductors

    NASA Astrophysics Data System (ADS)

    Burch, Kenneth

    2008-03-01

    We discuss the important role optical studies have played in our understanding of the electronic structure of III-Mn-V ferromagnetic semiconductors. These extensive studies have established the electronic structure is strongly affected by the strength of the exchange between the Mn local moments and the holes they introduce. Particular focus is given to Ga1-xMnxAs, where spectroscopic studies suggest the metallic state is unconventional. Finally, we will detail our recent experiments into the ultrafast manipulation of magnetism on the nanoscale. This work is in collaboration with D.B. Shrekenhamer, E.J. Singley, D.N. Basov (University of California, San Diego) J. Stephens, S. Mack, R.K. Kawakami, D.D. Awschalom(University of California, Santa Barbara), B.L. Sheu, N. Samarth (Pennsylvania State University), F. Chen, A. Azad, J. O'Hara, A.M. Dattelbaum, G. Montano, S. Crooker, and A.J. Taylor (Los Alamos National Laboratory).

  17. Spectroelectrochemical insights into structural and redox properties of immobilized endonuclease III and its catalytically inactive mutant.

    PubMed

    Moe, Elin; Rollo, Filipe; Silveira, Célia M; Sezer, Murat; Hildebrandt, Peter; Todorovic, Smilja

    2018-01-05

    Endonuclease III is a Fe-S containing bifunctional DNA glycosylase which is involved in the repair of oxidation damaged DNA. Here we employ surface enhanced IR spectroelectrochemistry and electrochemistry to study the enzyme from the highly radiation- and desiccation-resistant bacterium Deinococcus radiodurans (DrEndoIII2). The experiments are designed to shed more light onto specific parameters that are currently proposed to govern damage search and recognition by endonucleases III. We demonstrate that electrostatic interactions required for the redox activation of DrEndoIII2 may result in high electric fields that alter its structural and thermodynamic properties. Analysis of inactive DrEndoIII2 (K132A/D150A double mutant) interacting with undamaged DNA, and the active enzyme interacting with damaged DNA also indicate that the electron transfer is modulated by subtle differences in the protein-DNA complex. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Thermoregulation and rheological properties of blood in primary Raynaud's phenomenon and the vibration-induced white-finger syndrome.

    PubMed

    Ziegler, Sophie; Zöch, Carina; Gschwandtner, Michael; Eckhardt, Gerald; Windberger, Ursula; Minar, Erich; Rüdiger, Hugo; Osterode, Wolf

    2005-04-01

    Frequent use of vibrating tools may lead to typical attacks of Raynaud's phenomenon (RP). The present study assesses the feasibility of the use of thermographic measurements of blood rheometry in the diagnosis of vibration-induced white-finger (VWF) syndrome. We studied 38 patients that were suffering from RP (primary RP, n=29; VWF, n=9) and 13 controls (six men and 45 women; mean age 49.1+/-11.6 years). Superficial finger skin blood flow was assessed with an infrared thermocamera before and after exposure to heat and cold. Fibrinogen, whole-blood viscosity and erythrocyte aggregation at different shear rates and plasma viscosity were measured. In patients with RP finger temperatures after re-warming were lower than those in controls [right hand digit (DIG) I P<0.02; DIG II-V P<0.01; left hand DIG I P<0.01; DIG II-V p<0.02], male patients with primary RP had higher Fg-values (P<0.02) and a trend to higher plasma viscosity. Patients with VWF had a trend to lower plasma viscosity than controls. Whole-blood viscosity at each shear rate was highest in patients with VWF. Provocation manoeuvres are essential in the diagnosis of RP. We speculate that the decreased plasma viscosity in VWF is a compensatory physiological mechanism, probably counteracting the chronic effects of vasospasm. The rise in whole-blood viscosity could be due to endothelial injury or to a reduction in the venous blood pH level. The abnormal cold reactivity of patients with RP may be partly related to rheological factors.

  8. 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

  9. 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 ...

  10. 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.

  11. Properties of Group-IV, III-V and II-VI Semiconductors

    NASA Astrophysics Data System (ADS)

    Adachi, Sadao

    2005-03-01

    Almost all the semiconductors of practical interest are the group-IV, III-V and II-VI semiconductors and the range of technical applications of such semiconductors is extremely wide. The purpose of this book is twofold: * to discuss the key properties of the group-IV, III-V and II-VI semiconductors * to systemize these properties from a solid-state physics aspect The majority of the text is devoted to the description of the lattice structural, thermal, elastic, lattice dynamic, electronic energy-band structural, optical and carrier transport properties of these semiconductors. Some corrective effects and related properties, such as piezoelectric, elastooptic and electrooptic properties, are also discussed. The book contains convenient tables summarizing the various material parameters and the definitions of important semiconductor properties. In addition, graphs are included in order to make the information more quantitative and intuitive. The book is intended not only for semiconductor device engineers, but also physicists and physical chemists, and particularly students specializing in the fields of semiconductor synthesis, crystal growth, semiconductor device physics and technology.

  12. 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.

  13. 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.

  14. Magnetic properties of a manganese(III) Chain with monoatomic bridges: catena-MnF(salen).

    PubMed

    Birk, Torben; Pedersen, Kasper S; Piligkos, Stergios; Thuesen, Christian Aa; Weihe, Högni; Bendix, Jesper

    2011-06-20

    In the solid state, MnF(salen) forms chains wherein fairly linear fluoride bridges between high-spin Mn(III) centers are observed. We interpret the magnetic properties of these chains by use of the classical Fisher model and by use of the high-temperature expansion approach, as well as by exact matrix diagonalization of the spin Hamiltonian, of model rings. In solution, electron paramagnetic resonance shows the chains to be symmetrically cleaved to monomeric MnF(salen).

  15. Vibrational properties of III-V semiconductor in wurtzite phase: A comparative density functional theory study

    NASA Astrophysics Data System (ADS)

    Gajaria, Trupti K.; Dabhi, Shweta D.; Baraiya, Bhumi A.; Mankad, Venu; Jha, Prafulla K.

    2017-05-01

    A First principles study of structural, vibrational and thermal properties of III-V semiconductor compounds viz. Indium Arsenide (InAs) and Gallium Arsenide (GaAs) are investigated in their wurtzite phase which is normally observed in the case of nanosystems. Phonon dispersion curve, Debye temperature and specific heat behavior for both the compounds are compared and discussed. The present work will have its implication for making devices with tunable properties using InAs and GaAs based heterojuction solar cells.

  16. Binary group III-nitride based heterostructures: band offsets and transport properties

    NASA Astrophysics Data System (ADS)

    Roul, Basanta; Kumar, Mahesh; Rajpalke, Mohana K.; Bhat, Thirumaleshwara N.; Krupanidhi, S. B.

    2015-10-01

    In the last few years, there has been remarkable progress in the development of group III-nitride based materials because of their potential application in fabricating various optoelectronic devices such as light emitting diodes, laser diodes, tandem solar cells and field effect transistors. In order to realize these devices, growth of device quality heterostructures are required. One of the most interesting properties of a semiconductor heterostructure interface is its Schottky barrier height, which is a measure of the mismatch of the energy levels for the majority carriers across the heterojunction interface. Recently, the growth of non-polar III-nitrides has been an important subject due to its potential improvement on the efficiency of III-nitride-based opto-electronic devices. It is well known that the c-axis oriented optoelectronic devices are strongly affected by the intrinsic spontaneous and piezoelectric polarization fields, which results in the low electron-hole recombination efficiency. One of the useful approaches for eliminating the piezoelectric polarization effects is to fabricate nitride-based devices along non-polar and semi-polar directions. Heterostructures grown on these orientations are receiving a lot of focus due to enhanced behaviour. In the present review article discussion has been carried out on the growth of III-nitride binary alloys and properties of GaN/Si, InN/Si, polar InN/GaN, and nonpolar InN/GaN heterostructures followed by studies on band offsets of III-nitride semiconductor heterostructures using the x-ray photoelectron spectroscopy technique. Current transport mechanisms of these heterostructures are also discussed.

  17. A review on III-V core-multishell nanowires: growth, properties, and applications

    NASA Astrophysics Data System (ADS)

    Royo, Miquel; De Luca, Marta; Rurali, Riccardo; Zardo, Ilaria

    2017-04-01

    This review focuses on the emerging field of core-multishell (CMS) semiconductor nanowires (NWs). In these kinds of wires, a NW grown vertically on a substrate acts as a template for the coaxial growth of two or more layers wrapped around it. Thanks to the peculiar geometry, the strain is partially released along the radial direction, thus allowing the creation of fascinating heterostructures, even based on lattice mismatched materials that would hardly grow in a planar geometry. Enabling the unique bridging of the 1D nature of NWs with the exciting properties of 2D heterostructures, these novel systems are becoming attractive for material science, as well as fundamental and applied physics. We will focus on NWs made of III-V and III-V-based alloys as they represent a model system in which present growth techniques have reached a high degree of control on the material structural properties, and many physical properties have been assessed, from both the theoretical and experimental points of view. In particular, we provide an overview on the growth methods and structural properties of CMS NWs, on the modulation doping mechanisms enabled by these heterostructures, on the effects of a magnetic field, and on the phononic and optical properties typical of CMS NWs. Moreover, we review the main technological applications based on these systems, such as optoelectronic and photovoltaic devices.

  18. 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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.

  20. 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

  1. 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

  2. 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.

  3. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Lutetium(III) acetate phthalocyanines for photodynamic therapy applications: Synthesis and photophysicochemical properties.

    PubMed

    Mantareva, Vanya; Durmuş, Mahmut; Aliosman, Meliha; Stoineva, Ivanka; Angelov, Ivan

    2016-06-01

    The development of new water-soluble photosensitizers for photodynamic therapy (PDT) applications is a very active research topic. Efforts have been made to obtain the far-red absorbing phthalocyanine complexes with molecular design that facilitates the uptake and selectivity for a high PDT efficiency. The monomolecular lutetium(III) acetate phthalocyanines (LuPcs) substituted with methylpyridyloxy groups at non-peripheral (5) and peripheral (6) positions were synthesized by following the modification of the well-known synthetical routes. The photo-physicochemical properties of the both quaternized LuPcs were evaluated by the steady-state and time-resolved spectroscopy. The photochemical technique was applied to study the generation of the singlet oxygen. Two water-soluble and cationic LuPcs were synthesized and chemically characterized. The photo-physicochemical properties of absorption (675 and 685nm) and the red shifted fluorescence (704 and 721nm) as well as the fluorescence lifetimes (2.24 and 3.27ns) were studied. The promising values of singlet oxygen quantum yields (0.32 for 5 and 0.35 for 6) were determined. Lutetium(III) acetate phthalocyanine complexes were synthesized and evaluated with physicochemical properties suitable for future photodynamic therapy applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. 1D cerium(III) coordination polymer with pivalate bridges: Synthesis, structure and magnetic properties

    NASA Astrophysics Data System (ADS)

    Akhtar, Muhammad Nadeem; Mateen, Muhammad; Sadakiyo, Masaaki; Warsi, Muhammad Farooq; AlDamen, Murad A.; Song, You

    2017-08-01

    In the present work, synthesis, characterization, and properties of a new 1D-polymeric chain of [Ce(piv)3(MeOH)2]n (1D-Ce) are described. This polymeric structure was synthesized via reaction of Ce(NO3)3·6H2O with pivalic acid in presence of triethylamine. Crystal structure consists of cerium coordinated to eight oxygen atoms from five pivalate and two methanol moieties. Magnetic studies on the complex revealed a strong antiferromagnetic interaction between CeIII ions in the 1D chain.

  6. Carboxy derivatised Ir(III) complexes: synthesis, electrochemistry, photophysical properties and photocatalytic hydrogen generation.

    PubMed

    Paul, Avishek; Das, Nivedita; Halpin, Yvonne; Vos, Johannes G; Pryce, Mary T

    2015-06-14

    In this contribution the synthesis and characterisation of a series of novel mixed ligand iridium(iii) complexes, functionalised with a carboxy ester or phosphonate groups are reported. These groupings are introduced on the 4-position of either the phenyl pyridine or the 2,2'-bipyridyl ligands. A low temperature high yield synthesis for the precursor [Ir(ppy-COOEt)2(μ-Cl)]2 was developed. The photophysical and electrochemical properties of these compounds are also described, together with their behaviour as photosensitisers for the generation of hydrogen from water.

  7. 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.

  8. Luminescent dendritic cyclometalated iridium(III) polypyridine complexes: synthesis, emission behavior, and biological properties.

    PubMed

    Zhang, Kenneth Yin; Liu, Hua-Wei; Fong, Tommy Tsz-Him; Chen, Xian-Guang; Lo, Kenneth Kam-Wing

    2010-06-21

    Luminescent dendritic cyclometalated iridium(III) polypyridine complexes [{Ir(N--C)(2)}(n)(bpy-n)](PF(6))(n) (HN--C = 2-phenylpyridine, Hppy, n = 8 (ppy-8), 4 (ppy-4), 3 (ppy-3); HN--C = 2-phenylquinoline, Hpq, n = 8 (pq-8), 4 (pq-4), 3 (pq-3)) have been designed and synthesized. The properties of these dendrimers have been compared to those of their monomeric counterparts [Ir(N--C)(2)(bpy-1)](PF(6)) (HN--C = Hppy (ppy-1), Hpq (pq-1)). Cyclic voltammetric studies revealed that the iridium(IV/III) oxidation and bpy-based reduction occurred at about +1.24 to +1.29 V and -1.21 to -1.27 V versus SCE, respectively, for all the complexes. The molar absorptivity of the dendritic iridium(III) complexes is approximately proportional to the number of [Ir(N--C)(2)(N--N)] moieties in one complex molecule. However, the emission lifetimes and quantum yields are relatively independent of the number of [Ir(N--C)(2)(N--N)] units, suggesting negligible electronic communications between these units. Upon photoexcitation, the complexes displayed triplet metal-to-ligand charge-transfer ((3)MLCT) (dpi(Ir) --> pi*(bpy-n)) emission. The interaction of these complexes with plasmid DNA has been investigated by agarose gel retardation assays. The results showed that the dendritic iridium(III) complexes, unlike their monomeric counterparts, bound to the plasmid, and the interaction was electrostatic in nature. The lipophilicity of all the complexes has been determined by reversed-phase high-performance liquid chromatography (HPLC). Additionally, the cellular uptake of the complexes by the human cervix epithelioid carcinoma (HeLa) cell line has been examined by inductively coupled plasma mass spectrometry (ICP-MS), laser-scanning confocal microscopy, and flow cytometry. Upon internalization, all the complexes were localized in the perinuclear region, forming very sharp luminescent rings surrounding the nuclei. Interestingly, in addition to these rings, HeLa cells treated with the dendritic

  9. 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.

  10. 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.

  11. 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.

  12. Progress in the growth and optical properties of dilute bismide III-V semiconductor alloys

    NASA Astrophysics Data System (ADS)

    Beaton, Daniel A.; Christian, T.; Lewis, R. B.; Alberi, K.; Mascarenhas, A.

    2015-03-01

    The dilute bismuth containing III-V semiconducting alloys of have great potential for application in many areas of semiconductor technology, such as multijunction photvoltaics and solid-state lighting. There is a large reduction of the fundamental bandgap of GaAs with bismuth incorporation resultant from the raising of the valence band maximum. Dilute bismide alloys have long been compared to the dilute nitride alloy because bismuth introduces a state near the valence band edge of the host GaAs (instrad of near the conduction band edge in the nitride alloys) that affects its optical and electronic properties. Here I will discuss some recent advances in our understanding of the surface processes involved in dilute bismide alloy growth by molecular beam epitaxy which have lead to improved film quality and the growth of new bismide alloys. The improved film quality has made it possible to further explore the properties of this material.

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. Photochemistry of Fe(Iii)-Carboxylates in Polysaccharide-Based Materials with Tunable Mechanical Properties

    NASA Astrophysics Data System (ADS)

    Giammanco, Giuseppe E.

    We present the formulation and study of light-responsive materials based on carboxylate-containing polysaccharides. The functional groups in these natural polymers allow for strong interactions with transition metal ions such as Fe(III). The known photochemistry of hydroxycarboxylic acids in natural waters inspired us in exploring the visible light induced photochemistry of the carboxylates in these polysaccharides when coordinated to Fe(III) ions. Described in this dissertation are the design and characterization of the Fe(III)-polysaccharide materials, specifically the mechanistic aspects of the photochemistry and the effects that these reactions have on the structure of the polymer materials. We present a study of the quantitative photochemistry of different polysaccharide systems, where the presence of uronic acids was important for the photoreaction to take place. Alginate (Alg), pectate (Pec), hyaluronic acid (Hya), xanthan gum (Xan), and a polysaccharide extracted from the Noni fruit (NoniPs), were among the natural uronic acid-containing polysaccharide (UCPS) systems we analyzed. Potato starch, lacking of uronate groups, did not present any photochemistry in the presence of Fe(III); however, we were able to induce a photochemical response in this polysaccharide upon chemical manipulation of its functional groups. Important structure-function relationships were drawn from this study. The uronate moiety present in these polysaccharides is then envisioned as a tool to induce response to light in a variety of materials. Following this approach, we report the formulation of materials for controlled drug release, able to encapsulate and release different drug models only upon illumination with visible light. Furthermore, hybrid hydrogels were prepared from UPCS and non-responsive polymers. Different properties of these materials could be tuned by controlling the irradiation time, intensity and location. These hybrid gels were evaluated as scaffolds for tissue

  18. 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

  19. 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

  20. Synthesis and immunological properties of conjugates composed of group B streptococcus type III capsular polysaccharide covalently bound to tetanus toxoid.

    PubMed Central

    Lagergard, T; Shiloach, J; Robbins, J B; Schneerson, R

    1990-01-01

    A synthetic scheme for covalently binding group B streptococcus type III to tetanus toxoid (TT), using adipic acid dihydrazide as a spacer, is described. Type III alone or as a conjugate with TT was injected subcutaneously into laboratory mice, and the type-specific and TT antibody responses elicited by these immunogens were assayed. Type III-TT elicited significantly higher levels of type-specific antibodies after each immunization than did the type III alone. These levels were related to the dosage of the conjugate, enhanced by Freund adjuvant, and exhibited booster responses. Type III alone elicited only immunoglobulin M (IgM) antibodies in Swiss albino mice and mostly IgM and low levels of IgG antibodies of the IgG3 subclass in BALB/c mice. Type III-TT conjugates, in contrast, elicited mostly IgG antibodies in both strains of mice. IgA type III antibodies were not detected. The first two immunizations with the conjugates elicited type III antibodies in the IgG1 and in the IgG3 subclasses. Low levels of IgG2a type III antibodies were detected after a third injection of type III-TT. Conjugate-induced antibodies facilitated opsonization of group B streptococcus type III organisms and did not react with the structurally related pneumococcus type 14. TT alone or as a component of type III-TT induced mostly antibodies of the IgG class: IgG1 levels were the highest of the four subclasses. No IgA TT antibodies were detected. The conjugation procedure, therefore, enhanced the immunogenicity of and conferred T-cell dependent properties to the type III while preserving the immunogenicity of the TT component. The T-cell dependent properties of the conjugates were responsible for stimulating IgG type III antibodies which could be boosted. Evaluation of type III-TT conjugates in antibody-negative women of child-bearing age is planned. PMID:2407652

  1. Synthesis and luminescence properties of new red-shifted absorption lanthanide(III) chelates suitable for peptide and protein labelling.

    PubMed

    Maindron, Nicolas; Poupart, Séverine; Hamon, Maxime; Langlois, Jean-Baptiste; Plé, Nelly; Jean, Ludovic; Romieu, Anthony; Renard, Pierre-Yves

    2011-04-07

    The synthesis and photo-physical properties of an original bis-pyridinylpyrazine chromophore efficiently sensitising europium(III) and samarium(III) are described. The corresponding lanthanide(III) complexes display in aqueous solutions a maximum excitation wavelength which is significantly red-shifted compared to the usual terpyridine-based chelates, and a valuable luminescence brightness above 2,000 dm(3) mol(-1) cm(-1) at 345 nm was obtained with a europium(III) derivative. Further functionalisation with three different bioconjugatable handles was also investigated and their ability to efficiently label a model hexapeptide was evaluated and compared. Finally, the best bioconjugatable europium(III) chelate was used in representative labelling experiments involving monoclonal antibodies and the luminescence features of the corresponding bioconjugates remained satisfactory.

  2. 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.

  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. 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.

  5. 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.

  6. 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. Copyright © 2014. Published by Elsevier Inc.

  7. 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.

  8. 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.

  9. Synthesis and photophysical properties of europium(III)-β-diketonate complexes applied in LEDs.

    PubMed

    Shao, Guang; Yu, Huijuan; Zhang, Na; He, Yanjian; Feng, Kejun; Yang, Xin; Cao, Rihui; Gong, Menglian

    2014-01-14

    Six β-diketonate ligands were used to prepare the corresponding antenna europium(III) ternary complexes using 1,10-phenanthroline as an ancillary ligand. All the complexes exhibited high decomposition temperatures. Photophysical properties such as FT-IR spectra, UV-Vis absorption spectra, excitation and emission spectra, relative luminescent intensity ratios, luminescence decay curves and quantum yields based on the complexes were systematically studied and compared with each other. The energy-transfer mechanism was proposed as a ligand-sensitized luminescence process. Bright red light-emitting diodes (LEDs) were then fabricated by coating the complexes onto 395 nm-emitting InGaN chips. The light emission from the InGaN chips could be completely absorbed in the spectra of LEDs. The Commission International de I'Eclairage (CIE) chromaticity coordinates are close to the National Television Standard Committee (NTSC) standard value for the red color. All these findings indicate that these Eu(III) complexes are promising red phosphors for fabrication of near UV-based white LEDs.

  10. 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

  11. Synthesis and the Optical and Electrochemical Properties of Indium(III) Bis(arylimino)acenaphthene Complexes.

    PubMed

    Wang, Jingyi; Ganguly, Rakesh; Yongxin, Li; Díaz, Jesus; Soo, Han Sen; García, Felipe

    2017-07-17

    Aryl bis(imino)acenaphthenes (Ar-BIANs) are well-established rigid and sterically bulky diimine ligands, which are redox-noninnocent and versatile π-acceptors due to their low-lying π* orbitals and are frequently used to bind transition metals. However, the coordination chemistry of Ar-BIAN ligands to main group elements is not as well-developed as that of their transition metal counterparts. In particular, there are no comprehensive studies describing the spectroscopic and electrochemical properties of main group Ar-BIAN complexes. Herein, we report the synthesis and full characterization of a series of new indium(III) Ar-BIAN complexes, bearing 2,6-dialkyl (1b and 2b), 4-nitro (3b), and 4-dimethylamino (4b) groups at the aryl-diimine part of the ligand. Their optical and electrochemical properties have been revealed by UV-vis spectroscopy and cyclic voltammetry, respectively. Additionally, DFT calculations were performed to gain insights into the nature of the properties displayed.

  12. 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.

  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. 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.

  15. 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

  16. Broad-band properties of the CfA Seyfert galaxies. III - Ultraviolet variability

    NASA Technical Reports Server (NTRS)

    Edelson, R. A.; Pike, G. F.; Krolik, J. H.

    1990-01-01

    A total of 657 archived IUE spectra are used to study the UV variability properties of six members of the CfA Seyfert I galaxy sample. All show strong evidence for continuum and line variations and a tendency for less luminous objects to be more strongly variable. Most objects show a clear correlation at zero lag between UV spectral index and luminosity, evidence that the variable component is an accretion disk around a black hole which is systematically smaller in less luminous sources. No correlation is seen between the continuum luminosity and equivalent width of the C IV, Mg II, and semiforbidden C III emission lines when the entire sample is examined, but a clear anticorrelation is present when only repeated observations of individual objects are considered. This is due to a combination of light-travel time effects in the broad-line region and the nonlinear responses of lines to continuum fluctuations.

  17. 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

  18. 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

  19. 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

  20. 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.

  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. 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.

  3. 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.

  4. Role of host cell polarity and leading edge properties in Pseudomonas type III secretion

    PubMed Central

    Bridge, Dacie R.; Novotny, Matthew J.; Moore, Elizabeth R.; Olson, Joan C.

    2010-01-01

    Type III secretion (T3S) functions in establishing infections in a large number of Gram-negative bacteria, yet little is known about how host cell properties might function in this process. We used the opportunistic pathogen Pseudomonas aeruginosa and the ability to alter host cell sensitivity to Pseudomonas T3S to explore this problem. HT-29 epithelial cells were used to study cellular changes associated with loss of T3S sensitivity, which could be induced by treatment with methyl-beta-cyclodextrin or perfringolysin O. HL-60 promyelocytic cells are innately resistant to Pseudomonas T3S and were used to study cellular changes occurring in response to induction of T3S sensitivity, which occurred following treatment with phorbol esters. Using both cell models, a positive correlation was observed between eukaryotic cell adherence to tissue culture wells and T3S sensitivity. In examining the type of adhesion process linked to T3S sensitivity in HT-29 cells, a hierarchical order of protein involvement was identified that paralleled the architecture of leading edge (LE) focal complexes. Conversely, in HL-60 cells, induction of T3S sensitivity coincided with the onset of LE properties and the development of actin-rich projections associated with polarized cell migration. When LE architecture was examined by immunofluorescent staining for actin, Rac1, IQ-motif-containing GTPase-activating protein 1 (IQGAP1) and phosphatidylinositol 3 kinase (PI3 kinase), intact LE structure was found to closely correlate with host cell sensitivity to P. aeruginosa T3S. Our model for host cell involvement in Pseudomonas T3S proposes that cortical actin polymerization at the LE alters membrane properties to favour T3S translocon function and the establishment of infections, which is consistent with Pseudomonas infections targeting wounded epithelial barriers undergoing cell migration. PMID:19910414

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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)

  10. 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)

  11. 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.

  12. 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

  13. Complexing properties of Diphonix, a new chelating resin with diphosphonate ligands, toward Ga(III) and In(III)

    SciTech Connect

    Trochimczuk, A.W.; Alexandratos, S.D. ); Horwitz, E.P. )

    1994-02-01

    The complexing properties of Diphonix, a new chelating ion-exchange resin, toward indium and gallium cations was investigated. Variables included bead size, contact time, solution pH, and the presence of competing cations. The resin, which contains diphosphonic acid ligands, displayed rapid rates of complexation and high selectivity under acidic conditions. Metal uptake from 1 M sulfuric acid solution under continuous flow conditions was 0.47 mmol/g (33.0 mg/g) for gallium and 0.76 mmol/g (87.8 mg/g) for indium. The resin may be regenerated by elution with 1-hydroxyethane-1,1-diphosphonic acid or hydrochloric acid. 11 refs., 5 figs.

  14. 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

  15. Synthesis and luminescence properties of two novel lanthanide (III) perchlorate complexes with bis(benzoylmethyl) sulfoxide and benzoic acid.

    PubMed

    Li, Wen-Xian; Chai, Wen-Juan; Sun, Xiao-Jun; Ren, Tie; Shi, Xiao-Yan

    2010-07-01

    Two novel ternary rare earth complexes of Tb(III) and Dy(III) perchlorates with bis(benzoylmethyl) sulfoxide (L) and benzoic acid (L') had been synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC, (1)HNMR and UV spectra. The results indicated that the composition of these complexes was REL(5)L'(ClO(4))(2) x nH(2)O (RE = Tb(III), Dy(III); L = C(6)H(5)COCH(2)SOCH(2)COC(6)H(5), L' = C(6)H(5)COO; n = 6,8). The fluorescence spectra illustrated that the ternary rare earth complexes presented stronger fluorescence intensities, longer lifetimes and higher fluorescence quantum efficiencies than the binary rare earth complexes REL(5) x (ClO(4))(3) x 2 H(2)O. After the introduction of the second ligand benzoic acid group, the relative fluorescence emission intensities and fluorescence lifetimes of the ternary complexes REL(5)L'(ClO(4))(2) x nH(2)O (RE = Tb(III), Dy(III)) enhanced more obviously than the binary complexes. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand benzoic acid could sensitize fluorescence intensities of rare earth ions, and the introduction of benzoic acid group was resulted in the enhancement of the fluorescence properties of the ternary rare earth complexes. The phosphorescence spectra were also discussed.

  16. Study of Adsorption Property of Ga(III) onto Strongly Basic Resin for Ga Extraction from Bayer Liquor

    NASA Astrophysics Data System (ADS)

    Zhao, Zhuo; Yang, Yongxiang; Lu, Hao; Hua, Zhongsheng; Ma, Xiaoling

    Ion-exchange is the main technology used in industry for gallium recovery from Bayer liquor, the largest gallium production resource. However, the co-extraction of vanadium and the degradation of resins are the major issues. Further investigations related to fundamental theory are needed. This paper reports the study of the adsorption properties of a strongly basic resin having a combination of one =NOH group and another active group -NH2 for Ga(III) extraction. The influence of operational conditions such as contact time, initial Ga(III) concentration and temperature on Ga(III) adsorption were extensively investigated. The results revealed that the resin has high adsorption capacity and Ga(III) selectivity. The optimal adsorption condition was obtained at temperatures of 40-50°C and contact time of 40-60 min. The Ga(III) adsorption data on the resin fit well with the pseudo second-order kinetics. Langmuir and Freundlich models were used to describe Ga(III) adsorption isotherms on the resin.

  17. The structural and optical properties of type III human collagen biosynthetic corneal substitutes

    PubMed Central

    Hayes, Sally; Lewis, Phillip; Islam, M. Mirazul; Doutch, James; Sorensen, Thomas; White, Tomas; Griffith, May; Meek, Keith M.

    2015-01-01

    The structural and optical properties of clinically biocompatible, cell-free hydrogels comprised of synthetically cross-linked and moulded recombinant human collagen type III (RHCIII) with and without the incorporation of 2-methacryloyloxyethyl phosphorylcholine (MPC) were assessed using transmission electron microscopy (TEM), X-ray scattering, spectroscopy and refractometry. These findings were examined alongside similarly obtained data from 21 human donor corneas. TEM demonstrated the presence of loosely bundled aggregates of fine collagen filaments within both RHCIII and RHCIII-MPC implants, which X-ray scattering showed to lack D-banding and be preferentially aligned in a uniaxial orientation throughout. This arrangement differs from the predominantly biaxial alignment of collagen fibrils that exists in the human cornea. By virtue of their high water content (90%), very fine collagen filaments (2–9 nm) and lack of cells, the collagen hydrogels were found to transmit almost all incident light in the visible spectrum. They also transmitted a large proportion of UV light compared to the cornea which acts as an effective UV filter. Patients implanted with these hydrogels should be cautious about UV exposure prior to regrowth of the epithelium and in-growth of corneal cells into the implants. PMID:26159106

  18. Nanoscale investigation of the piezoelectric properties of perovskite ferroelectrics and III-nitrides

    NASA Astrophysics Data System (ADS)

    Rodriguez, Brian Joseph

    Nanoscale characterization of the piezoelectric and polarization related properties of III-Nitrides by piezoresponse force microscopy (PFM), electrostatic force microscopy (EFM) and scanning Kelvin probe microscopy (SKPM) resulted in the measurement of piezoelectric constants, surface charge and surface potential. Photo-electron emission microscopy (PEEM) was used to determine the local electronic band structure of a GaN-based lateral polarity heterostructure (GaN-LPH). Nanoscale characterization of the imprint and switching behavior of ferroelectric thin films by PFM resulted in the observation of domain pinning, while nanoscale characterization of the spatial variations in the imprint and switching behavior of integrated (111)-oriented PZT-based ferroelectric random access memory (FRAM) capacitors by PFM have revealed a significant difference in imprint and switching behavior between the inner and outer parts of capacitors. The inner regions of the capacitors are typically negatively imprinted and consequently tend to switch back after being poled by a positive bias, while regions at the edge of the capacitors tend to exhibit more symmetric hysteresis behavior. Evidence was obtained indicating that mechanical stress conditions in the central regions of the capacitors can lead to incomplete switching. A combination of vertical and lateral piezoresponse force microscopy (VPFM and LPFM, respectively) has been used to map the out-of-plane and in-plane polarization distribution, respectively, of integrated (111)-oriented PZT-based capacitors, which revealed poled capacitors are in a polydomain state.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. The Lazarus phenomenon

    PubMed Central

    Adhiyaman, Vedamurthy; Adhiyaman, Sonja; Sundaram, Radha

    2007-01-01

    Even though Lazarus phenomenon is rare, it is probably under reported. There is no doubt that Lazarus phenomenon is a reality but so far the scientific explanations have been inadequate. So far the only plausible explanation at least in some cases is auto-PEEP and impaired venous return. In patients with PEA or asystole, dynamic hyperinflation should considered as a cause and a short period of apnoea (30-60 seconds) should be tried before stopping resuscitation. Since ROSC occurred within 10 minutes in most cases, patients should be passively monitored for at least 10 minutes after the cessation of CPR before confirming death. PMID:18065707

  4. 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.

  5. Octanuclear [Ni(II)₄Ln(III)₄] complexes. Synthesis, crystal structures and magnetocaloric properties.

    PubMed

    Pasatoiu, Traian D; Ghirri, Alberto; Madalan, Augustin M; Affronte, Marco; Andruh, Marius

    2014-06-28

    Two original heterooctanuclear [Ni(II)4Ln(III)4] complexes (Ln(III) = Sm(III), Gd(III)) have been obtained starting from the [Ni(II)(valpn)(H2O)2] mononuclear precursor [H2valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)] and the corresponding lanthanide nitrates, in the presence of azide anions, through slow capture of atmospheric CO2. Three weak and competitive exchange interactions, J(GdGd), J(GdNi), J(NiNi), make the ground state of this magnetic system degenerate at cryogenic temperature and zero field. This, along with the high spin of Gd(III), lead to a significant magnetocaloric effect spread in the temperature range 1 to 20 K (ΔSm[0-7 T, 3.5 K] = 19 J kg(-1) K(-1)).

  6. 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.

  7. 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

  8. 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)

  9. Raynaud's phenomenon (primary)

    PubMed Central

    2008-01-01

    Introduction Raynaud’s phenomenon is an episodic vasospasm of the peripheral arteries, causing pallor followed by cyanosis and redness with pain and sometimes paraesthesia. On rare occasions it can lead to ulceration of the fingers and toes (and in some cases of the ears or nose). This review focuses on primary (idiopathic) Raynaud's phenomenon occurring in the absence of an underlying disease. The prevalence of primary Raynaud's phenomenon varies by sex, country, and exposure to workplace vibration. Methods and outcomes We conducted a systematic review and aimed to answer the following clinical question: What are the effects of treatments for primary Raynaud’s phenomenon? We searched: Medline, Embase, The Cochrane Library, and other important databases up to May 2008 (Clinical Evidence reviews are updated periodically, please check our website for the most up-to-date version of this review). We included harms alerts from relevant organisations such as the US Food and Drug Administration (FDA) and the UK Medicines and Healthcare products Regulatory Agency (MHRA). Results We found 15 systematic reviews, RCTs, or observational studies that met our inclusion criteria. We performed a GRADE evaluation of the quality of evidence for interventions. Conclusions In this systematic review we present information relating to the effectiveness and safety of the following interventions: amlodipine, diltiazem, exercise, inositol nicotinate, keeping warm, moxisylyte (thymoxamine), naftidrofuryl oxalate, nicardipine, nifedipine, prazosin, and smoking cessation. PMID:19445785

  10. Raynaud's phenomenon (primary)

    PubMed Central

    2011-01-01

    Introduction Raynaud’s phenomenon is an episodic vasospasm of the peripheral arteries, causing pallor, followed by cyanosis and redness with pain, and sometimes paraesthesia. On rare occasions it can lead to ulceration of the fingers and toes (and in some cases of the ears or nose). This review focuses on primary (idiopathic) Raynaud's phenomenon, occurring in the absence of an underlying disease. The prevalence of primary Raynaud's phenomenon varies by sex, country, and exposure to workplace vibration. Methods and outcomes We conducted a systematic review and aimed to answer the following clinical question: What are the effects of treatments for primary Raynaud’s phenomenon? We searched: Medline, Embase, The Cochrane Library, and other important databases up to May 2010 (Clinical Evidence reviews are updated periodically; please check our website for the most up-to-date version of this review). We included harms alerts from relevant organisations such as the US Food and Drug Administration (FDA) and the UK Medicines and Healthcare products Regulatory Agency (MHRA). Results We found 16 systematic reviews, RCTs, or observational studies that met our inclusion criteria. We performed a GRADE evaluation of the quality of evidence for interventions. Conclusions In this systematic review we present information relating to the effectiveness and safety of the following interventions: amlodipine, diltiazem, exercise, inositol nicotinate, keeping warm, moxisylyte (thymoxamine), naftidrofuryl oxalate, nicardipine, nifedipine, prazosin, and smoking cessation. PMID:21401971

  11. Raynaud's phenomenon (primary)

    PubMed Central

    2013-01-01

    Introduction Raynaud’s phenomenon is an episodic, reversible vasospasm of the peripheral arteries (usually digital). It causes pallor, followed by cyanosis and/or redness, often with pain and, at times, paraesthesia. On rare occasions, it can lead to ulceration of the fingers and toes (and, in some cases, of the ears or nose). This review focuses on primary (idiopathic) Raynaud's phenomenon, occurring in the absence of an underlying disease. The prevalence of primary Raynaud's phenomenon varies by sex, country, and exposure to workplace vibration. Methods and outcomes We conducted a systematic review and aimed to answer the following clinical question: What are the effects of drug treatments for primary Raynaud’s phenomenon? We searched: Medline, Embase, The Cochrane Library, and other important databases up to August 2013 (Clinical Evidence reviews are updated periodically; please check our website for the most up-to-date version of this review). We included harms alerts from relevant organisations such as the US Food and Drug Administration (FDA) and the UK Medicines and Healthcare products Regulatory Agency (MHRA). Results We found 9 systematic reviews, RCTs, or observational studies that met our inclusion criteria. We performed a GRADE evaluation of the quality of evidence for interventions. Conclusions In this systematic review we present information relating to the effectiveness and safety of the following interventions: amlodipine, diltiazem, nicardipine, and nifedipine. PMID:24112969

  12. 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)

  13. Light induced magnetic properties of spiropyrane tris(oxalato)chromate (III) single crystals

    SciTech Connect

    Morgunov, R.B.; Mushenok, F.B.; Aldoshin, S.M.; Yur'eva, E.A.; Shilov, G.V.; Tanimoto, Y.

    2009-06-15

    The effect of UV light on Weiss temperature and ESR spectra in 1-isopropyl-3, 3, 5', 6'-tetramethylspiro[indolin-2,2'-[2H]pyrano[3,2-b]pyridinium] tris(oxalato)chromate (III) (Sp{sub 3}Cr(C{sub 2}O{sub 4}){sub 3}) has been found. Additional line has been observed in the ESR spectra of irradiated samples in 'strong' magnetic fields of {approx}15 kOe. The analysis of angular dependences of the ESR spectra allowed a contribution of Cr{sup 3+} ions to magnetic properties of Sp{sub 3}Cr(C{sub 2}O{sub 4}){sub 3} to be determined. The zero-field splitting parameters D=0.619 cm{sup -1}, E=0.024 cm{sup -1} were derived from the experimental data. The parameters were typical for Cr{sup 3+} in the chromium oxalate. Weiss temperature changed sign from 25 to -25 K under UV irradiation. The value of Weiss temperature and its changing cannot be explained by exchange interaction, dipole-dipole interaction or the effect of crystal field. The existence of Weiss temperature is explained by the changes in amount and spin of paramagnetic particles. The change is due to thermoactivated redistribution of electrons between chromium ions and spiropyrane molecules. Light-induced transfer of electrons is also explaining the change in sign of Weiss temperature under UV irradiation. - Graphical abstract: Fragment of crystal structure of (Sp{sub 3}Cr(C{sub 2}O{sub 4}){sub 3}). Temperature dependences of reciprocal molar magnetic moment of the sample at T=2 K: (1) before irradiation, and (2) after UV irradiation.

  14. 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.

  15. Raynaud's phenomenon (secondary)

    PubMed Central

    2008-01-01

    Introduction Raynaud’s phenomenon is episodic vasospasm of the peripheral vessels, causing pallor followed by cyanosis and redness with pain and sometimes paraesthesia, and, rarely, ulceration of the fingers and toes. It presents as episodic colour changes of the digits, usually in response to cold exposure or stress. The classic triphasic colour change is white (ischaemia), then blue (deoxygenation), then red (reperfusion). Raynaud’s phenomenon can be primary (idiopathic) or secondary to several different conditions and causes. This review deals with secondary Raynaud’s phenomenon. Methods and outcomes We conducted a systematic review and aimed to answer the following clinical questions: What are the effects of self-help measures for secondary Raynaud’s phenomenon? What are the effects of drug treatments for secondary Raynaud’s phenomenon? We searched: Medline, Embase, The Cochrane Library, and other important databases up to May 2007 (Clinical Evidence reviews are updated periodically; please check our website for the most up-to-date version of this review). We included harms alerts from relevant organisations such as the US Food and Drug Administration (FDA) and the UK Medicines and Healthcare products Regulatory Agency (MHRA). Results We found 25 systematic reviews, RCTs, or observational studies that met our inclusion criteria. We performed a GRADE evaluation of the quality of evidence for interventions. Conclusions In this systematic review, we present information relating to the effectiveness and safety of the following interventions: alpha-blockers; angiotensin-converting enzyme (ACE) inhibitors; angiotensin II receptor antagonists; antithrombotics/inhibitors of platelet aggregation; biofeedback; calcium channel blockers; endothelin-1 receptor antagonists; glyceryl trinitrate (transdermal); hand exercises; inositol nicotinate; moxisylyte; naftidrofuryl oxylate; phosphodiesterase inhibitors; prostaglandins (oral, intravenous); relaxation therapy

  16. 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.

  17. 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.

  18. 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.

  19. Synthesis, crystal structures, photoluminescent, magnetic and chiroptical properties of two homochiral ErIII complexes with different nuclearity

    NASA Astrophysics Data System (ADS)

    Li, Xi-Li; Liu, Ying-Fan; Zhang, Xue-Li; Cheng, Conghui; Zheng, Xianjun; Zhu, Cancan; Zhou, Liming

    2017-06-01

    Employing chiral bis-bidentate N-donor ligand, (+)-2,5-bis(4,5-pinene-2-pyridyl) pyrazine (L), as a bridging ligand for Er(dbm)3H2O, and depending on the ratio control of reactants, two mono- and dinuclear homochiral ErIII complexes with the formulae Er(dbm)3L·2H2O (1) (dbm- = dibenzoylmethanate) and Er2(dbm)6L·6H2O (2) have been synthesized and structurally characterized. Circular dichroic (CD) spectra verify their chiroptical activities. Investigations on the luminescent properties of complexes 1 and 2 demonstrate that they exhibit characteristic near-infrared (NIR) luminescence of the ErIII ion at around 1533 nm and the emission intensity of the mononuclear complex 1 is much larger than that of dinuclear species 2, the reason of which is elucidated in this work. In addition, the measurements of magnetic properties indicate that the direct-current (dc) magnetic behaviors of complexes 1 and 2 mainly result from the thermal depopulation of the excited MJ sublevels of the ErIII ions. Notablely, complex 2 is the first example of chiral polynuclear lanthanide complexes with NIR-luminescence property.

  20. 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.

  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. 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.

  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. 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.

  5. 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.

  6. 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.

  7. PARACEST Properties of a Dinuclear Neodymium(III) Complex Bound to DNA or Carbonate

    PubMed Central

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

    2009-01-01

    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 Ln2(1) complexes (Ln(III) = Nd(III), Eu(III)) bind tightly to anionic ligands including carbonate, diethylphosphate and DNA. The CEST amide peak of Nd2(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 Eu2(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 Eu2(1) carbonate complex (Kd = 15 µM). 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. PMID:19555071

  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. 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.

  10. 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. Copyright © 2015 Elsevier España, S.L.U. and Sociedad Española de Reumatología y Colegio Mexicano de Reumatología. All rights reserved.

  11. 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

  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. 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)

  17. Winter Cardiovascular Diseases Phenomenon

    PubMed Central

    Fares, Auda

    2013-01-01

    This paper review seasonal patterns across twelve cardiovascular diseases: Deep venous thrombosis, pulmonary embolism, aortic dissection and rupture, stroke, intracerebral hemorrhage, hypertension, heart failure, angina pectoris, myocardial infarction, sudden cardiac death, venricular arrythmia and atrial fibrillation, and discuss a possible cause of the occurrence of these diseases. There is a clear seasonal trend of cardiovascular diseases, with the highest incidence occurring during the colder winter months, which have been described in many countries. This phenomenon likely contributes to the numbers of deaths occurring in winter. The implications of this finding are important for testing the relative importance of the proposed mechanisms. Understanding the influence of season and other factors is essential when seeking to implement effective public health measures. PMID:23724401

  18. Magnetic properties of diruthenium(II,III) carboxylate compounds with large zero-field splitting and strong antiferromagnetic coupling.

    PubMed

    Jiménez-Aparicio, R; Urbanos, F A; Arrieta, J M

    2001-02-12

    The magnetic properties of mixed-valent compounds of general formula Ru2Cl(mu-O2CR)4 [R = CH2-CH3 (1), C(Me)=CHEt) (2)] have been studied in the 2-300 K temperature range. This magnetic study also includes a revision of the magnetic properties of the complex Ru2Cl(mu-O2CCMePh2)4 (3). Compounds 1-3 show a linear structure and a strong antiferromagnetic coupling between the diruthenium units through the chlorine atoms according to previous studies. Two fitting models to explain the magnetic properties of these complexes that incorporate a large zero-field splitting together with a strong antiferromagnetic coupling are described. These models consider that each diruthenium unit (S = 3/2) is magnetically coupled to the nearest diruthenium unit and ignores the longer distance magnetic coupling. The fitting models were found to be successful in fitting the magnetic data of the linear diruthenium(II,III) complexes. The zero-field splitting, D, and the antiferromagnetic coupling, zJ, vary from 37.8 to 48.0 cm-1 and from -7.43 to -13.30 cm-1, respectively, for complexes. The D values are similar to those calculated for the nonlinear diruthenium(II,III) compounds and confirm the validity of the proposed fitting models.

  19. 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.

  20. 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.

  1. 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).

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

    PubMed

    Vilaplana, R; Romero, M A; Quirós, M; Salas, J M; González-Vílchez, F

    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.

  3. 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

  4. [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.

  5. Mononuclear ruthenium(III) complexes containing chelating thiosemicarbazones: Synthesis, characterization and catalytic property

    NASA Astrophysics Data System (ADS)

    Raja, N.; Ramesh, R.

    2010-02-01

    Mononuclear ruthenium(III) complexes of the type [RuX(EPh 3) 2(L)] (E = P or As; X = Cl or Br; L = dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX 3(EPh 3) 3] (where E = P, X = Cl; E = As, X = Cl or Br) and [RuBr 3(PPh 3) 2(CH 3OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh 3) 2(DHA-PTSC)] ( 5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.

  6. Structural and catalytic properties of some azo-rhodanine Ruthenium(III) complexes

    NASA Astrophysics Data System (ADS)

    Shoair, A. F.; El-Bindary, A. A.; Abd El-Kader, M. K.

    2017-09-01

    Novel azo-rhodanine ruthenium(III) complexes of the type trans-[Ru(Ln)2(AsPh3)2]Cl (Ln = monobasic bidentate anions of 5-(4‧-methoxyphenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL1), 5-(phenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL2) and 5-(4‧-chlorophenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL3); AsPh3 = triphenylarsine) have been synthesized and characterized by elemental analysis, spectroscopic (IR, 1H NMR and UV-VIS), magnetic, X-ray diffraction, mass spectra and thermal analysis techniques. These techniques confirm the formation of octahedral ruthenium(III) complexes. The Ru(III) complexes were tested as a catalysts for the oxidation of benzyl alcohol to benzaldehyde with N-methylmorpholine-N-oxide as a co-oxidant. The effect of time, temperature, and solvent were also studied and the mechanism of this catalytic oxidation reaction is suggested. Molecular docking was used to predict the binding between azo rhodanine derivatives (HLn) with the receptor of 3qum- immune system receptor of human prostate specific antigen (PSA) in a Fab sandwich with a high affinity and a PCa selective antibody.

  7. 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.

  8. 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.

  9. Gas sorption and luminescence properties of a terbium(III)-phosphine oxide coordination material with two-dimensional pore topology.

    PubMed

    Ibarra, Ilich A; Hesterberg, Travis W; Holliday, Bradley J; Lynch, Vincent M; Humphrey, Simon M

    2012-07-14

    The structure, stability, gas sorption properties and luminescence behaviour of a new lanthanide-phosphine oxide coordination material are reported. The polymer PCM-15 is based on Tb(III) and tris(p-carboxylated) triphenylphosphine oxide and has a 5,5-connected net topology. It exhibits an infinite three-dimensional structure that incorporates an open, two-dimensional pore structure. The material is thermally robust and remains crystalline under high vacuum at 150 °C. When desolvated, the solid has a CO(2) BET surface area of 1187 m(2) g(-1) and shows the highest reported uptake of both O(2) and H(2) at 77 K and 1 bar for a lanthanide-based coordination polymer. Isolated Tb(III) centres in the as-synthesized polymer exhibit moderate photoluminescence. However, upon removal of coordinated OH(2) ligands, the luminescence intensity was found to approximately double; this process was reversible. Thus, the Tb(III) centre was used as a probe to detect directly the desolvation and resolvation of the polymer.

  10. Effect of n-propyl substituents on the emission properties of blue phosphorescent iridium(iii) complexes

    NASA Astrophysics Data System (ADS)

    Zhou, Xiuwen; Burn, Paul L.; Powell, Benjamin J.

    2017-05-01

    Ligand substitution is often used for tuning the emission color of phosphorescent iridium(iii) complexes that are used in organic light-emitting diodes. However, in addition to tuning the emission color, the substituents can also affect the radiative and non-radiative decay rates of the excited state and hence the photoluminescence quantum yield. Understanding the substituent effect is therefore important for the design of new iridium(iii) complexes with specific emission properties. Using (time dependent) density functional methods, we investigate the substituent effect of n-propyl groups on the structure, emission color, and emission efficiency of fac-tris(1-methyl-5-phenyl-[1,2,4]triazolyl)iridium(iii) based phosphorescent complexes by comparing the calculated results for structural models with and without the n-propyl substituents. We find that attachment of the n-propyl groups increases the length of three Ir-N bonds, and although the emission color does not change significantly, the radiative and non-radiative rates do, leading to a prediction of enhanced blue phosphorescence emission efficiency. Furthermore, the calculations show that the attachment of the n-propyl groups leads to a larger activation energy to degradation and the formation of dark states.

  11. Effect of n-propyl substituents on the emission properties of blue phosphorescent iridium(iii) complexes.

    PubMed

    Zhou, Xiuwen; Burn, Paul L; Powell, Benjamin J

    2017-05-07

    Ligand substitution is often used for tuning the emission color of phosphorescent iridium(iii) complexes that are used in organic light-emitting diodes. However, in addition to tuning the emission color, the substituents can also affect the radiative and non-radiative decay rates of the excited state and hence the photoluminescence quantum yield. Understanding the substituent effect is therefore important for the design of new iridium(iii) complexes with specific emission properties. Using (time dependent) density functional methods, we investigate the substituent effect of n-propyl groups on the structure, emission color, and emission efficiency of fac-tris(1-methyl-5-phenyl-[1,2,4]triazolyl)iridium(iii) based phosphorescent complexes by comparing the calculated results for structural models with and without the n-propyl substituents. We find that attachment of the n-propyl groups increases the length of three Ir-N bonds, and although the emission color does not change significantly, the radiative and non-radiative rates do, leading to a prediction of enhanced blue phosphorescence emission efficiency. Furthermore, the calculations show that the attachment of the n-propyl groups leads to a larger activation energy to degradation and the formation of dark states.

  12. PHENOMENON OF SUPERCONDUCTIVITY.

    DTIC Science & Technology

    SUPERCONDUCTORS, NIOBIUM ALLOYS), (* NIOBIUM ALLOYS, TIN ALLOYS), METALLURGY, SINGLE CRYSTALS, CRYSTAL LATTICES, TANTALUM ALLOYS, SPECIFIC HEAT...DAMAGE, RADIATION EFFECTS, ELECTRON MICROSCOPES, RADIOFREQUENCY, TABLES(DATA), TEST METHODS, TEMPERATURE, ANOMALIES , MAGNETIC PROPERTIES.

  13. 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.

  14. The Formation of Supermassive Black Holes from Population III.1 Seeds. I. Cosmic Formation Histories and Clustering Properties

    SciTech Connect

    Banik, Nilanjan; Tan, Jonathan C.; Monaco, Pierluigi

    2016-08-15

    We calculate the cosmic distributions in space and time of the formation sites of the first, "Pop III.1" stars, exploring a model in which these are the progenitors of all supermassive black holes (SMBHs). Pop III.1 stars are defined to form from primordial composition gas in dark matter minihalos with $\\sim10^6\\:M_\\odot$ that are isolated from neighboring astrophysical sources by a given isolation distance, $d_{\\rm{iso}}$. We assume Pop III.1 sources are seeds of SMBHs, based on protostellar support by dark matter annihilation heating that allows them to accrete a large fraction of their minihalo gas, i.e., $\\sim 10^5\\:M_\\odot$. Exploring $d_{\\rm{iso}}$ from 10--$100\\:\\rm{kpc}$ (proper distances), we predict the redshift evolution of Pop III.1 source and SMBH remnant number densities. The local, $z=0$ density of SMBHs constrains $d_{\\rm{iso}}\\lesssim 100\\:\\rm{kpc}$ (i.e., $3\\:\\rm{Mpc}$ comoving distance at $z\\simeq30$). In our simulated ($\\sim60\\:\\rm{Mpc}$)$^3$ comoving volume, Pop III.1 stars start forming just after $z=40$. Their formation is largely complete by $z\\simeq25$ to 20 for $d_{\\rm{iso}}=100$ to $50\\:\\rm{kpc}$. We follow source evolution to $z=10$, by which point most SMBHs reside in halos with $\\gtrsim10^8\\:M_\\odot$. Over this period, there is relatively limited merging of SMBHs for these values of $d_{\\rm{iso}}$. We also predict SMBH clustering properties at $z=10$: feedback suppression of neighboring sources leads to relatively flat angular correlation functions. Finally, we consider a simple "Str\\"omgren" model for $d_{\\rm iso}$, based on ionizing feedback from zero age main sequence supermassive Pop III.1 stars that may be the direct progenitors of SMBHs in this scenario. Such models naturally produce feedback effects on scales of $\\sim100\\:$kpc and thus self-consistently generate a SMBH number density similar to the observed value.

  15. 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

  16. 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.

  17. Spin freezing phenomenon and transport properties in La 1/3Nd 1/3Ba 1/3MnO 3

    NASA Astrophysics Data System (ADS)

    Li, Guoqing; Xianyu, Ze; Kim, Chong-Oh; Kim, Hyo-Jin; Lee, Young-Woo

    2002-02-01

    The magnetic and transport properties of La 1/3Nd 1/3Ba 1/3MnO 3 with the colossal magnetoresistant (CMR) effect were studied by using SQUID. The irreversible curve for magnetizing intensity vs. temperature in an applied magnetic field of 13 Oe indicates that the spins of electrons are frozen, and therefore spin-glass state is probably formed below the Curie temperature. This fact implied that La 1/3Nd 1/3Ba 1/3MnO 3 is mictomagnetic, that is, ferromagnetism and antiferromagnetism co-exist in this kind of material.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. Type III and N Einstein spacetimes in higher dimensions: General properties

    SciTech Connect

    Ortaggio, Marcello; Pravda, Vojtech; Pravdova, Alena

    2010-09-15

    The Sachs equations governing the evolution of the optical matrix of geodetic WANDs (Weyl aligned null directions) are explicitly solved in n dimensions in several cases which are of interest in potential applications. This is then used to study Einstein spacetimes of type III and N in the higher dimensional Newman-Penrose formalism, considering both Kundt and expanding (possibly twisting) solutions. In particular, the general dependence of the metric and of the Weyl tensor on an affine parameter r is obtained in a closed form. This allows us to characterize the peeling behavior of the Weyl 'physical' components for large values of r, and thus to discuss, e.g., how the presence of twist affects polarization modes, and qualitative differences between four and higher dimensions. Further, the r dependence of certain nonzero scalar curvature invariants of expanding spacetimes is used to demonstrate that curvature singularities may generically be present. As an illustration, several explicit type N/III spacetimes that solve Einstein's vacuum equations (with a possible cosmological constant) in higher dimensions are finally presented.

  5. 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.

  6. On the structural-optical properties of Al-containing amorphous Si thin films and the metal-induced crystallization phenomenon

    SciTech Connect

    Zanatta, A. R.; Kordesch, M. E.

    2014-08-21

    Amorphous (a-)Si-based materials always attracted attention of the scientific community, especially after their use in commercial devices like solar cells and thin film transistors in the 1980s. In addition to their technological importance, the study of a-Si-based materials also present some interesting theoretical-practical challenges. Their crystallization as induced by metal species is one example, which is expected to influence the development of electronic-photovoltaic devices. In fact, the amorphous-to-crystalline transformation of the a-SiAl system has been successfully applied to produce solar cells suggesting that further improvements can be achieved. Stimulated by these facts, this work presents a comprehensive study of the a-SiAl system. The samples, with Al contents in the ∼0−15 at. % range, were made in the form of thin films and were characterized by different spectroscopic techniques. The experimental results indicated that: (a) increasing amounts of Al changed both the atomic structure and the optical properties of the samples; (b) thermal annealing induced the crystallization of the samples at temperatures that depend on the Al concentration; and (c) the crystallization process was also influenced by the annealing duration and the structural disorder of the samples. All of these aspects were addressed in view of the existing models of the a-Si crystallization, which were also discussed to some extent. Finally, the ensemble of experimental results suggest an alternative method to produce cost-effective crystalline Si films with tunable structural-optical properties.

  7. [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)

  8. 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.

  9. 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.

  10. 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.

  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. Electronic structure and transport properties of III-V core/shell nanowires

    NASA Astrophysics Data System (ADS)

    Viñas, Florinda; Leijnse, Martin

    We have modeled electron structure and low-temperature transport in III-V core/shell nanowires to establish a relationship between electron-hole hybridization and signatures in thermoelectrical measurements. Nanowires with a GaSb core and an InAs shell (and inverted) are interesting for studies of hybridization effects due to the bulk broken band gap alignment at the material interface. By varying the core radius and shell thickness of such wires we can modify the size of the band gap and create wires with band structures that exhibit hole-electron hybridization states. The band structures are obtained using 8-band k . p theory together with the envelope function approximation. The calculated energy dispersions are used as input to the Boltzmann equation to study thermoelectric transport quantities such as the Seebeck coefficient, in the diffusive limit.

  13. 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.

  14. 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.

  15. Photophysical properties of lanthanide(III) chelates-doped DNA-CTMA complex

    NASA Astrophysics Data System (ADS)

    Nakamura, Kazuki; Sagara, Amika; Kobayashi, Norihisa

    2011-09-01

    The photophysical properties of the DNA-CTMA/Eu(tta)3(H2O)2 were investigated in order to apply them for novel photonic materials. From absorption and CD measurements, the intercalation of Eu(tta)3(H2O)2 into DNA-CTMA backbones was indicated. Furthermore, the emission properties of the DNA-CTMA/Eu(tta)3(H2O)2 were superior to that of PMMA/Eu(tta)3(H2O)2 films. We expect achievements of our research help development of organic electronic device used biomaterials as typified by DNA-hybrid materials.

  16. Synthesis, structure, and properties of low-spin manganese(III)-poly(pyrazolyl)borate complexes.

    PubMed

    Hossain, Ferdaus; Rigsby, Matthew A; Duncan, Cole T; Milligan, Paul L; Lord, Richard L; Baik, Mu-Hyun; Schultz, Franklin A

    2007-04-02

    The manganese(III)-bis[poly(pyrazolyl)borate] complexes, Mn(pzb)2SbF6, where pzb- = tetrakis(pyrazolyl)borate (pzTp) (1), hydrotris(pyrazolyl)borate (Tp) (2), or hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) (3), have been synthesized by oxidation of the corresponding Mn(pzb)2 compounds with NOSbF6. The Mn(III) complexes are low-spin in solution and the solid state (microeff = 2.9-3.8 microB). X-ray crystallography confirms their uncommon low-spin character. The close conformity of mean Mn-N distances of 1.974(4), 1.984(5), and 1.996(4) A in 1, 2, and 3, respectively, indicates absence of the characteristic Jahn-Teller distortion of a high-spin d4 center. N-Mn-N bite angles of slightly less than 90 degrees within the facially coordinated pzb- ligands produce a small trigonal distortion and effective D3d symmetry in 1 and 2. These angles increase to 90.0(4)degrees in 3, yielding an almost perfectly octahedral disposition of N donors in Mn(Tp*)2+. Examination of structural data from 23 metal-bis(pzb) complexes reveals systematic changes within the metal-(pyrazolyl)borate framework as the ligand is changed from pzTp to Tp to Tp*. These deformations consist of significant increases in M-N-N, N-B-N, and N-N-B angles and a minimal increase in Mn-N distance as a consequence of the steric demands of the 3-methyl groups. Less effective overlap of pyrazole lone pairs with metal atom orbitals resulting from the M-N-N angular displacement is suggested to contribute to the lower ligand field strength of Tp* complexes. Mn(pzb)2+ complexes undergo electrochemical reduction and oxidation in CH3CN. The electrochemical rate constant (ks,h) for reduction of t2g4 Mn(pzb)2+ to t2g3eg2 Mn(pzb)2 (a coupled electron-transfer and spin-crossover reaction) is 1-2 orders of magnitude smaller than that for oxidation of t2g4 Mn(pzb)2+ to t2g3 Mn(pzb)22+. ks,h values decrease as Tp* > pzTp > Tp for the Mn(pzb)2+/0 electrode reactions, which contrasts with the behavior of the comparable Fe(pzb)2

  17. 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

  18. 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.

  19. 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) .

  20. 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). Copyright © 2012 Elsevier B.V. All rights reserved.

  1. 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.

  2. 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

  3. Thermoelectric properties of Cu/Ag doped type-III Ba24Ge100 clathrates

    NASA Astrophysics Data System (ADS)

    Fu, Jiefei; Su, Xianli; Yan, Yonggao; Liu, Wei; Zhang, Zhengkai; She, Xiaoyu; Uher, Ctirad; Tang, Xinfeng

    2017-09-01

    Type-III Ba24Ge100 clathrates possess low thermal conductivity and high electrical conductivity at room temperature and, as such, have a great potential as thermoelectric materials for power generation. However, the Seebeck coefficient is very low due to the intrinsically high carrier concentration. In this paper, a series of Ba24CuxGe100-x and Ba24AgyGe100-y specimens were prepared by vacuum melting combined with the subsequent spark plasma sintering (SPS) process. Doping Cu or Ag on the Ge site not only suppresses the concentration of electrons but it also decreases the thermal conductivity. In addition, the carrier mobility and the Seebeck coefficient increase due to the decrease in the carrier concentration. Thus, the power factor is greatly improved, leading to an improvement in the dimensionless figure of merit ZT. Cu-doped Ba24Cu6Ge94 reaches the maximum ZT value of about 0.17 at 873 K, while Ag-doped Ba24Ag6Ge94 attains the dimensionless figure of merit ZT of 0.31 at 873 K, more than 2 times higher value compared to un-doped Ba24Ge100.

  4. 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.

  5. [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.

  6. 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.

  7. 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

  8. Metabolism of Pentoses and Pentitols by Aerobacter aerogenes III. Physical and Immunological Properties of Pentitol Dehydrogenases and Pentulokinases1

    PubMed Central

    Mortlock, R. P.; Fossitt, D. D.; Petering, D. H.; Wood, W. A.

    1965-01-01

    Mortlock, R. P. (Michigan State University, East Lansing), D. D. Fossitt, D. H. Petering, and W. A. Wood. Metabolism of pentoses and pentitols by Aerobacter aerogenes. III. Physical and immunological properties of pentitol dehydrogenases and pentulokinases. J. Bacteriol. 89:129–135. 1965.—Four pentulokinases and three pentitol dehydrogenases were purified from Aerobacter aerogenes PRL-R3, and the properties of the enzymes within each family were compared. d-Ribulokinase was purified from cells grown on ribitol, d-arabitol, and xylitol, and from a mutant constitutive for ribitol dehydrogenase; d-xylulokinase, from cells grown on d-xylose and xylitol; l-ribulokinase, from cells grown on l-arabinose; and l-xylulokinase, after growth on l-xylose. Similarly, ribitol dehydrogenase was purified after growth on ribitol, d-arabinose, and xylitol, and from the ribitol dehydrogenase-constitutive mutant. d-Arabitol dehydrogenase was obtained after growth on d-arabitol or d-xylose, and xylitol dehydrogenase was obtained after growth on xylitol. Except for l-xylulokinase, which also had a different S20 value, the pentulokinases had identical pH optima, Km for the ketopentose, and sedimentation constants, and fractionated identically by a number of procedures. These kinases could be distinguished only by their substrate and immunological specificity. Ribitol dehydrogenase and d-arabitol dehydrogenase could be distinguished by several properties, but the properties of xylitol dehydrogenase were always similar to ribitol dehydrogenase. In all cases, individual kinases or dehydrogenases produced by different inducers had identical properties. These data constitute evidence against multiple forms of the same enzyme being produced by different inducers and against the dehydrogenase family containing essentially identical proteins differing only at the active site. For the kinases, three of the four appear to differ only at the active site. PMID:14255652

  9. 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.

  10. Mechanical Properties versus Morphology of Ordered Polymers. Volume III. Part I

    DTIC Science & Technology

    1982-08-01

    heat treament and a modified heat 115 treatment chamber is currently under construction. Therefore, the interpretation of our present heat treatment...laser Raman and Fourier transform infrared spectroscopy. Heat treated fibers have been produced with a modulus of 2100 grams per denier (g/d) and a...Fiber heat treatment ........... . . 114 B. Temperature Dependence of Tensile Properties .. . 119 C. Fiber Torsional Modulus . . ............ . 121 D

  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. Synthesis, structures, and magnetic properties of tetranuclear CuII-LnIII complexes.

    PubMed

    Costes, Jean-Pierre; Auchel, Magali; Dahan, Françoise; Peyrou, Viviane; Shova, Sergiu; Wernsdorfer, Wolfgang

    2006-03-06

    The copper(II)-gadolinium(III) and copper(II)-terbium(III) complexes studied in this report derive from disymmetric trianionic ligands abbreviated H3Li (i = 4-6). These ligands are obtained through reaction of different aldehydes with "half-units" having an amide function, the latter resulting from the monocondensation of different diamines with phenyl 2-hydroxy-3-methoxybenzoate. Upon deprotonation, the Li ligands (i = 4-10) possess an inner N2O2 coordination site with one amido, one imine, and two phenoxo functions, an outer O2O2 or O2O coordination site, and an amido oxygen atom positioned out of these two sites. The trianionic character of such ligands yields original anionic complexes in the presence of copper(II) or nickel(II) ions, with a 1/1 L/M stoichiometry. The crystal and molecular structures of four complexes, two 3d (1, 5) and two 3d-4f (12, 13) complexes, have been determined. Complex 1 crystallizes in the monoclinic space group C2/c: a = 27.528(2) A, b = 7.0944(7) A, c = 22.914(2) A, beta = 92.130(6) degrees , V = 4471.9(7) A(3), Z = 8 for C(21.5)H(27)CuKN(2)O(6.5). Complex 5 crystallizes in the monoclinic space group P2(1)/n (No. 14): a = 11.0760(9) A, b = 21.454(2) A, c = 15.336(1) A, beta = 101.474(1) degrees , V = 3571.5(5) A(3), Z = 4. Complex 12 crystallizes in the triclinic space group P (No. 2): a = 8.682(2) A, b = 11.848(2) A, c = 11.928(2) A, alpha = 81.77(3) degrees , beta = 89.17(3) degrees , gamma = 85.49(3) degrees , V = 1210.6(4) A(3), Z = 2 for C20H22CuN5O11Tb. Complex 13 belongs to the monoclinic space group C2/c: a = 25.475(5)A, b = 12.934(3)A, c = 15.023(3) A, beta = 91.06(3) degrees , V = 4949.02A3, Z = 8 for C21H25CuN4O12Tb. The structural determinations confirm that the dinuclear entities involved in 12 and 13 are disposed in a head-to-tail arrangement to give tetranuclear complexes in which the copper and lanthanide ions are positioned at the vertexes of a rectangle. In the [Cu-Gd]2 species, there are two different

  14. 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.

  15. X-ray diffraction, vibrational properties, and dielectric studies of 3-ammoniumpropyl imidazolium pentabromoantimonate (III)

    NASA Astrophysics Data System (ADS)

    Taher, Marwa Ben; Chaari, Najla; Bechir, Mohamed Ben; Chaabouni, Slaheddine

    2017-04-01

    A new organic-inorganic material 3-ammoniumpropyl imidazolium pentabromoantimonate (III) was reported. The title compound was synthesized at room temperature by slow evaporation and then characterized by single-crystal and powder X-ray diffraction, spectroscopic measurements, thermal analysis, and dielectric technique. It crystallizes in the non-centrosymmetric space group P212121 with the following unit cell parameters: a = 8.7120(7), b = 12.6608(1), c = 14.3498(1) Å with Z = 4. The crystal is built up of separated SbBr5 2- polyhedra anions and 3-ammoniumpropyl imidazolium cations. The cohesion of the structure is ensured by network of N-H…Br hydrogen bonds between the 3-ammoniumpropyl imidazolium cations and [SbBr5]2- anions, in which they may be effective in the stabilization of the crystal structure. The Raman and infrared spectra confirm the presence of both cationic [C6H13N3]2+ and anionic [SbBr5]2- entities. Dielectric data were analyzed using complex permittivity ɛ* and complex electrical modulus M* for the sample at various temperatures. The conductivity follows the Arrhenius low. The Z' and Zʺ versus frequency plots are well fitted to an equivalent circuit model. The circuits consist of the parallel combination of bulk resistance Rp and constant phase elements CPE. [C6H13N3]SbBr5 crystals undergo one endothermic peak at 333 K. This transition was detected by DSC and by dielectric measurements using the impedance and modulus spectroscopy techniques.

  16. Tunable optoelectronic and ferroelectric properties in Sc-based III-nitrides

    NASA Astrophysics Data System (ADS)

    Zhang, Siyuan; Holec, David; Fu, Wai Yuen; Humphreys, Colin J.; Moram, Michelle A.

    2013-10-01

    Sc-based III-nitride alloys were studied using density functional theory with special quasi-random structure methodology. ScxAl1-xN and ScxGa1-xN alloys are found to be stable in hexagonal phases up to x ≈ 0.56 and x ≈ 0.66, respectively, above which rock-salt structures are more stable. Epitaxial strain stabilization can prevent spinodal decomposition up to x ≈ 0.4 (ScxAl1-xN on AlN or GaN) and x = 0.27 (ScxGa1-xN on GaN). The increase in Sc content expands the in-plane lattice parameter of ScxAl1-xN and ScxGa1-xN alloys, leads to composition- and strain-tunable band gaps and polarization, and ultimately introduces ferroelectric functionality in ScxGa1-xN at x ≈ 0.625. A modified Becke-Johnson exchange-correlation potential was applied to study the electronic structures, which yielded band gaps comparable to those from hybrid functional calculations, yet in a much shorter computational time. The alloys were found to retain wide band gaps, which stay direct up to x = 0.25 (ScxAl1-xN) and x = 0.5 (ScxGa1-xN). The band gaps decrease with increasing x for ScxAl1-xN, in which the Sc-3d states dominate at the conduction band minimum and lead to flat electron dispersion at the Γ point. Conversely, the band gaps increase with increasing x for ScxGa1-xN (up to x = 0.5), in which Sc-3d states do not contribute to the conduction band minimum at the Γ point.

  17. 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.

  18. Raynaud's phenomenon induced by sulphasalazine.

    PubMed Central

    Reid, J.; Holt, S.; Housley, E.; Sneddon, D. J.

    1980-01-01

    Sulphasalazine-induced Raynaud's phenomenon is reported in a patient who showed no other features of a drug-induced lupus syndrome. The vascular disturbance disappeared when the drug was withdrawn on 3 occasions. A simple technique for assessing the circulatory abnormality in Raynaud's phenomenon is described. PMID:6104805

  19. Optical properties of Eu(III) doped strontium gadolinium niobate oxide

    SciTech Connect

    Vishwnath, Verma E-mail: vermavicky.1988@gmail.com; Srinivas, M.; Patel, Nimesh; Modi, Dhaval; Murthy, K. V. R.

    2016-05-23

    Sr{sub 2}GdNbO{sub 6} doped with trivalent ion of Eu phosphors having monoclinic phase of space group P2{sub 1}/n have been synthesized via solid state reaction method, and their photoluminescence properties have been examined under UV excitation. The emission peaks exhibited around 580, 596, and 610 nm wavelength. By using xenon lamp as a source of excitation having wavelengths at 254 and 262 nm, it is observed that the maximum light emission yielded in red region. It is inferred that the dopant Eu{sup +3} ions may take the substitutional positions at non-centrosymmetric site.

  20. Bidirectional negative differential thermal resistance phenomenon and its physical mechanism in the Frenkel-Kontorova lattices

    SciTech Connect

    Jianqiang, Zhang; Linru, Nie Chongyang, Chen; Xinyu, Zhang

    2016-07-15

    Thermal conduction of the Frenkel-Kontorova (FK) lattices with interfacial coupling is investigated numerically. The results indicate that: (i) For appropriate lattice periods, as the system is symmetric, a bidirectional negative differential thermal resistance (NDTR) phenomenon will appear. If the system is asymmetric, the bidirectional NDTR is gradually converted into an unidirectional NDTR. (ii) The bidirectional NDTR phenomenon effect also depends on the period of the FK lattice as the other parameters remains unchanged. With the increment of the lattice period, the bidirectional NDTR will gradually disappear. (iii) From a stochastic dynamics point of view, thermal transport properties of the system are determined by the competition between the two types of thermal conduction: one comes from the collusion between atoms, the other is due to the elastic coupling between atoms. For the smaller lattice periods, the former type of thermal conduction occupies the dominating position and the NDTR effect will appear.

  1. 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.

  2. 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

  3. 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.

  4. Ursell Operators in Statistical Physics III: Thermodynamic Properties of Degenerate Gases

    NASA Astrophysics Data System (ADS)

    Grüter, P.; Laloë, F.; Meyerovich, A. E.; Mullin, W.

    1997-03-01

    We study in more details the properties of the generalized Beth Uhlenbeck formula obtained in a preceding article. This formula leads to a simple integral expression of the grand potential of any dilute system, where the interaction potential appears only through the matrix elements of the second order Ursell operator U_2. Our results remain valid for significant degree of degeneracy of the gas, but not when Bose Einstein (or BCS) condensation is reached, or even too close to this transition point. We apply them to the study of the thermodynamic properties of degenerate quantum gases: equation of state, magnetic susceptibility, effects of exchange between bound states and free particles, etc. We compare our predictions to those obtained within other approaches, especially the “pseudo potential” approximation, where the real potential is replaced by a potential with zero range (Dirac delta function). This comparison is conveniently made in terms of a temperature dependent quantity, the “Ursell length”, which we define in the text. This length plays a role which is analogous to the scattering length for pseudopotentials, but it is temperature dependent and may include more physical effects than just binary collision effects; for instance, for fermions at very low temperatures, it may change sign or increase almost exponentially. As an illustration, numerical results for quantum hard spheres are given.

  5. The Viscoelastic Properties of Passive Eye Muscle in Primates. III: Force Elicited by Natural Elongations

    PubMed Central

    Quaia, Christian; Ying, Howard S.; Optican, Lance M.

    2010-01-01

    We have recently shown that in monkey passive extraocular muscles the force induced by a stretch does not depend on the entire length history, but to a great extent is only a function of the last elongation applied. This led us to conclude that Fung's quasi-linear viscoelastic (QLV) model, and more general nonlinear models based on a single convolution integral, cannot faithfully mimic passive eye muscles. Here we present additional data about the mechanical properties of passive eye muscles in deeply anesthetized monkeys. We show that, in addition to the aforementioned failures, previous models also grossly overestimate the force exerted by passive eye muscles during smooth elongations similar to those experienced during normal eye movements. Importantly, we also show that the force exerted by a muscle following an elongation is largely independent of the elongation itself, and it is mostly determined by the final muscle length. These additional findings conclusively rule out the use of classical viscoelastic models to mimic the mechanical properties of passive eye muscles. We describe here a new model that extends previous ones using principles derived from research on thixotropic materials. This model is able to account reasonably well for our data, and could thus be incorporated into models of the eye plant. PMID:20221406

  6. The viscoelastic properties of passive eye muscle in primates. III: force elicited by natural elongations.

    PubMed

    Quaia, Christian; Ying, Howard S; Optican, Lance M

    2010-03-08

    We have recently shown that in monkey passive extraocular muscles the force induced by a stretch does not depend on the entire length history, but to a great extent is only a function of the last elongation applied. This led us to conclude that Fung's quasi-linear viscoelastic (QLV) model, and more general nonlinear models based on a single convolution integral, cannot faithfully mimic passive eye muscles. Here we present additional data about the mechanical properties of passive eye muscles in deeply anesthetized monkeys. We show that, in addition to the aforementioned failures, previous models also grossly overestimate the force exerted by passive eye muscles during smooth elongations similar to those experienced during normal eye movements. Importantly, we also show that the force exerted by a muscle following an elongation is largely independent of the elongation itself, and it is mostly determined by the final muscle length. These additional findings conclusively rule out the use of classical viscoelastic models to mimic the mechanical properties of passive eye muscles. We describe here a new model that extends previous ones using principles derived from research on thixotropic materials. This model is able to account reasonably well for our data, and could thus be incorporated into models of the eye plant.

  7. 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.

  8. The Swift BAT X-Ray Survey. III. X-Ray Spectra and Statistical Properties

    NASA Astrophysics Data System (ADS)

    Ajello, M.; Rau, A.; Greiner, J.; Kanbach, G.; Salvato, M.; Strong, A. W.; Barthelmy, S. D.; Gehrels, N.; Markwardt, C. B.; Tueller, J.

    2008-01-01

    In this concluding part of the series of three papers dedicated to the Swift BAT hard X-ray survey (BXS), we focus on the X-ray spectral analysis and statistical properties of the source sample. Using a dedicated method to extract time-averaged spectra of BAT sources, we show that Galactic sources have, generally, softer spectra than extragalactic objects and that Seyfert 2 galaxies are harder than Seyfert 1s. The averaged spectrum of all Seyfert galaxies is consistent with a power-law with a photon index of 2.00 +/- 0.07. The cumulative flux-number relation for the extragalactic sources in the 14-170 keV band is best described by a power-law with a slope α = 1.55 +/- 0.20 and a normalization of 9.6 +/- 1.9 × 10-3 AGNs deg-2 (or 396 +/- 80 AGNs all-sky) above a flux level of 2 × 10-11 ergs cm-2 s-1 (~0.85 mcrab). The integration of the cumulative flux per unit area indicates that BAT resolves 1%-2% of the X-ray background emission in the 14-170 keV band. A subsample of 24 extragalactic sources above the 4.5 σ detection limit is used to study the statistical properties of AGNs. This sample is composed of local Seyfert galaxies (z = 0.026, median value) and ~10% blazars. We find that 55% of the Seyfert galaxies are absorbed by column densities of NH > 1022 H atoms cm-2 but that none is genuinely bona fide Compton thick. This study shows the capabilities of BAT to probe the hard X-ray sky to the millicrab level.

  9. 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

  10. Synthesis, characterization and photo-physical properties of Eu(III) complexes and its luminescent thin films

    NASA Astrophysics Data System (ADS)

    Sahoo, Jashobanta; lakshmi, D. Shanthana; Subramanian, Palani S.; George, T. M.; Reddy, M. L. P.

    2017-08-01

    Luminescent chiral europium(III) complexes EuLRCl3 (1) and EuLSCl3 (2) were synthesised [where LR and LS are schiff-base ligands of 2,9-dialdehyde 1,10-phenanthroline and (R) and (S) isomer of 2-amino-3-phenylpropanol]. These europium complexes depicting intense ;red luminescence; upon incorporating them in polyvinyl alcohol (PVA) matrices a series of transparent, flexible thin films were fabricated. These complexes 1, 2 and the films 1a-1c, 2a-2c were investigated for their photophysical properties such as radiative (ARAD) and non-radiative (ANR) decay rates, lifetimes (τobs), radiative lifetime (τRAD), intrinsic quantum yield (ΦLn), energy transfer efficiencies (Φsen) and total quantum yields (Φoverall). This PVA material at higher concentration demonstrates an interesting LRET (Luminescence Resonance Energy Transfer) behaviour. Based on the detailed investigation of the photo-luminescent properties, a plausible mechanism was proposed for energy transfer process.

  11. 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.

  12. 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.

  13. WINGS-SPE. III. Equivalent width measurements, spectral properties, and evolution of local cluster galaxies

    NASA Astrophysics Data System (ADS)

    Fritz, J.; Poggianti, B. M.; Cava, A.; Moretti, A.; Varela, J.; Bettoni, D.; Couch, W. J.; D'Onofrio D'Onofrio, M.; Dressler, A.; Fasano, G.; Kjærgaard, P.; Marziani, P.; Moles, M.; Omizzolo, A.

    2014-06-01

    Context. Cluster galaxies are the ideal sites to look at when studying the influence of the environment on the various aspects of the evolution of galaxies, such as the changes in their stellar content and morphological transformations. In the framework of wings, the WIde-field Nearby Galaxy-cluster Survey, we have obtained optical spectra for ~6000 galaxies selected in fields centred on 48 local (0.04 < z < 0.07) X-ray selected clusters to tackle these issues. Aims: By classifying the spectra based on given spectral lines, we investigate the frequency of the various spectral types as a function of both the clusters' properties and the galaxies' characteristics. In this way, using the same classification criteria adopted for studies at higher redshift, we can consistently compare the properties of the local cluster population to those of their more distant counterparts. Methods: We describe a method that we have developed to automatically measure the equivalent width of spectral lines in a robust way, even in spectra with a non optimal signal-to-noise ratio. This way, we can derive a spectral classification reflecting the stellar content, based on the presence and strength of the [Oii] and Hδ lines. Results: After a quality check, we are able to measure 4381 of the ~6000 originally observed spectra in the fields of 48 clusters, of which 2744 are spectroscopically confirmed cluster members. The spectral classification is then analysed as a function of galaxies' luminosity, stellar mass, morphology, local density, and host cluster's global properties and compared to higher redshift samples (MORPHS and EDisCS). The vast majority of galaxies in the local clusters population are passive objects, being also the most luminous and massive. At a magnitude limit of MV < -18, galaxies in a post-starburst phase represent only ~11% of the cluster population, and this fraction is reduced to ~5% at MV < -19.5, which compares to the 18% at the same magnitude limit for high

  14. 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.

  15. 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.

  16. The targeting of starch binding domains from starch synthase III to the cell wall alters cell wall composition and properties.

    PubMed

    Grisolia, Mauricio J; Peralta, Diego A; Valdez, Hugo A; Barchiesi, Julieta; Gomez-Casati, Diego F; Busi, María V

    2017-01-01

    Starch binding domains of starch synthase III from Arabidopsis thaliana (SBD123) binds preferentially to cell wall polysaccharides rather than to starch in vitro. Transgenic plants overexpressing SBD123 in the cell wall are larger than wild type. Cell wall components are altered in transgenic plants. Transgenic plants are more susceptible to digestion than wild type and present higher released glucose content. Our results suggest that the transgenic plants have an advantage for the production of bioethanol in terms of saccharification of essential substrates. The plant cell wall, which represents a major source of biomass for biofuel production, is composed of cellulose, hemicelluloses, pectins and lignin. A potential biotechnological target for improving the production of biofuels is the modification of plant cell walls. This modification is achieved via several strategies, including, among others, altering biosynthetic pathways and modifying the associations and structures of various cell wall components. In this study, we modified the cell wall of A. thaliana by targeting the starch-binding domains of A. thaliana starch synthase III to this structure. The resulting transgenic plants (E8-SDB123) showed an increased biomass, higher levels of both fermentable sugars and hydrolyzed cellulose and altered cell wall properties such as higher laxity and degradability, which are valuable characteristics for the second-generation biofuels industry. The increased biomass and degradability phenotype of E8-SBD123 plants could be explained by the putative cell-wall loosening effect of the in tandem starch binding domains. Based on these results, our approach represents a promising biotechnological tool for reducing of biomass recalcitrance and therefore, the need for pretreatments.

  17. 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

  18. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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%)

  11. 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.

  12. [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.

  13. [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.

  14. Synthetic control of excited-state properties in cyclometalated Ir(III) complexes using ancillary ligands.

    PubMed

    Li, Jian; Djurovich, Peter I; Alleyne, Bert D; Yousufuddin, Muhammed; Ho, Nam N; Thomas, J Christopher; Peters, Jonas C; Bau, Robert; Thompson, Mark E

    2005-03-21

    (nr) = nonradiative decay rate). Decreased 1MLCT character in the T1 state also increases the Huang-Rhys factors in the emission spectra, decreases the extinction coefficient of the T1 transition, and consequently decreases the radiative decay rates (k(r)). Overall, the luminescence quantum yields decline with increasing emission energies. A linear dependence of the radiative decay rate (k(r)) or extinction coefficient (epsilon) on (1/deltaE)2 has been demonstrated, where deltaE is the energy difference between the 1MLCT and 3LC transitions. A value of 200 cm(-1) for the spin-orbital coupling matrix element 3LC absolute value(H(SO)) 1MLCT of the (tpy)2 Ir(LL') complexes can be deduced from this linear relationship. The (fppy)2 Ir(LL') complexes with corresponding ancillary ligands display similar trends in excited-state properties.

  15. 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

  16. Effect of γ- irradiation on structural, optical and electrical properties of thermally evaporated iron (III) chloride tetraphenylporphyrin thin films

    NASA Astrophysics Data System (ADS)

    El-Nahass, M. M.; Zayed, H. A.; Elgarhy, E. E.; Hassanien, A. M.

    2017-10-01

    Influence of γ-irradiation on structural, optical and electrical properties of thermally evaporated iron (III) chloride tetraphenylporphyrin (FeTPPCl) thin films have been reported. The structural features are investigated by scanning electron microscope (SEM) and transmission electron microscope (TEM) techniques. The optical constants of as-deposited and γ-irradiated FeTPPCl thin films have been determined in the wavelength range 200-2500 nm using spectrophotometric measurements at nearly normal incidence of light. The calculated values of the absorption coefficient,α, are used to estimate the type of transitions for as-deposited and γ-irradiated FeTPPCl thin films. The real part of the refractive index in the transparent region is discussed by using a single-oscillator and Drude models. According to Miller's rule, the single oscillator model is used to deduce the third-order nonlinear susceptibility, χ(3). The temperature dependence of DC electrical conductivity, σDC, confirms the semiconducting behaviour of FeTPPCl thin films. A free band type in the higher temperature region and hopping type in the low-temperature region have been used to explain the DC conduction mechanisms of FeTPPCl thin films.

  17. Structure, spectroscopic measurement, thermal studies and optical properties of a new hybrid compound of aquapentachloroindoidate(III) complex

    NASA Astrophysics Data System (ADS)

    Lassoued, Mohamed Saber; Abdelbaky, Mohammed S. M.; Meroño, Rafael Mendoza; Gadri, Abdellatif; Ammar, Salah; Ben Salah, Abdelhamid; García-Granda, Santiago

    2017-08-01

    A new organic-inorganic complex, bis(4-amine pyridinium) aquapentachloroindoidate(III) (C5H7N2)2[InCl5(H2O)], was synthesized and characterized by single crystal and powder X-ray diffraction, Hirshfeld surface, vibrational spectra, thermal analyses (TGA and DTA) and NMR 13C. Compound crystallizes in triclinic P-1 space group (a = 6.8852(3) Å, b = 11.6914(5) Å, c = 11.9603(6) Å, α = 108.812(4)°, β = 102.028(4)°, γ = 92.835(3)°, Z = 2) with alternation of organic and inorganic layers along the a-axis. The crystal packing was governed by the Nsbnd H⋯Cl and Osbnd H⋯Cl hydrogen bonding interaction between the 4-amine pyridinium cations and the octahedral [InCl5(H2O)] anions, and π-π stacking interactions in which they may be effective in the stabilization of the crystal structure. The optical and photoluminescence properties of the compound were investigated in the solid-state at room temperature.

  18. 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.

  19. 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.

  20. 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.

  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. 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.

  3. 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.

  4. Pink tooth phenomenon: an enigma?

    PubMed

    Thapar, Raveena; Choudhry, Swati; Sinha, Anju; Bali, Ruchita; Shukla, Deepika

    2013-10-01

    The appearance of pink teeth is a common phenomenon which has been observed after death in certain circumstances on post-mortem examination. Extra fibrinolytic activity of pulp facilitates rapid breakdown of red blood cells and diffusion of hemoglobin and its derivatives to flow into dentine. We reviewed various studies on pink tooth phenomenon which have stated the various factors that lead to pink tooth formation. Most of the authors have stressed that post-mortem pink teeth must not be considered as a reliable odontological parameter for determining cause of death. No correlation has been found between the occurrence of pink teeth and the cause of death but condition of the surroundings certainly plays an important role in the development of this phenomenon. This paper reviews the factors and conditions responsible for formation of pink teeth. Copyright © 2013 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

  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. Protection of open-metal V(III) sites and their associated CO₂/CH₄/N₂/O₂/H₂O adsorption properties in mesoporous V-MOFs.

    PubMed

    Yang, Jiangfeng; Wang, Yong; Li, Libo; Zhang, Zhuoming; Li, Jinping

    2015-10-15

    Metal-organic frameworks with open metal site are potential sorbents for the separation of gas mixtures; however, low valence metal will bind to oxygen in the open air causing a decrease in adsorption ability. We now report open-metal sites V(III) on both MIL-100V(III/IV) and MIL-101V(III/IV) that can be protected with water molecules, and which associated CO2/CH4/N2/O2 adsorption properties on these two mesoporous V-MOFs were investigated. The protective properties of water were investigated and evaluated using density functional theory simulations. The binding energy of single O2 on open-metal V(III) site was 93.278 kJ/mol, which decreased to 26.5 kJ/mol when H2O occupies the site. When the water coating is removed, the X-ray photoelectron spectroscopy pattern of V2p showed that the V-MOF changes to MIL-100V(IV) and MIL-101V(IV) at 298 K because of the action of O2. Under these conditions, O2 binds strongly on the open V site significantly reducing the BET (Brunauer-Emmett-Teller) surface and CH4 adsorption volume of the V-MOFs. From the ideal adsorbed solution theory calculated, the adsorption selectivity of CH4/N2 is higher before than after binding of O2 (with V(III) site). In contrast, the adsorption selectivity of CO2/CH4 is higher after than before O2 binding (with no more V(III) sites). Copyright © 2015 Elsevier Inc. All rights reserved.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Effect of V/III ratio on the surface morphology and electrical properties of m-plane (10 1 bar 0) GaN homoepitaxial layers

    NASA Astrophysics Data System (ADS)

    Barry, Ousmane I.; Tanaka, Atsushi; Nagamatsu, Kentaro; Bae, Si-Young; Lekhal, Kaddour; Matsushita, Junya; Deki, Manato; Nitta, Shugo; Honda, Yoshio; Amano, Hiroshi

    2017-06-01

    We have investigated the effect of V/III ratio on the surface morphology, impurity concentration and electrical properties of m-plane (10 1 bar 0) Gallium Nitride (GaN) homoepitaxial layers. Four-sided pyramidal hillocks are observed on the nominally on-axis m-plane GaN films. Hillocks sizes relatively increase by increasing the V/III ratio. All facets of pyramidal hillocks exhibit well-defined step-terrace features. Secondary ion mass spectrometry depth profiles reveal that carbon impurities decrease by increasing the V/III ratio while the lowest oxygen content is found at an optimized V/III ratio of 900. Vertical Schottky barrier diodes fabricated on the m-GaN samples were characterized. Low leakage current densities of the order of 10-10 A/cm2 at -5 V are obtained at the optimum V/III ratio. Oxygen impurities and screw-component dislocations around hillocks are found to have more detrimental impact on the leakage current mechanism.

  12. 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…

  13. 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…

  14. Fluorescent and ultraviolet-visible spectroscopy studies on the antioxidation and DNA binding properties of binuclear Tb(III) complexes.

    PubMed

    Liu, Yongchun; Jiang, Xinhui; Yang, Zhengyin; Zheng, Xudong; Liu, Jianning; Zhou, Tianlin

    2010-09-01

    Tb(III) complexes were prepared from Tb(NO(3))(3)·6H(2)O and four Schiff-base ligands derived from 8-hydroxyquinoline-2-carboxaldehyde with aroylhydrazines. X-ray crystal and other structural analyses indicate that Tb(III) and every ligand can form a binuclear Tb(III) complex with 1:1 metal-to-ligand stoichiometry and nine-coordination at the Tb(III) center. Viscosity titration experiments and fluorescent and ultraviolet-visible (UV-Vis) spectroscopy results indicate that all the Tb(III) complexes can bind to Calf thymus DNA through intercalation with the binding constants at the order of magnitude of 10(6)-10(7) M(-1), and they may be used as potential anticancer drugs, but complexes containing active phenolic hydroxy groups may have stronger antitumor activities. Antioxidation results indicate that all the Tb(III) complexes have strong abilities of scavenging hydroxyl radicals and superoxide radicals, but complexes containing active phenolic hydroxy groups show stronger scavenging effects on hydroxyl radicals and complexes containing N-heteroaromatic substituent show stronger scavenging effects on superoxide radicals. However, Tb(III) emission with these systems is not observed, for these ligands rather are quenchers and unable to sensitize this metal ion.

  15. Differences and Comparisons of the Properties and Reactivities of Iron(III)–hydroperoxo Complexes with Saturated Coordination Sphere

    PubMed Central

    Faponle, Abayomi S; Quesne, Matthew G; Sastri, Chivukula V; Banse, Frédéric; de Visser, Sam P

    2015-01-01

    Heme and nonheme monoxygenases and dioxygenases catalyze important oxygen atom transfer reactions to substrates in the body. It is now well established that the cytochrome P450 enzymes react through the formation of a high-valent iron(IV)–oxo heme cation radical. Its precursor in the catalytic cycle, the iron(III)–hydroperoxo complex, was tested for catalytic activity and found to be a sluggish oxidant of hydroxylation, epoxidation and sulfoxidation reactions. In a recent twist of events, evidence has emerged of several nonheme iron(III)–hydroperoxo complexes that appear to react with substrates via oxygen atom transfer processes. Although it was not clear from these studies whether the iron(III)–hydroperoxo reacted directly with substrates or that an initial O–O bond cleavage preceded the reaction. Clearly, the catalytic activity of heme and nonheme iron(III)–hydroperoxo complexes is substantially different, but the origins of this are still poorly understood and warrant a detailed analysis. In this work, an extensive computational analysis of aromatic hydroxylation by biomimetic nonheme and heme iron systems is presented, starting from an iron(III)–hydroperoxo complex with pentadentate ligand system (L52). Direct C–O bond formation by an iron(III)–hydroperoxo complex is investigated, as well as the initial heterolytic and homolytic bond cleavage of the hydroperoxo group. The calculations show that [(L52)FeIII(OOH)]2+ should be able to initiate an aromatic hydroxylation process, although a low-energy homolytic cleavage pathway is only slightly higher in energy. A detailed valence bond and thermochemical analysis rationalizes the differences in chemical reactivity of heme and nonheme iron(III)–hydroperoxo and show that the main reason for this particular nonheme complex to be reactive comes from the fact that they homolytically split the O–O bond, whereas a heterolytic O–O bond breaking in heme iron(III)–hydroperoxo is found. PMID:25399782

  16. 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.

  17. 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.

  18. 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.

  19. Properties of the ANB angle and the Wits appraisal in the skeletal estimation of Angle's Class III patients.

    PubMed

    Iwasaki, Hiroshi; Ishikawa, Hiroyuki; Chowdhury, Lamiya; Nakamura, Shinji; Iida, Junichiro

    2002-10-01

    The aims of the present study were: (1) to investigate the statistical differences in jaw relationship assessments with the ANB angle and the Wits appraisal in Angle Class III children, and (2) to suggest guidelines for the use of these two parameters in this group of children. Seventy-five Angle Class I children with anterior crowding (male, 37; female, 38) and 96 Angle Class III children with anterior crossbite (male, 38; female, 58) were examined. All had undergone treatment that started at 8 or 9 years of age. Pre-treatment lateral cephalograms were used cross-sectionally for the analysis. The mean age was 8 years 7 months +/- 9 months in the Class I subjects, and 9 years 0 month +/- 7 months in the Class III subjects. To compare the assessments using ANB angle and the Wits appraisal in the Angle's Class III subjects, nine measured values from each individual subject were converted into Z scores in relation to the means and standard deviations of the two parameters in the Angle Class I subjects. The jaw discrepancy is assessed more severely using the ANB angle than by the Wits appraisal in these Angle Class III subjects. The paired t-test showed that the Z score of the ANB angle was significantly smaller than that of the Wits appraisal (P < 0.001). In Angle Class III subjects with a counter-clockwise mandibular rotation and a flattened occlusal plane, the ANB angle is a more critical cephalometric parameter than the Wits appraisal.

  20. 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.

  1. 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

  2. Wellness as a worldwide phenomenon?

    PubMed

    Elliott, Heather; Bernstein, Jennifer; Bowman, Diana M

    2014-10-01

    This article examines the concept of wellness through a comparative political economy and legal framework. It asks whether wellness, an increasingly defined term within US federal and state legislative instruments including, for example, the Patient Protection and Affordable Care Act, is primarily a US-centric phenomenon. Or is wellness, in its various different guises, a worldwide phenomenon? By focusing on three distinctly different jurisdictions - the United States, Germany, and Australia - this article examines wellness through the lens of employers, the health care system, employment and tort law, and the greater political economy. It notes that while improving employee health, well-being, and productivity is common across the three countries and their respective cultures, the focus on wellness as a distinct legal concept is unique to the United States. Copyright © 2014 by Duke University Press.

  3. Lattice Dynamical, Elastic and Thermodynamical Properties of III-V Semiconductor AlSb, GaSb and Their Mixed Semiconductor Ga_{1-x}AlxSb

    NASA Astrophysics Data System (ADS)

    Kushwaha, A. K.

    2017-07-01

    A proposed eleven-parameter three-body shell model is used to study the lattice dynamical properties such as phonon dispersion relations along high symmetry directions, phonon density of states, variation of specific heat and Debye characteristic temperature with absolute temperature, elastic constants and related properties for III-V semiconductor AlSb, GaSb and their mixed semiconductor Ga_{1-x}AlxSb having zinc-blende structure. We found an overall good agreement with the available experimental and theoretical results available in the literature.

  4. STUDIES ON THE SHWARTZMAN PHENOMENON

    PubMed Central

    Klein, Herbert M.

    1932-01-01

    Formalin induces a considerable change in meningococcus culture filtrates. This consists of a marked decrease in toxidty as concerns both the Shwartzman phenomenon and the lethal effect, with relative preservation of the antibody-combining capacity and antigenicity. A similar modification occurs spontaneously in meningococcus culture filtrates on standing. Inasmuch as these changes parallel those occurring in the conversion of diphtheria toxin into toxoid, it is justifiable to consider such altered meningococcus toxin as meningococcus toxoid. PMID:19870087

  5. 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).

  6. 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).

  7. 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…

  8. Nutcracker Phenomenon and Nutcracker Syndrome

    PubMed Central

    Kurklinsky, Andrew K.; Rooke, Thom W.

    2010-01-01

    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. PMID:20511485

  9. 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

  10. Properties of impurity-bearing ferrihydrite III. Effects of Si on the structure of 2-line ferrihydrite

    NASA Astrophysics Data System (ADS)

    Cismasu, A. Cristina; Michel, F. Marc; Tcaciuc, A. Patricia; Brown, Gordon E.

    2014-05-01

    Siliceous ferrihydrites are abundant nanoparticles in natural environments. Although it is well known that the physical properties of ferrihydrite are affected when formed in the presence of silicate oxoanions (SiO44-), the structure of siliceous ferrihydrites (SiFh), and the speciation of Si within these nanosolids are not well understood. In this study we evaluate the effects of Si (at concentrations ranging from 5 to 40 mol% Si) on synthetic ferrihydrite precipitates using structural data derived from synchrotron-based high energy X-ray scattering and pair distribution function (PDF) analysis, in combination with X-ray absorption near edge structure (XANES) spectroscopy, and transmission electron microscopy (TEM). Silicate oxoanions have a major effect on Fe(O,OH)x polyhedral polymerization and ferrihydrite particle growth, illustrated by the formation of smaller, poorly crystalline, structurally disordered/strained ferrihydrite nanocrystallites. Variation in Fh unit-cell parameters is suggested to arise from substantial particle size-induced structural disorder. As a result of this significant size-dependent structural disorder, it was not possible to identify evidence for Si4+ for Fe3+ substitution in these samples based on unit cell parameter variations or refinement of different structural models. Principal component analyses (PCA) and linear combination fits carried out on the PDFs suggest that iron partitions between several phases (e.g., ferrihydrite and an Fe-bearing amorphous silica phase (Amorph. SiO2 + Fe)) in these co-precipitates. A mechanism of co-precipitation is proposed, in which silicate binds to Fe polymers and Fh particles, thus inhibiting particle growth at low Si content. At higher Si content, SiO44- polymerization traps significant Fe, and we suggest that the occurrence of this second Fe pool limits further the availability of Fe required for ferrihydrite particle development. Such Si-ferrihydrite co-precipitates are expected to be more

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. Enhancing the luminescence properties and stability of cationic iridium(III) complexes based on phenylbenzoimidazole ligand: a combined experimental and theoretical study.

    PubMed

    Shan, Guo-Gang; Li, Hai-Bin; Sun, Hai-Zhu; Cao, Hong-Tao; Zhu, Dong-Xia; Su, Zhong-Min

    2013-08-21

    Herein we designed and synthesized a series of cationic iridium(III) complexes with a phenylbenzoimidazole-based cyclometalated ligand, containing different numbers of carbazole moieties from zero to three (complexes 1-4). The photophysical and electrochemical properties of this series have been systematically investigated. The complexes exhibit strong luminescence in both solution and in neat films, as well as excellent redox reversibility. Introducing carbazole groups into the complexes is found to lead to substantially enhanced photoluminescence quantum efficiency in the neat film, but has little effect on the emitting color and excited-state characteristics as supported by density functional theory (DFT) results. DFT calculations also suggest that functionalized complexes 2-4 reveal better hole-transporting properties than 1. More importantly, all complexes effectively reduce the degradation reaction to some extent in metal-centered (³MC) excited-states, demonstrating their stability. Further studies indicate that restriction of opening of the structures in the ³MC state is caused by the unique molecular conformation of the phenylbenzoimidazole ligand, which is first demonstrated here in cationic iridium(III) complexes without intramolecular π-π stacking. These results presented here would provide valuable information for designing and synthesizing highly efficient and stable cationic iridium(III) complexes suitable for the optical devices.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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).

  5. 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.

  6. 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.

  7. 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.

  8. The effect of the synthetic route on the structural, textural, morphological and catalytic properties of iron(iii) oxides and oxyhydroxides.

    PubMed

    Oulego, Paula; Villa-García, María A; Laca, Adriana; Diaz, Mario

    2016-06-21

    A variety of iron(iii) oxides and oxyhydroxides were synthesised and characterised using three distinct methods of preparation: microemulsion, precipitation and sol-gel. The results clearly showed that the structure, textural properties, crystal morphology and catalytic performance of the phases obtained were highly dependent on the chemical routes used for the synthesis. Precipitation and microemulsion methods allowed obtaining mesoporous nanostructured iron(iii) oxides with mean particle sizes of 4 nm (amorphous hematite) and 7 nm (ferrihydrite), which exhibited a high surface area (291.4 m(2) g(-1) and 192.3 m(2) g(-1), respectively) and a very good catalytic behaviour in the advanced oxidation of highly non-biodegradable wastewaters. The different conditions employed in the synthesis of these materials through the sol-gel method yielded two goethites with practically the same catalytic properties, but dissimilar morphologies and texture. When soft agitation and slow addition of the precipitating agent were used, the resulting material (G1) was made up of shorter and finer particles, markedly acicular, with an average length of 400 ± 50 nm and width of 15 ± 5 nm. However, vigorous agitation and rapid addition of the precipitating agent led to the formation of longer and coarser particles, moderately acicular, the average length and width being 950 ± 100 nm and 140 ± 20 nm, respectively. The use of the sol-gel technique also resulted in the formation of a solid consisting of a mixture of hematite as the main crystalline phase and goethite particles dispersed among the hematite particles. This solid presented a low specific surface area (13.2 m(2) g(-1)) and lower catalytic activity. Therefore, precipitation and microemulsion proved to be the most suitable techniques to synthesise catalytically active disordered iron(iii) oxide nanoparticles, due to the presence of highly reactive non-stoichiometric iron(iii) ions, a higher surface area and smaller particle

  9. 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.

  10. First-Principles Study of Structural, Electronic, Mechanical, Thermal, and Phonon Properties of III-Phosphides (BP, AlP, GaP, and InP)

    NASA Astrophysics Data System (ADS)

    Ehsanfar, S.; Kanjouri, F.; Tashakori, H.; Esmailian, A.

    2017-10-01

    Based on first-principles calculations with generalized gradient approximation as exchange-correlation functional, the structural, electronic, mechanical, thermal, and phonon properties of III-phosphide binary compounds, namely BP, AlP, GaP, and InP, with cubic zincblende structure have been investigated. The calculations were performed in the framework of density functional theory and density functional perturbation theory (DFPT) implemented in the Quantum ESPRESSO package. The results obtained for the structural and electronic properties are in good agreement with available theoretical and experimental results. The results of our electronic calculations indicate semiconducting properties for these binary compounds. Furthermore, the frequency bandgaps and phonon density of states were also investigated. The computed mechanical constants predict that BP, AlP, GaP, and InP are elastically stable. Finally, we determined the heat capacity and entropy for these binary compounds within a quasiharmonic Debye model using DFPT for comparison.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. The phenomenon of microbial uncultivability.

    PubMed

    Epstein, S S

    2013-10-01

    Most of the microbial diversity on our planet cannot be cultivated, and remains inaccessible. To bring the missing species into culture, microbiologists have introduced over the past decade a number of innovations aiming to meet the demands of new microbes and better mimic their natural conditions. This resulted in a significant increase in microbial recovery yet the real reasons why so many microbes do not grow on artificial media remain largely unknown. The recently proposed scout model of microbial life cycle may provide a partial explanation for the phenomenon. It postulates that transition from dormancy to activity is a stochastic process originating in noise-driven bistability. The model helps explain several otherwise perplexing observations, and informs the future cultivation efforts. Copyright © 2013. Published by Elsevier Ltd.

  17. Phosphene phenomenon: a new concept.

    PubMed

    Bókkon, István

    2008-05-01

    This paper proposes a new biopsychophysical concept of phosphene phenomenon. Namely, visual sensation of phosphenes is due to the intrinsic perception of ultraweak bioluminescent photon emission of cells in the visual system. In other words, phosphenes are bioluminescent biophotons in the visual system induced by various stimuli (mechanical, electrical, magnetic, ionizing radiation, etc.) as well as random bioluminescent biophotons firings of cells in the visual pathway. This biophoton emission can become conscious if induced or spontaneous biophoton emission of cells in the visual system exceeds a distinct threshold. Neuronal biophoton communication can occur by means of non-visual neuronal opsins and natural photosensitive biomolecules. Our interpretation is in direct connection with the functional roles of free radicals and excited biomolecules in living cells.

  18. 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.

  19. 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. Copyright © 2015. Published by Elsevier Ltd.

  20. Synthesis of MPTS-modified cobalt ferrite nanoparticles and their adsorption properties in relation to Au(III).

    PubMed

    Kraus, Andrea; Jainae, Kunawoot; Unob, Fuangfa; Sukpirom, Nipaka

    2009-10-15

    Cobalt ferrite magnetic nanoparticles (Co-MNP) were prepared by a co-precipitation method and subsequently coated with (3-mercaptopropyl)trimethoxysilane (MPTS) for the extraction and recovery of Au(III) from aqueous chloride solutions. Physical characterization of the MPTS-modified particles (Co-MPTS) was performed using FT-IR, TGA, and SEM. Results from FT-IR confirmed that MPTS was present on the surface of the magnetic nanoparticles. The amount of MPTS was 0.36 mmol g(-1) of Co-MPTS, obtained by elemental analysis. SEM images revealed aggregates composed of nanocrystalline Co-MPTS particles. The extraction efficiency as a function of the pH, contact time, and initial Au(III) concentration was evaluated. The modified particles showed maximum adsorption in the pH range from 1.0 to 4.0. The adsorption behavior of Co-MPTS toward Au(III) followed a Langmuir isotherm and the maximum adsorption capacity was found to be 120.5 mg g(-1). The stability of the modified materials was improved as compared to that of bare Co-MNP. The subsequent desorption of gold could be achieved by using acidified thiourea solution; the highest gold recovery reached 85%.

  1. The effect of alkali and Ce(III) ions on the response properties of benzoxazine supramolecules prepared via molecular assembly.

    PubMed

    Kaewvilai, Attaphon; Rujitanapanich, Sawittree; Wattanathana, Worawat; Veranitisagul, Chatchai; Suramitr, Songwut; Koonsaeng, Nattamon; Laobuthee, Apirat

    2012-01-05

    A series of benzoxazine monomer supramolecules with different substituted groups on their benzene ring was prepared with a Mannich reaction and characterized by FTIR, 1H-NMR and MS. The obtained products were 3,4-dihydro-3-(2'-hydroxyethylene)-6-methyl-2H-benzoxazine (BM1), 3,4-dihydro-3-(2'-hydroxyethylene)-6-ethyl-2H-benz-oxazine (BM2), and 3,4-dihydro-3-(2'-hydroxyethylene)-6-methoxy-2H-benzoxazine (BM3). The efficiency of alkali metal ion extraction from the products was determined with Pedersen's technique, while the complexation of the Ce(III) ion was confirmed by the Job's and the mole ratio methods. The evidence of complex formation between benzoxazine monomers and Ce(III) ions was obtained with FTIR and a computational simulation. Single phase ceria (CeO₂) as observed with XRD was successfully prepared by calcinating the Ce(III)-benzoxazine monomer complexes at 600 °C for 2 h. In addition, the geometry of the ceria nanoparticles confirmed by TEM is spherical, with an average diameter of 10-20 nm.

  2. A one-dimensional azido-bridged manganese(III) complex with bidentate Schiff base: Crystal structure and magnetic properties

    SciTech Connect

    Li Wei; Li Zongwei; Li Licun Liao Daizheng; Jiang Zonghui

    2007-10-15

    The synthesis, structural characterization, and magnetic behavior of a novel one-dimensional azido-bridged manganese(III) complex of formula [Mn(L){sub 2}N{sub 3}] (1) is reported, where HL is the bidentate Schiff base obtained from the condensation of salicylaldehyde with 4-methoxy aniline. Complex 1 crystallizes in the monoclinic system, space group P2{sub 1}/n, with a=11.743(4) A, b=24.986(9) A, c=13.081(5) A, {beta}=95.387(7){sup o} and Z=2. The complex is of one-dimensional chain structure with single end-to-end azido bridges and the manganese(III) ion has an elongated octahedral geometry. Magnetic studies show that the weak antiferromagnetic interaction is mediated by the single end-to-end azido bridge with the exchange parameter J=-5.84 cm{sup -1}. - Graphical abstract: A novel azido-bridged manganese(III) complex with bidentate Schiff base ligands has been prepared and characterized structurally and magnetically. The complex is of one-dimensional chain structure with single end-to-end azido bridges in axial positions. Two bidentate Schiff base ligands coordinate in the equatorial mode. The magnetic measurements show that the complex exhibits weak antiferromagnetic interaction.

  3. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Theoretical investigation on the electronic structures and photophysical properties of a series of iridium(III) complexes with different main ligands

    NASA Astrophysics Data System (ADS)

    Zhang, Qiang; Zhao, Lihui; Han, Deming; Zhang, Gang

    2015-07-01

    The influence of different substituent groups and π-conjugation degree on the optical and electronic properties of six Ir(III) complexes has been theoretically studied. The injection abilities of holes and electrons into these complexes have been evaluated with the ionization potential and electron affinity. The lowest energy absorption wavelengths calculated for these complexes are in good agreement with the available experimental values. The lowest energy emissions of these complexes are localized at 569, 584, 634, 554, 569, and 851 nm, respectively. The study could provide good information for designing the potential phosphorescent material for use in the organic light-emitting diodes.

  5. Electrical properties of III-Nitride LEDs: Recombination-based injection model and theoretical limits to electrical efficiency and electroluminescent cooling

    SciTech Connect

    David, Aurelien Hurni, Christophe A.; Young, Nathan G.; Craven, Michael D.

    2016-08-22

    The current-voltage characteristic and ideality factor of III-Nitride quantum well light-emitting diodes (LEDs) grown on bulk GaN substrates are investigated. At operating temperature, these electrical properties exhibit a simple behavior. A model in which only active-region recombinations have a contribution to the LED current is found to account for experimental results. The limit of LED electrical efficiency is discussed based on the model and on thermodynamic arguments, and implications for electroluminescent cooling are examined.

  6. Electrical properties of III-Nitride LEDs: Recombination-based injection model and theoretical limits to electrical efficiency and electroluminescent cooling

    NASA Astrophysics Data System (ADS)

    David, Aurelien; Hurni, Christophe A.; Young, Nathan G.; Craven, Michael D.

    2016-08-01

    The current-voltage characteristic and ideality factor of III-Nitride quantum well light-emitting diodes (LEDs) grown on bulk GaN substrates are investigated. At operating temperature, these electrical properties exhibit a simple behavior. A model in which only active-region recombinations have a contribution to the LED current is found to account for experimental results. The limit of LED electrical efficiency is discussed based on the model and on thermodynamic arguments, and implications for electroluminescent cooling are examined.

  7. 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.

  8. [Psychometric properties of the third version of family adaptability and cohesion evaluation scales (FACES-III): a study of peruvian adolescents].

    PubMed

    Bazo-Alvarez, Juan Carlos; Bazo-Alvarez, Oscar Alfredo; Aguila, Jeins; Peralta, Frank; Mormontoy, Wilfredo; Bennett, Ian M

    2016-01-01

    Our aim was to evaluate the psychometric properties of the FACES-III among Peruvian high school students. This is a psychometric cross-sectional study. A probabilistic sampling was applied, defined by three stages: stratum one (school), stratum two (grade) and cluster (section). The participants were 910 adolescent students of both sexes, between 11 and 18 years of age. The instrument was also the object of study: the Olson's FACES-III. The analysis included a review of the structure / construct validity of the measure by factor analysis and assessment of internal consistency (reliability). The real-cohesion scale had moderately high reliability (Ω=.85) while the real-flexibility scale had moderate reliability (Ω=.74). The reliability found for the ideal-cohesion was moderately high (Ω=.89) like for the scale of ideal-flexibility (Ω=.86). Construct validity was confirmed by the goodness of fit of a two factor model (cohesion and flexibility) with 10 items each [Adjusted goodness of fit index (AGFI) = 0.96; Expected Cross Validation Index (ECVI) = 0.87; Normed fit index (NFI) = 0.93; Goodness of fit index (GFI) = 0.97; Root mean square error of approximation (RMSEA) = 0.06]. FACES-III has sufficient reliability and validity to be used in Peruvian adolescents for the purpose of group or individual assessment.

  9. 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

  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. 1H-n.m.r. study of the solution properties and secondary structure of neurotoxin III from the sea anemone Anemonia sulcata.

    PubMed

    Norton, R S; Cross, K; Braach-Maksvytis, V; Wachter, E

    1993-07-15

    The solution properties, secondary structure and global fold of the 27-residue polypeptide neurotoxin III (ATX III), from the sea anemone Anemonia sulcata, have been investigated using high-resolution 1H-n.m.r. spectroscopy. Studies of the concentration dependence of the n.m.r. spectrum indicate that the molecule self-associates in the millimolar concentration range useable for n.m.r. analysis, the association being less pronounced at acidic pH values. The dependence on pH of association implies that electrostatic interactions play a role in this process, while the significant concentration-dependent shifts of the aromatic resonances of Tyr-7 and Trp-13 indicate that hydrophobic interactions also contribute. Individual pKa values have been determined for most ionizable groups in the molecule. Sequence-specific resonance assignments were obtained for all protons using a range of two-dimensional homonuclear-correlated and nuclear-Overhauser-effect (nOe) spectra. The secondary structure of the polypeptide was identified from sequential (i, i+1) and medium-range (i, i+2/3/4) nOe connectivities, NH to C alpha H coupling constants, C alpha H chemical shifts, and the location of slowly exchanging backbone-amide protons. ATX III contains no regular alpha-helix or beta-sheet, consisting instead of a network of reverse turns. nOe connectivities between half-cystine residues are consistent with the disulphide pairings 3-17, 4-11 and 6-22. ATX III has a well-defined structure and appears to lack the disordered loop which, in the longer sea anemone toxins (46-49 residues), may be part of the receptor-binding surface.

  12. 1H-n.m.r. study of the solution properties and secondary structure of neurotoxin III from the sea anemone Anemonia sulcata.

    PubMed Central

    Norton, R S; Cross, K; Braach-Maksvytis, V; Wachter, E

    1993-01-01

    The solution properties, secondary structure and global fold of the 27-residue polypeptide neurotoxin III (ATX III), from the sea anemone Anemonia sulcata, have been investigated using high-resolution 1H-n.m.r. spectroscopy. Studies of the concentration dependence of the n.m.r. spectrum indicate that the molecule self-associates in the millimolar concentration range useable for n.m.r. analysis, the association being less pronounced at acidic pH values. The dependence on pH of association implies that electrostatic interactions play a role in this process, while the significant concentration-dependent shifts of the aromatic resonances of Tyr-7 and Trp-13 indicate that hydrophobic interactions also contribute. Individual pKa values have been determined for most ionizable groups in the molecule. Sequence-specific resonance assignments were obtained for all protons using a range of two-dimensional homonuclear-correlated and nuclear-Overhauser-effect (nOe) spectra. The secondary structure of the polypeptide was identified from sequential (i, i+1) and medium-range (i, i+2/3/4) nOe connectivities, NH to C alpha H coupling constants, C alpha H chemical shifts, and the location of slowly exchanging backbone-amide protons. ATX III contains no regular alpha-helix or beta-sheet, consisting instead of a network of reverse turns. nOe connectivities between half-cystine residues are consistent with the disulphide pairings 3-17, 4-11 and 6-22. ATX III has a well-defined structure and appears to lack the disordered loop which, in the longer sea anemone toxins (46-49 residues), may be part of the receptor-binding surface. PMID:8102051

  13. 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.

  14. Synthesis, Characterization, and Luminescent Properties of Polymer Complexes of Nd(III) with β-Dicarbonyl Ligands

    NASA Astrophysics Data System (ADS)

    Berezhnytska, Oleksandra; Savchenko, Irina; Ivakha, Nadiya; Trunova, Olena; Rusakova, Nataliya; Smola, Sergiy; Rogovtsov, Oleksandr

    2017-05-01

    The neodymium(III) complexes with 2-methyl-5-phenylpenten-1-3,5-dione and allyl-3-oxo-butanoate were synthesized. The polycomplexes on their basis and copolymers with styrene and N-vinylcarbazole in ratio 5:95 were obtained by free-radical polymerization. The results of above studies have shown that the configuration of the chelate unit is unchanged during the polymerization. As a result, the type of coordination was determined and the structure of coordination polyhedra was assumed. The luminescence spectra of obtained metallocomplexes and polymers in solutions and solid state are investigated and analyzed.

  15. Syntheses, crystal structures and properties of series of 4d–4f ln(III)–Ag(I) heterometallic coordination polymers

    SciTech Connect

    Ran, Xing-Rui; Wang, Ning; Xie, Wei-Ping; Xiong, Yan-Ju; Cheng, Qian; Long, Yi; Yue, Shan-Tang; Liu, Ying-Liang

    2015-05-15

    By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, ([Ln{sup III}Ag{sup I}(na)(ina)(ox)]·2(H{sub 2}O)){sub n} [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail. - Graphical abstract: Series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction which are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. - Highlights: • Complexes 1–8 are first built by three kinds of organic ligands based on nicotinic acid and isonicotinic acid. • PCPs 1–8 are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. • The total solvent-accessible volume of PCP 2 comprises 11.6% of the crystal volume after dislodging the free water molecules. • Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence, while compounds 3 and 5 show antiferromagnetic behaviors.

  16. 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.

  17. Leidenfrost phenomenon on conical surfaces

    NASA Astrophysics Data System (ADS)

    Hidalgo-Caballero, S.; Escobar-Ortega, Y.; Pacheco-Vázquez, F.

    2016-09-01

    The Leidenfrost state is typically studied by placing droplets on flat or slightly curved surfaces. Here this phenomenon is investigated by depositing water in hot conical bowls. We found that this phase exists even for large amounts of liquid in very narrow cones without considerable effect of the confinement on the Leidenfrost transition temperature TL. At a fixed temperature, T >TL , the total evaporation time τ has a nonmonotonic dependence on the angle of confinement θ : for large volumes (˜20 ml) on flat surfaces (θ ˜0∘ ), vapor chimneys appear and accelerate the evaporation rate, their frequency diminishes as θ augments and becomes zero at a certain angle θc, at which τ reaches its maximum value; then, τ decreases again at larger angles because the vapor layer holding up the water becomes thinner due to the increase of hydrostatic pressure and because the geometry facilitates the vapor expulsion along the conical wall. For small volumes (˜1 ml), surface tension mainly determines the drop curvature and the lifetime is practically independent of θ . Different chimney regimes and oscillation patterns were observed and summarized in a phase diagram. Finally, we developed a simple model to decipher the shape adopted by the liquid volume and its evolution as a function of time, and the predictions are in good agreement with the experimental results.

  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. DFT Simulation of Structural and Optical Properties of 9-Aminoacridine Half-Sandwich Ru(II), Rh(III), and Ir(III) Antitumoral Complexes and Their Interaction with DNA.

    PubMed

    Cerón-Carrasco, José Pedro; Ruiz, José; Vicente, Consuelo; de Haro, Concepción; Bautista, Delia; Zúñiga, José; Requena, Alberto

    2017-08-08

    In this work, we use DFT-based methods to simulate the chemical structures, optical properties, and interaction with DNA of a recently synthesized chelated C^N 9-aminoacridine arene Ru(II) anticancer agent and two new closely related Rh(III) and Ir(III) complexes using DFT-based methods. Four chemical models and a number of theoretical approaches, which representatively include the PBE0, B97D, ωB97X, ωB97X-D, M06, and M06-L density functionals and the LANL2DZ, def2-SVP, and def2-TZVP basis sets, are tested. The best overall accuracy/cost performance for the optimization process is reached at the ωB97X-D/def2-SVP and M06/def2-SVP levels of theory. Inclusion of explicit solvent molecules (CHCl3) further refines the geometry, while taking into account the crystal network gives no significant improvements of the computed bond distances and angles. The analysis of the excited states reveals that the M06 level matches better the experimental absorption spectra, compared to ωB97X-D. The use of the M06/def2-SVP approach is therefore a well-balanced method to study theoretically the bioactivity of this type of antitumoral complexes, so we couple this TD-DFT approach to molecular dynamics simulations in order to assess their reactivity with DNA. The reported results demonstrate that these drugs could be used to inject electrons into DNA, which might broaden their applications in photoactivated chemotherapy and as new materials for DNA-based electrochemical nanodevices.

  20. 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.

  1. 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.

  2. Influence of the supramolecular architecture on the magnetic properties of a DyIII single-molecule magnet: an ab initio investigation

    PubMed Central

    Jung, Julie; Cador, Olivier; Bernot, Kevin; Pointillart, Fabrice; Luzon, Javier

    2014-01-01

    Summary Single-crystal angular-resolved magnetometry and wavefunction-based calculations have been used to reconsider the magnetic properties of a recently reported DyIII-based single-molecule magnet, namely [Dy(hfac)3(L1)] with hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate and L1 = 2-(4,5-bis(propylthio)-1,3-dithiol-2-ylidene)-6-(pyridin-2-yl)-5H-[1,3]dithiolo[4',5':4,5]benzo[1,2-d]imidazole. The magnetic susceptibility and magnetization at low temperature are found to be strongly influenced by supramolecular interactions. Moreover, taking into account the hydrogen-bond networks in the calculations allows to explain the orientation of the magnetic axes. This strongly suggests that hydrogen bonds play an important role in the modulation of the electrostatic environment around the DyIII center that governs the nature of its magnetic ground-state and the orientation of its anisotropy axes. We thus show here that SMM properties that rely on supramolecular organization may not be transferable into single-molecule devices. PMID:25551055

  3. 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.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Surface phenomenon in Electrochemical Systems

    NASA Astrophysics Data System (ADS)

    Gupta, Tanya

    Interfaces play a critical role in the performance of electrochemical systems. This thesis focusses on interfaces in batteries and covers aspects of interfacial morphologies of metal anodes, including Silicon, Lithium and Zinc. Growth and cycling of electrochemically grown Lithium and Zinc metal structures is investigated. A new morphology of Zinc, called Hyper Dendritic Zinc is introduced. It is cycled against Prussian Blue Analogues and is shown to improve the performance of this couple significantly. Characterization of materials is done using various electron microscopy techniques ranging from Low Energy Electron Microscope (LEEM), to high energy Transmission Electron Microscope (TEM). LEEM is used for capturing subtle surface phenomenon occurring during epitaxial process of electrolyte on anode. The system studied is Silicon (100) during Chemical Vapor Deposition of Ethylene Carbonate. A strain driven relaxation theory is modeled to explain the unusual restructuring of Si substrate. The other extreme, TEM, is often used to study electrochemical processes, without clear understanding of how the high-energy electron beam can influence the sample under investigation. Here, we study the radiolysis in liquid cell TEM and emphasize on the enhancement of radiation dose at interfaces of the liquid due to generation of secondary and backscattered electrons from adjoining materials. It is shown that this effect is localized in a 10 nm region around the interface and can play a dominating role if there is an interface of liquid with heavy metals like Gold and Platinum which are frequently used as electrode materials. This analysis can be used to establish guidelines for experimentalists to follow, for accurate interpretation of their results.

  11. Versatility in the binding of 2-pyrazinecarboxylate with iron. Synthesis, structure and magnetic properties of iron(II) and iron(III) complexes.

    PubMed

    Tanase, Stefania; Marqués Gallego, Patricia; Bouwman, Elisabeth; Long, Gary J; Rebbouh, Leila; Grandjean, Fernande; de Gelder, René; Mutikainen, Ilpo; Turpeinen, Urho; Reedijk, Jan

    2006-04-07

    The synthesis and characterization of two new iron(II) complexes, [Fe(pca)2(py)2].py (1) and {[Fe(pca)2(H2O)].H2O}n (2) and one new iron(III) complex, Na2{[Fe(pca)()]2O}.2H2O.2CH3CN (3) (pca- stands for 2-pyrazinecarboxylate), are reported. Complex 1 is obtained from the reaction of iron powder with 2-pyrazinecarboxylic acid. The reaction of Fe(ClO4)3.10H2O with Hpca in the presence of 3 equiv. of Bu4NOH yields 2, whereas the presence of NaOH yields 3. The molecular structure of 1 contains an iron(II) ion with a pseudo-octahedral environment resulting from the coordination of two pca- ligands in a bidentate chelating fashion and two pyridine molecules; pi-pi stacking interactions between pyridine and pyrazine rings lead to a one-dimensional chain. Complex 2 is an iron(II) coordination polymer with an infinite zig-zag motif and an Fe...Fe separation of 7.1 A. In 2, the pi-pi stacking interactions involving the pyrazine rings and the strong hydrogen bonds between the coordinated water molecule and the carboxylate oxygens of two pca- ligands result in a three-dimensional network structure. Complex 3 consists of an anionic micro-oxo-bridged diiron(III) core with two crystallographically distinct iron(iii) ions; the negative charge is compensated by two sodium cations. Complex 3 is assembled in a three dimensional network structure through coordination of Na(I) and hydrogen bond interactions. Temperature dependent magnetic susceptibility and Mössbauer spectroscopic studies indicate that 1 and 2 have similar magnetic properties. Both complexes are paramagnetic above 12 K, whereas antiferromagnetic ordering is observed below 12 K. The magnetic properties of reveal strong intramolecular antiferromagnetic interactions between the two iron(III) ions with a J value of -221 cm(-1); no long range intermolecular magnetic coupling is observed between 295 and 4.2 K.

  12. 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

  13. 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.

  14. The hydration properties of Eu(II) and Eu(III): An ab initio quantum mechanical molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Canaval, Lorenz R.; Rode, Bernd M.

    2015-01-01

    A comparison of the hydration characteristics of di- and trivalent europium ions in aqueous solution is presented. The established quantum mechanical charge-field molecular dynamics (QMCF-MD) approach yielded two 30 ps simulations. Significant differences among the two species were found in the Eu-O radial distribution functions, both in good agreement with experiments. The first shell coordination numbers of 8.1 and 8.9 were observed for Eu(II) and Eu(III), respectively. The mean residence time of first shell ligands differ by more than one order of magnitude, the divalent ion's hydration shell being more flexible, which is underlined by a weak ion-water bond strength.

  15. Theory and Calculation of the Phosphorescence Phenomenon.

    PubMed

    Baryshnikov, Gleb; Minaev, Boris; Ågren, Hans

    2017-05-10

    Phosphorescence is a phenomenon of delayed luminescence that corresponds to the radiative decay of the molecular triplet state. As a general property of molecules, phosphorescence represents a cornerstone problem of chemical physics due to the spin prohibition of the underlying triplet-singlet emission and because its analysis embraces a deep knowledge of electronic molecular structure. Phosphorescence is the simplest physical process which provides an example of spin-forbidden transformation with a characteristic spin selectivity and magnetic field dependence, being the model also for more complicated chemical reactions and for spin catalysis applications. The bridging of the spin prohibition in phosphorescence is commonly analyzed by perturbation theory, which considers the intensity borrowing from spin-allowed electronic transitions. In this review, we highlight the basic theoretical principles and computational aspects for the estimation of various phosphorescence parameters, like intensity, radiative rate constant, lifetime, polarization, zero-field splitting, and spin sublevel population. Qualitative aspects of the phosphorescence phenomenon are discussed in terms of concepts like structure-activity relationships, donor-acceptor interactions, vibronic activity, and the role of spin-orbit coupling under charge-transfer perturbations. We illustrate the theory and principles of computational phosphorescence by highlighting studies of classical examples like molecular nitrogen and oxygen, benzene, naphthalene and their azaderivatives, porphyrins, as well as by reviewing current research on systems like electrophosphorescent transition metal complexes, nucleobases, and amino acids. We furthermore discuss modern studies of phosphorescence that cover topics of applied relevance, like the design of novel photofunctional materials for organic light-emitting diodes (OLEDs), photovoltaic cells, chemical sensors, and bioimaging.

  16. 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.

  17. Photoluminescence properties of a novel cyclometalated iridium(III) complex with coumarin-boronate and its recognition of hydrogen peroxide.

    PubMed

    Li, Chunxiang; Wang, Shuqin; Huang, Yangmei; Wen, Qin; Wang, Lei; Kan, Yuhe

    2014-04-14

    A novel neutral iridium(III) complex-based phosphorescent probe (Ir-2) for hydrogen peroxide (H2O2) has been designed and synthesized by incorporating a benzeneboronic acid pinacol ester (bpe) moiety into 3-(benzothiazol-2-yl)-7-hydroxy-coumarin (Bthc) as a cyclometalated ligand (Bthc-bpe). The photophysical behavior of Ir-2 was investigated by UV-Vis absorption spectroscopy, photoluminescence spectroscopy, and quantum mechanical calculations. The absorption spectra of the complex Ir-2 are dominated by the cyclometalated ligand; thus it shows an intense absorption band in the visible region at 460 nm with a molar extinction coefficient (ε) of about 3 × 10(4) M(-1) cm(-1), which is rarely found for typical polypyridine iridium(III) complexes. The complex Ir-2 displays efficient phosphorescent emission at 560 nm at room temperature originating from a mixed triplet metal-to-ligand charge-transfer ((3)MLCT, dπ(Ir) → π* (Bthc-bpe)) and triplet intraligand ((3)ILCT, π-π* (Bthc-bpe)) excited states as suggested by the DFT computational studies. Upon reaction with H2O2, the complex displays an emission decrease induced by an intense intermolecular aggregation due to the cleavage of the bulky benzeneboronic acid pinacol ester substituent, indicating that Ir-2 could act as an ON-OFF-type phosphorescent probe for H2O2. Additionally, selectivity studies reveal that the complex Ir-2 possesses high selectivity toward H2O2 over other reactive oxygen species (ROS).

  18. Weight-based discrimination: an ubiquitary phenomenon?

    PubMed

    Sikorski, C; Spahlholz, J; Hartlev, M; Riedel-Heller, S G

    2016-02-01

    Despite strong indications of a high prevalence of weight-related stigmatization in individuals with obesity, limited attention has been given to the role of weight discrimination in examining the stigma obesity. Studies, up to date, rely on a limited basis of data sets and additional studies are needed to confirm the findings of previous studies. In particular, data for Europe are lacking, and are needed in light of a recent ruling of the European Court of Justice that addressed weight-based discrimination. The data were derived from a large representative telephone survey in Germany (n=3003). The dependent variable, weight-based discrimination, was assessed with a one-item question. The lifetime prevalence of weight discrimination across different sociodemographic variables was determined. Logistic regression models were used to assess the association of independent and dependent variables. A sub-group analysis was conducted analyzing all participants with a body mass index ⩾25 kg m(-)(2). The overall prevalence of weight-based discrimination was 7.3%. Large differences, however, were observed regarding weight status. In normal weight and overweight participants the prevalence was 5.6%, but this number doubled in participants with obesity class I (10.2%), and quadrupled in participants with obesity class II (18.7%) and underweight (19.7%). In participants with obesity class III, every third participant reported accounts of weight-based discrimination (38%). In regression models, after adjustment, the associations of weight status and female gender (odds ratio: 2.59, P<0.001) remained highly significant. Discrimination seems to be an ubiquitary phenomenon at least for some groups that are at special risk, such as heavier individuals and women. Our findings therefore emphasize the need for research and intervention on weight discrimination among adults with obesity, including anti-discrimination legislation.

  19. 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…

  20. Cytotoxicity of Pyrazine-Based Cyclometalated (C^Npz^C)Au(III) Carbene Complexes: Impact of the Nature of the Ancillary Ligand on the Biological Properties

    PubMed Central

    2017-01-01

    The synthesis of a series of cyclometalated gold(III) complexes supported by pyrazine-based (C^N^C)-type pincer ligands is reported, including the crystal structure of a cationic example. The compounds provide a new platform for the study of antiproliferative properties of gold(III) complexes. Seven complexes were tested: the neutral series (C^Npz^C)AuX [X = Cl (1), 6-thioguanine (4), C≡CPh (5), SPh (6)] and an ionic series that included the N-methyl complex [(C^NpzMe^C)AuCl]BF4 (7) and the N-heterocyclic carbene complexes [(C^Npz^C)AuL]+ with L = 1,3-dimethylbenzimidazol-2-ylidene (2) or 1,3,7,9-tetramethylxanthin-8-ylidene (3). Tests against human leukemia cells identified 1, 2, 3, and 4 as particularly promising, whereas protecting the noncoordinated N atom on the pyrazine ring by methylation (as in 7) reduced the cytotoxicity. Complex 2 proved to be the most effective of the entire series against the HL60 leukemia, MCF-7 breast cancer, and A549 lung cancer cell lines, with IC50 values down to submicromolar levels, associated with a lower toxicity toward healthy human lung fibroblast cells. The benzimidazolylidene complex 2 accumulated more effectively in human lung cancer cells than its caffeine-based analogue 3 and the gold(III) chloride 1. Compound 2 proved to be unaffected by glutathione under physiological conditions for periods of up to 6 days and stabilizes the DNA G-quadruplex and i-motif structures; the latter is the first such report for gold compounds. We also show the first evidence of inhibition of MDM2–p53 protein–protein interactions by a gold-based compound and identified the binding mode of the compound with MDM2 using saturation transfer difference NMR spectroscopy combined with docking calculations. PMID:28441013

  1. Cytotoxicity of Pyrazine-Based Cyclometalated (C^N(pz)^C)Au(III) Carbene Complexes: Impact of the Nature of the Ancillary Ligand on the Biological Properties.

    PubMed

    Bertrand, Benoît; Fernandez-Cestau, Julio; Angulo, Jesus; Cominetti, Marco M D; Waller, Zoë A E; Searcey, Mark; O'Connell, Maria A; Bochmann, Manfred

    2017-05-15

    The synthesis of a series of cyclometalated gold(III) complexes supported by pyrazine-based (C^N^C)-type pincer ligands is reported, including the crystal structure of a cationic example. The compounds provide a new platform for the study of antiproliferative properties of gold(III) complexes. Seven complexes were tested: the neutral series (C^N(pz)^C)AuX [X = Cl (1), 6-thioguanine (4), C≡CPh (5), SPh (6)] and an ionic series that included the N-methyl complex [(C^N(pzMe)^C)AuCl]BF4 (7) and the N-heterocyclic carbene complexes [(C^N(pz)^C)AuL](+) with L = 1,3-dimethylbenzimidazol-2-ylidene (2) or 1,3,7,9-tetramethylxanthin-8-ylidene (3). Tests against human leukemia cells identified 1, 2, 3, and 4 as particularly promising, whereas protecting the noncoordinated N atom on the pyrazine ring by methylation (as in 7) reduced the cytotoxicity. Complex 2 proved to be the most effective of the entire series against the HL60 leukemia, MCF-7 breast cancer, and A549 lung cancer cell lines, with IC50 values down to submicromolar levels, associated with a lower toxicity toward healthy human lung fibroblast cells. The benzimidazolylidene complex 2 accumulated more effectively in human lung cancer cells than its caffeine-based analogue 3 and the gold(III) chloride 1. Compound 2 proved to be unaffected by glutathione under physiological conditions for periods of up to 6 days and stabilizes the DNA G-quadruplex and i-motif structures; the latter is the first such report for gold compounds. We also show the first evidence of inhibition of MDM2-p53 protein-protein interactions by a gold-based compound and identified the binding mode of the compound with MDM2 using saturation transfer difference NMR spectroscopy combined with docking calculations.

  2. 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

  3. SAGE III

    Atmospheric Science Data Center

    2017-01-13

    SAGE III Data and Information The Stratospheric Aerosol and Gas ... on the spacecraft. SAGE III produced L1 and L2 scientific data from 5/07/2002 until 12/31/2005. The flight of the second instrument is as ... Additional Info:  Data Format: HDF-EOS or Big Endian/IEEE Binary SCAR-B Block:  ...

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. Effect of electronic and steric properties of 8-substituted quinolines in gold(III) complexes: Synthesis, electrochemistry, stability, interactions and antiproliferative studies.

    PubMed

    Casado-Sánchez, Antonio; Martín-Santos, Cecilia; Padrón, José M; Mas-Ballesté, Rubén; Navarro-Ranninger, Carmen; Alemán, José; Cabrera, Silvia

    2017-09-01

    In this work the synthesis and characterization of new gold(III) complexes with quinoline ligands are described. These complexes contain different steric and electronic properties of the donor atom at 8-position of the quinoline in order to modulate their stability and their biological activity. Their redox potential, stability in organic and aqueous solvents, and their biological activity in a panel of six different human tumor cell lines are also presented. In addition, interaction studies of the complexes with model biological molecules (pBR322 and L-acetyl-N-cysteine) were carried out, suggesting that their main target are proteins. From these studies, we have found that the gold(III) complex with an N-tosyl-8-aminoquinoline ligand is the most active complex in all the tumor cell lines, including the cisplatin resistant T-47D and WiDr cell lines. Moreover, this complex showed to be the most stable compound in DMSO and saline solution, even after several hours. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Ln(iii) complexes (Ln = Eu, Gd, Tb, Dy) with a chiral ligand containing 1,10-phenanthroline and (-)-menthol fragments: synthesis, structure, magnetic properties and photoluminescence.

    PubMed

    Larionov, Stanislav V; Bryleva, Yuliya A; Glinskaya, Ludmila A; Plyusnin, Victor F; Kupryakov, Arkady S; Agafontsev, Alexander M; Tkachev, Alexey V; Bogomyakov, Artem S; Piryazev, Dmitry A; Korolkov, Ilya V

    2017-08-29

    A series of lanthanide(iii) complexes based on the new chiral ligand L, which contains 1,10-phenanthroline and (-)-menthol fragments, namely [LnL2(NO3)3] (Ln = Eu (1), Gd (2), Tb (3), Dy (4)), have been synthesized and structurally characterized. Complexes 1-4 are isostructural and crystallize in the non-centrosymmetric space group P41212. The mononuclear complexes comprise a 10-coordinate Ln(3+) ion with two bidentate N,N-donor ligands (L) and three bidentate chelating nitrate groups. The magnetic properties of complexes 1-4 are determined mainly by the Ln(3+) ions. In the case of complexes 3 and 4, significant anisotropy results in nonlinear field dependences of magnetization at low temperature. Complexes 1, 3 and 4 exhibit metal-centered red (Eu(3+)), green (Tb(3+)) and yellow (Dy(3+)) luminescence, respectively, whereas complex 2 displays blue ligand-based luminescence in the solid state at room temperature. The luminescence quantum yield for the solid samples increases in the order 4 < 2 ≈ 3 < 1. The europium(iii) complex shows long luminescence lifetimes (up to 1750 μs) and a very high quantum yield (φf = 0.87); these make this compound promising for application in sensing and optoelectronics.

  10. Measurement of cold challenge responses in primary Raynaud's phenomenon and Raynaud's phenomenon associated with systemic sclerosis.

    PubMed Central

    O'Reilly, D; Taylor, L; el-Hadidy, K; Jayson, M I

    1992-01-01

    Using computed thermography continuous temperature recordings were made before and after cold challenge of the fingers of control subjects and patients with primary Raynaud's phenomenon and Raynaud's phenomenon associated with systemic sclerosis. Basal skin temperature measurements (Tpre) were significantly lower in patients with primary Raynaud's phenomenon and Raynaud's phenomenon associated with systemic sclerosis than in the controls. Temperatures immediately after cold challenge (T0) were significantly lower in patients with primary Raynaud's phenomenon and Raynaud's phenomenon associated with systemic sclerosis than in controls. The lag phase before the start of temperature recovery (Tlag) was significantly greater in patients with primary Raynaud's phenomenon and Raynaud's phenomenon associated with systemic sclerosis than in control subjects. The maximum recovery index (R%) was significantly less in patients with primary Raynaud's phenomenon and Raynaud's phenomenon associated with systemic sclerosis than in controls. The maximum rate of change of temperature during the rapid phase of rewarming (Gmax) was significantly greater in controls than in patients with primary Raynaud's phenomenon and Raynaud's phenomenon associated with systemic sclerosis. Discriminant analysis showed that the dynamic parameters of rewarming (Tlag, Gmax, and R%) showed greater variation between the patients with primary Raynaud's phenomenon and those with Raynaud's phenomenon associated with systemic sclerosis than did Tpre or T0. This method of analysis of cold challenge will be used in studies of the effects of treatment of Raynaud's phenomenon. PMID:1466594

  11. 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).

  12. Inter-band optoelectronic properties in quantum dot structure of low band gap III-V semiconductors

    SciTech Connect

    Dey, Anup; Maiti, Biswajit; Chanda, Debasree

    2014-04-14

    A generalized theory is developed to study inter-band optical absorption coefficient (IOAC) and material gain (MG) in quantum dot structures of narrow gap III-V compound semiconductor considering the wave-vector (k{sup →}) dependence of the optical transition matrix element. The band structures of these low band gap semiconducting materials with sufficiently separated split-off valance band are frequently described by the three energy band model of Kane. This has been adopted for analysis of the IOAC and MG taking InAs, InSb, Hg{sub 1−x}Cd{sub x}Te, and In{sub 1−x}Ga{sub x}As{sub y}P{sub 1−y} lattice matched to InP, as example of III–V compound semiconductors, having varied split-off energy band compared to their bulk band gap energy. It has been found that magnitude of the IOAC for quantum dots increases with increasing incident photon energy and the lines of absorption are more closely spaced in the three band model of Kane than those with parabolic energy band approximations reflecting the direct the influence of energy band parameters. The results show a significant deviation to the MG spectrum of narrow-gap materials having band nonparabolicity compared to the parabolic band model approximations. The results reflect the important role of valence band split-off energies in these narrow gap semiconductors.

  13. Solution properties of the Ln(III) complexes of a novel octadentate chelator with rigidified iminodiacetate arms.

    PubMed

    Tei, Lorenzo; Baranyai, Zsolt; Cassino, Claudio; Fekete, Marianna; Kálmán, Ferenc K; Botta, Mauro

    2012-11-07

    A novel octadentate ligand derived from the core structure of EGTA (ethyleneglycol-bis(2-aminoethylether)-N,N,N',N'-tetraacetic acid) with two piperidine-cis-dicarboxylic acid moieties spaced by a triethylenedioxy chain (L1) has been synthesised with the aim to assess the effect of the structural rigidity on the thermodynamic and kinetic stabilities of its Ln(III) complexes. The stability constants of [Ln(L1)](-) complexes show a weaker binding affinity for Ln(3+) ions of L1 than EGTA. On the other hand, the selectivity of L1 for Ca(2+) over Mg(2+) is one of the highest ever reported. The kinetic inertness has been also investigated and faster rates of both acid catalysed and metal assisted decomplexation have been measured for [Gd(L1)](-) as compared to [Gd(EGTA)](-). The (1)H- and (13)C NMR spectra of the diamagnetic La(3+), Y(3+) and Lu(3+) complexes in aqueous media show pronounced stereochemical rigidity and the occurrence of a structural change across the lanthanide series. Finally, a complete (1)H and (17)O NMR relaxometric study indicates that [Gd(L1)](-) possesses a nine-coordinate ground state with one inner coordination sphere water molecule characterized by a fast rate of exchange ((298)k(ex) = 59 × 10(6) s(-1)).

  14. 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.

  15. 3-D indium(III)-btc channel frameworks and their ion-exchange properties (btc=1,3,5-benzenetricarboxylate)

    SciTech Connect

    Lin Zhengzhong; Chen Lian; Yue Chengyang; Yuan Daqiang; Jiang Feilong . E-mail: fjiang@fjirsm.ac.cn; Hong Maochun

    2006-04-15

    Assembly of InCl{sub 3} with 1,3,5-benzenetricarboxylic acid (H{sub 3}btc) and pyridine or pyridine derivatives under hydrothermal conditions produces a series of isostructural coordination polymers with the interesting frameworks: {l_brace}(HL)[In{sub 4}(OH){sub 4}(btc){sub 3}].L.3H{sub 2}O{r_brace} {sub n} {sub ,} L=pyridine (1); L=2-picoline (2); L=4-picoline (3) and {l_brace}(Hdpea)[In{sub 4}(OH){sub 4}(btc){sub 3}].3H{sub 2}O{r_brace} {sub n} (4) (dpea=1,2-di(4-pyridyl)ethane). In these four complexes, carboxyl and hydroxyl oxygen atoms bridge indium(III) centers to form octahedral chain-like sinusoidal curves, which are further interlinked by btc{sup 3-} moieties to generate 3-D frameworks with 1-D channels. The protonated guests HL in 1-3 located at the channels can be fully exchanged by K{sup +} ion or partially exchanged by Sr{sup 2+}, and Ba{sup 2+} ions.

  16. 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.

  17. 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

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. The Photoluminescent Properties of New Cationic Iridium(III) Complexes Using Different Anions and Their Applications in White Light-Emitting Diodes.

    PubMed

    Yang, Hui; Meng, Guoyun; Zhou, Yayun; Tang, Huaijun; Zhao, Jishou; Wang, Zhengliang

    2015-09-14

    Three cationic iridium(III) complexes [Ir(ppy)₂(phen)][PF₆] (C1), [Ir(ppy)₂(phen)]₂SiF₆ (C2) and [Ir(ppy)₂(phen)]₂TiF₆ (C3) (ppy: 2-phenylpyridine, phen: 1, 10-phenanthroline) using different anions were synthesized and characterized by ¹H Nuclear magnetic resonance (¹HNMR), mass spectra (MS), Fourier transform infrared (FTIR) spectra and element analysis (EA). After the ultraviolet visible (UV-vis) absorption spectra, photoluminescent (PL) properties and thermal properties of the complexes were investigated, complex C1 and C3 with good optical properties and high thermal stability were used in white light-emitting diodes (WLEDs) as luminescence conversion materials by incorporation with 460 nm-emitting blue GaN chips. The integrative performances of the WLEDs fabricated with complex C1 and C3 are better than those fabricated with the widely used yellow phosphor Y₃Al₅O12:Ce(3+) (YAG). The color rendering indexes of the WLEDs with C1 and C3 are 82.0 and 82.6, the color temperatures of them are 5912 K and 3717 K, and the maximum power efficiencies of them are 10.61 Lm·W(-1) and 11.41 Lm·W(-1), respectively.

  3. 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.

  4. 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.

  5. A new europium(III) complex containing a neutral ligand of 2-(pyridin-2-yl)-1H-benzo[d]imidazole: Thermal, electrochemical, luminescent properties

    NASA Astrophysics Data System (ADS)

    Liu, Jian; Li, Shuigen; Liao, Weibing; Chen, Yong

    2013-04-01

    A new europium(III) complex i.e. Eu(ECTFBD)3PBI was synthesized, where ECTFBD and PBI are 4-(9-ethyl-9H-carbazol-3-yl)-1,1,1-trifluoro-4-oxobutan-2-olate anion and 2-(pyridin-2-yl)-1H-benzo[d]imidazole, respectively. Its IR, UV-Vis spectra, electrochemical, thermal properties as well as photoluminescent performances in solid state and in CH2Cl2 were investigated. Eu(ECTFBD)3PBI exhibited strong red emission without any emission from ECTFBD and PBI in solid state, but with a very weak emission from ECTFBD in CH2Cl2. We explored this difference of the luminesecences of Eu(ECTFBD)3PBI in solid state and in CH2Cl2 based on the excited triplet energy levels of ECTFBD and PBI.

  6. Electronic properties of III-nitride semiconductors: A first-principles investigation using the Tran-Blaha modified Becke-Johnson potential

    SciTech Connect

    Araujo, Rafael B. Almeida, J. S. de Ferreira da Silva, A.

    2013-11-14

    In this work, we use density functional theory to investigate the influence of semilocal exchange and correlation effects on the electronic properties of III-nitride semiconductors considering zinc-blende and wurtzite crystal structures. We find that the inclusion of such effects through the use of the Tran-Blaha modified Becke-Johnson potential yields an excellent description of the electronic structures of these materials giving energy band gaps which are systematically larger than the ones obtained with standard functionals such as the generalized gradient approximation. The discrepancy between the experimental and theoretical band gaps is then significantly reduced with semilocal exchange and correlation effects. However, the effective masses are overestimated in the zinc-blende nitrides, but no systematic trend is found in the wurtzite compounds. New results for energy band gaps and effective masses of zinc-blende and wurtzite indium nitrides are presented.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Mechanical Properties of Individual Southern Pine Fibers. Part III: Global Relationships Between Fiber Properties and Fiber Location Within An Individual Tree

    Treesearch

    Les Groom; Stephen Shaler; Laurence Mott

    2002-01-01

    This is the third and final paper in a three-part series investigating the effect of location within a tree on the mechanical properties of individual wood tracheids. This paper focuses on the definition of juvenile, transition, and mature zones as classified by fiber stiffness, strength, microfibril angle, and cross-sectional area. The average modulus of elasticity...

  12. Mechanical properties of individual southern pine fibers. Part III. Global relationships between fiber properties and fiber location within an individual tree.

    Treesearch

    Leslie H. Groom; Stephen Shaler; Laurence Mott

    2002-01-01

    This is the third and final paper in a three-part series investigating the effect of location within a tree on the mechanical properties of individual wood tracheids. This paper focuses on the definition of juvenile, transition, and mature zones as classified by fiber stiffness, strength, microfibril angle, and cross-sectional area. The average modulus of elasticity...

  13. Terrorism as a Social and Legal Phenomenon

    ERIC Educational Resources Information Center

    Serebrennikova, Anna; Mashkova, Yekaterina

    2017-01-01

    This article examines the concept of terrorism as a social and legal phenomenon, its international legal and criminal-legal characteristics. Highlighted are the main aspects of cooperation of the states and the international community to counter terrorist activities. Terrorism as a social phenomenon is determined by paragraph 1 of article 3 of the…

  14. H2O Southern Galactic Plane Survey (HOPS): Paper III - properties of dense molecular gas across the inner Milky Way

    NASA Astrophysics Data System (ADS)

    Longmore, S. N.; Walsh, A. J.; Purcell, C. R.; Burke, D. J.; Henshaw, J.; Walker, D.; Urquhart, J.; Barnes, A. T.; Whiting, M.; Burton, M. G.; Breen, S. L.; Britton, T.; Brooks, K. J.; Cunningham, M. R.; Green, J. A.; Harvey-Smith, L.; Hindson, L.; Hoare, M. G.; Indermuehle, B.; Jones, P. A.; Lo, N.; Lowe, V.; Moore, T. J. T.; Thompson, M. A.; Voronkov, M. A.

    2017-09-01

    The H2O Southern Galactic Plane Survey (HOPS) has mapped 100 deg2 of the Galactic plane for water masers and thermal molecular line emission using the 22 m Mopra telescope. We describe the automated spectral-line fitting pipelines used to determine the properties of emission detected in HOPS data cubes, and use these to derive the physical and kinematic properties of gas in the survey. A combination of the angular resolution, sensitivity, velocity resolution and high critical density of lines targeted make the HOPS data cubes ideally suited to finding precursor clouds to the most massive and dense stellar clusters in the Galaxy. We compile a list of the most massive HOPS ammonia regions and investigate whether any may be young massive cluster progenitor gas clouds. HOPS is also ideally suited to trace the flows of dense gas in the Galactic Centre. We find the kinematic structure of gas within the inner 500 pc of the Galaxy is consistent with recent predictions for the dynamical evolution of gas flows in the centre of the Milky Way. We confirm a recent finding that the dense gas in the inner 100 pc has an oscillatory kinematic structure with characteristic length-scale of 20 pc, and also identify similar oscillatory kinematic structure in the gas at radii larger than 100 pc. Finally, we make all of the above fits and the remaining HOPS data cubes across the 100 deg2 of the survey available to the community.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. A large perturbation on electronic and photophysical properties of Ir(III) carbene complexes caused by the variation of N-substitution in N,N‧-heteroaromatic ligands

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    DFT/TDDFT investigation was performed on the electronic and photophysical properties of blue-emitting Ir(III) carbene complexes (fpmi)3-xIr(N^N‧)x (x = 1, 2) [fpmi = 1-(4-fluorophenyl)-3-methylimidazolin-2-ylidene-C,C2‧, N^N‧ = 2-(1H-pyrazol-5-yl)pyridinato (1a(x = 1)/1a‧(x = 2)); 2-(1H-imidazol-5-yl)pyridinato (1b/1b‧); 2-(1H-imidazol-2-yl)pyridinato (1c/1c‧); 2-(1H-1,2,4-triazol-5-yl)pyridinato (2a/2a‧); 2-(1H-1,2,3-triazol-5-yl)pyridinato (2b/2b‧); 2-(4H-1,2,4-triazol-3-yl)pyridinato (2c/2c‧)]. The absorption intensities and band positions are obviously affected by the variation of N substitution in N^N‧ ligand. The emission properties show an apparent dependence on the solvent effects, and the N^N‧ ligand plays an important role in governing the emissive state. The pyrazolyl-pyridyl-based N^N‧ ligand is considered to be more beneficial for blue OLEDs emitters.

  20. 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.

  1. Pincer-CNC mononuclear, dinuclear and heterodinuclear Au(III) and Pt(II) complexes supported by mono- and poly-N-heterocyclic carbenes: synthesis and photophysical properties.

    PubMed

    Gonell, S; Poyatos, M; Peris, E

    2016-04-07

    A family of cyclometallated Au(iii) and Pt(ii) complexes containing a CNC-pincer ligand (CNC = 2,6-diphenylpyridine) supported by pyrene-based mono- or bis-NHC ligands have been synthesized and characterized, together with the preparation of a Pt-Au hetero-dimetallic complex based on a Y-shaped tris-NHC ligand. The photophysical properties of all the new species and of two related Ru(ii)-arene complexes were studied and compared. Whereas the pyrene-based complexes only exhibit emission in solution, those containing the Y-shaped tris-NHC ligand are only luminescent when dispersed in poly(methyl methacrylate) (PMMA). In particular, the pyrene-based complexes were found to be emissive in the range of 373-440 nm, with quantum yields ranging from 3.1 to 6.3%, and their emission spectra were found to be almost superimposable, pointing to the fluorescent pyrene-centered nature of the emission. This observation suggests that the emission properties of the pyrene fragment may be combined with some of the numerous applications of NHCs as supporting ligands allowing, for instance, the design of biological luminescent agents.

  2. Resonant Phenomenon in a Stochastic Delayed Bistable Chemical System

    NASA Astrophysics Data System (ADS)

    Li, Chunxuan; Yang, Tao

    2015-06-01

    In this paper, the resonant phenomenon for a bistable chemical system in the presence of noises and delayed feedback is investigated. The signal-to-noise ratio (SNR) is calculated when periodic signal is introduced additively (or multiplicatively). The impacts of the parameter μ of the reaction, time delay τ, strength K of the feedback loop, multiplicative ( D) and additive ( Q) noise strengths and cross-correlation strength λ between two noises on the SNR are discussed. When the periodic signal is introduced additively, our results show (i) the SNR as a function of the parameter μ exhibits a maximum, the existence of the maximum is a characteristic of the parametric resonance (PR) phenomenon; (ii) the SNR as a function of D exhibits only a maximum, however, for the case of SNR as a function of Q exhibits not only a maximum, but also a minimum. The existence of the maximum and minimum in the SNR is the identifying characteristics of the stochastic resonance (SR) and reverse-resonance (RR); and (iii) the increases of τ, K and λ enhance the SR and weaken the RR. Finally, we compare the resonant phenomenon for the additive periodic signal with that for multiplicative one in the chemical system.

  3. 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.

  4. Binding Properties of Streptococcus gordonii SspA and SspB (Antigen I/II Family) Polypeptides Expressed on the Cell Surface of Lactococcus lactis MG1363

    PubMed Central

    Holmes, Ann R.; Gilbert, Christophe; Wells, Jeremy M.; Jenkinson, Howard F.

    1998-01-01

    The oral bacterium Streptococcus gordonii expresses two cell wall-associated polypeptides, designated SspA (1,542 amino acid residues) and SspB (1,462 amino acid residues), that have 70% sequence identity. These polypeptides are members of the antigen I/II family of oral streptococcal adhesins and mediate the binding of streptococci to salivary glycoproteins, collagen, and other oral microorganisms such as Actinomyces naeslundii. To determine if SspA and SspB have differential binding properties, the coding sequences of the sspA and sspB genes were cloned into expression plasmid vector pTREX1-usp45LS to generate pTREX1-sspA and pTREX1-sspB, respectively, and the Ssp polypeptides were displayed on the cell surface of Lactococcus lactis MG1363. Lactococcal cells expressing similar levels of surface SspA or SspB polypeptide were then compared for their abilities to adhere to a range of antigen I/II polypeptide substrates. More than twice as many L. lactis cells expressing SspA bound to immobilized salivary agglutinin glycoprotein (SAG) as did L. lactis cells expressing SspB. In contrast, lactococci expressing SspB adhered twice as well as lactococci producing SspA to collagen type I and to Candida albicans. The binding of A. naeslundii to lactococci was only weakly enhanced by surface expression of Ssp polypeptides. L. lactis(pTREX1-sspB) cells bound in greater numbers to SAG than did Enterococcus faecalis JH2-2 cells expressing SspB from pAM401EB-5. The results suggest that SspA and SspB have markedly different binding affinities for their oral substrates and thus may function to promote site diversity in colonization by S. gordonii. PMID:9746559

  5. [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

  6. [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.

  7. 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. Copyright © 2014 John Wiley & Sons, Ltd.

  8. Immunochemistry of the Lewis blood-group system. III. Studies on the molecular basis of the Lex property.

    PubMed

    Schenkel-Brunner, H; Hanfland, P

    1981-05-01

    The antigen specificities of different anti-Lex sera were examined by immunoadsorption studies using adsorbents with well-defined carbohydrate units covalently bound to an inorganic matrix (Synsorb, Chembiomed). In contrast to those of normal anti-Lea and anti-Leb sera, the antibody binding site of Lex antibodies was found to be considerably smaller, comprising merely the structure Fuc alpha leads to 4GlcNAc--R. Based on this property, homogeneously recting Lex antibodies could be isolated from heterogeneous anti-Lea + b + x sera by means of affinity chromatography of Fuc alpha leads to 4GlcNAc-Synsorb. When the serological reactivity of the purified Lex antibodies against a Lea-active glycolipid isolated from human plasma was compared with that of normal anti-Lea serum using haemagglutination inhibition and quantitative passive haemagglutination tests, evidence was obtained that the Lex character of cord blood erythrocytes is not based on the existence of a separate Lex antigen, but rather on the ability of the anti-Lex antibodies to react already with traces of Lea substance present on fetal erythrocytes, not detectable by normal anti-Lea agglutinins.

  9. 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.

  10. 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.

  11. [NH2(C2H4)2O]MX5: a new family of morpholinium nonlinear optical materials among halogenoantimonate(III) and halogenobismuthate(III) compounds. Structural characterization, dielectric and piezoelectric properties.

    PubMed

    Owczarek, Magdalena; Szklarz, Przemysław; Jakubas, Ryszard; Miniewicz, Andrzej

    2012-06-28

    This paper presents the structural features of ionic complexes formed by morpholine and metal ions which belong to group VA, namely Sb(III) and Bi(III). A series of target inorganic-organic hybrid compounds of the general formula [NH(2)(C(2)H(4))(2)O](2)MX(5) (where M = Sb, Bi; X = Cl, Br) has been synthesized by incorporating the organic component (morpholine) into the highly polarizable one-dimensional halogenoantimonate(III)/halogenobismuthate(III) chain network. Among the studied compounds, four were found to crystallize in the room temperature phase in the piezoelectric, orthorhombic space group P2(1)2(1)2(1), Z = 4, the feature being confirmed by the powder second harmonic generation of light and piezoelectric measurements. Dielectric dispersion studies between 200 Hz and 2 MHz disclosed a relaxation process below room temperature well described by the Cole-Cole equation. Based on crystal structures available in Cambridge Structural Database (version 5.32, November 2010) we attempt to show a relationship between the acentric symmetry of compounds and the type of anionic network within the R(2)MX(5)-subgroup (where R denotes organic cation) of halogenoantimonates(III) and halogenobismuthates(III).

  12. The Fleischmann-Pons phenomenon; Different perspective

    SciTech Connect

    Ray, M.K.S.; Saini, R.D.; Das, D.; Chattopadhyay, G.; Parthasarathy, R.; Garg, S.P.; Venkataramani, R.; Sen, B.K.; Iyengar, T.S.; Kutty, K.K. )

    1992-11-01

    This paper reports on attempts which have been made to initiate the Fleischmann-Pons phenomenon through selective perturbations during experimental studies in divided electrolytic cells. Despite wide variations in the operating parameters and the attainment of high loading (sometimes up to D/Pd [approx] 2), the phenomenon was not observed either during the unperturbed electrolysis or on physical perturbation. However, instances of its occurrence were observed when the state of equilibrium of the deuterated cathode (having a scale free portion) was chemically perturbed by oxygen. This observation, viewed in light of available information, is indicative of oxygen playing a vital role in the phenomenon.

  13. [Gregg phenomenon and garden hose effect].

    PubMed

    Schipke, J D; Frehen, D

    2001-05-01

    Under physiologic circumstances, cardiac function determines myocardial oxygen consumption and consequently coronary perfusion. Surprisingly, in a reverse direction, improved coronary perfusion also increased myocardial oxygen consumption and contractile function. This experimental finding, now 40 years old, is termed the Gregg phenomenon. Some 10 years later, in experiments by Arnold and co-workers, an isolated increase in perfusion pressure improved ventricular function. In this context, the term 'gardenhose effect' was coined, implying a hydraulic explanation of the Gregg phenomenon. In the following, we attempt to distinguish the Gregg phenomenon from the gardenhose effect and to critically evaluate them.

  14. 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.

  15. 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.

  16. 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

  17. 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

  18. 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.

  19. The lean hunting phenomenon in gasoline engines

    SciTech Connect

    Tanaka, M.; Mochizuki, S.; Nishiwaki, N.; Miyake, M.

    1987-01-01

    A quite interesting self-excited oscillation phenomenon in engine speed, which may not be explained with the classical theory of mechanical hunting, is studied experimentally. The effects of the various engine operating variables on the phenomenon are examined using a four cycle single cylinder gasoline engine with an inertia governor. It was found that the phenomenon occurs when engines are operated at a lean air fuel ratio under light load conditions, and that the hunting phenomenon is ascribable to the temporary shift in air fuel ratio from the steady state value. This shift in air fuel ratio occurs due to the fuel flow delay into the cylinder caused by the fact that the fuel flow into the cylinder cannot follow the movement of the throttle valve.

  20. Orgasm Induced Seizures: A Rare Phenomenon.

    PubMed

    Chaukimath, S P; Patil, P S

    2015-01-01

    A variety of stimuli can cause reflex seizures, Some triggers include light, music and cognitive phenomenon. There are case reports however where the phenomenon of sexual activity has been a trigger for epileptic seizures. Most of these cases reported are in women so far, and were found to be localized to right cerebral hemisphere. We report a case of a 36-year-old male with orgasm-induced seizures, with other atypical features compared to majority of previous reports.

  1. 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

  2. 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.

  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. 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…

  5. 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…

  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. 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.

  8. 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.

  9. 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.

  10. Near-IR Emitting Iridium(III) Complexes with Heteroaromatic β-Diketonate Ancillary Ligands for Efficient Solution-Processed OLEDs: Structure-Property Correlations.

    PubMed

    Kesarkar, Sagar; Mróz, Wojciech; Penconi, Marta; Pasini, Mariacecilia; Destri, Silvia; Cazzaniga, Marco; Ceresoli, Davide; Mussini, Patrizia R; Baldoli, Clara; Giovanella, Umberto; Bossi, Alberto

    2016-02-18

    Three NIR-emitting neutral Ir(III) complexes [Ir(iqbt)2 (dpm)] (1), [Ir(iqbt)2 (tta)] (2), and [Ir(iqbt)2 (dtdk)] (3) based on the 1-(benzo[b]thiophen-2-yl)-isoquinolinate (iqtb) were synthesized and characterized (dpm=2,2,6,6-tetramethyl-3,5-heptanedionate; tta=2-thienoyltrifluoroacetonate; dtdk=1,3-di(thiophen-2-yl)propane-1,3-dionate). The compounds emit between λ=680 and 850 nm with high luminescence quantum yields (up to 16 %). By combining electrochemistry, photophysical measurements, and computational modelling, the relationship between the structure, energy levels, and properties were investigated. NIR-emitting, solution-processed phosphorescent organic light-emitting devices (PHOLEDs) were fabricated using the complexes. The devices show remarkable external quantum efficiencies (above 3 % with 1) with negligible efficiency roll-off values, exceeding the highest reported values for solution-processible NIR emitters. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. 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.

  13. Cyclometalated iridium(III)-polyamine complexes with intense and long-lived multicolor phosphorescence: synthesis, crystal structure, photophysical behavior, cellular uptake, and transfection properties.

    PubMed

    Li, Steve Po-Yam; Tang, Tommy Siu-Ming; Yiu, Ken Shek-Man; Lo, Kenneth Kam-Wing

    2012-10-15

    A new class of phosphorescent cyclometalated iridium(III)-polyamine complexes [{Ir(N^C)(2)}(n)(bPEI)](PF(6))(n)(bPEI=branched poly(ethyleneimine), average M(w =25 kDa, n=15.6-27.4; HN^C=2-phenylpyridine Hppy (1a), 2-((1,1'-biphenyl)-4-yl)pyridine Hpppy (2a), 2-phenylquinoline Hpq (3a), 2-phenylbenzothiazole Hbt (4a), 2-(1-naphthyl)benzothiazole Hbsn (5a)) and [Ir(N^C)(2)(en)](PF(6)) (en=ethylenediamine; HN^C=Hppy (1b), Hpppy (2b), Hpq (3b), Hbt (4b), Hbsn (5b)) have been synthesized and characterized. The X-ray crystal structure of complex 5b was also determined. All of these complexes showed a reversible iridium(IV/III) oxidation couple at +1.01 to +1.26 V and a quasi-reversible ligand-based reduction couple at -1.54 to -2.08 V (versus SCE). Upon photoexcitation, the complexes displayed intense and long-lived green to orange-red emission in fluid solutions at room temperature and in low-temperature glass. Lipophilicity measurements indicated that bPEI played a dominant role in the polar nature of complexes 1a-5a, thus rendering them very soluble in aqueous solutions. Inductively coupled plasma-mass spectrometry (ICP-MS) and confocal laser scanning microscopy (CLSM) data indicated that an energy-requiring process, such as endocytosis, was involved in the cellular uptake of all of the complexes. In addition, the cytotoxicity of the complexes toward human cervix epithelioid carcinoma (HeLa) and human embryonic kidney 293T (HEK293T) cell-lines has been evaluated by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay. The DNA-binding properties of complex 5a have been investigated by gel-retardation assays and the polyplexes that were formed from this complex with plasmid DNA (pDNA) were studied by zeta-potential measurements and particle-size estimation. Furthermore, complex 5a was grafted with poly(ethylene glycol) (PEG, average M(w)=2 kDa) to different extents, thereby yielding the phosphorescent copolymers PEG(12.3)-g-5a, PEG(25.4)-g-5a

  14. 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.

  15. 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

  16. 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

  17. 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.

  18. 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.

  19. Measurement of thermoacoustic convection heat transfer phenomenon

    NASA Technical Reports Server (NTRS)

    Parang, M.; Salah-Eddine, A.

    1983-01-01

    In this paper the results of an experimental investigation of thermoacoustic convection (TAC) heat transfer phenomenon in both zero-gravity and gravity environment are presented and compared with pure conduction heat transfer. The numerical solutions of the governing equations obtained by others for TAC heat transfer phenomenon are also discussed. The experimental results show that for rapid heating rate at a boundary, the contribution of TAC heat transfer to a gas could be significantly (one order of magnitude) higher than heat transfer rate from pure conduction. The results also show significantly reduced transient time in heat transfer processes involving thermoacoustic convective heat transfer mode in both space and gravity environment.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  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. 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…

  11. 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…

  12. 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)

  13. 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…

  14. Return to the "Getting Better Phenomenon"

    ERIC Educational Resources Information Center

    Carley, Glenn

    2007-01-01

    A school social work intervention called the "Getting Better Phenomenon" is redesigned as a curriculum resource for eighth- and ninth-grade teachers. The activities in the curriculum represent a synergy of provincial learning expectations; academic assessment and evaluation structures; teacher-guided delivery of student-generated "course" content;…

  15. 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…

  16. 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…

  17. 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)

  18. 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…

  19. 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.

  20. 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…

  1. [Raynaud's phenomenon in occupational vibration exposure].

    PubMed

    Letzel, S; Muttray, A

    2013-03-01

    A 34-year-old female stonemason was referred for expert opinion. The question at issue was, whether she suffered from vibration-induced white finger disease. She was exposed to high-frequency hand-arm vibrations for many years. She reported white finger attacks at the long fingers, which were associated with cold weather. Until this point, physical findings were normal. The cold water provocation test showed a slight delay of the rewarming for the long fingers of the right hand. The nailfold capillary microscopy was normal. The slight Raynaud's phenomenon was recognized as an occupational disease with a diagnosis of vibration-induced white finger disease. About three years later, the symptoms of the Raynaud's phenomenon had deteriorated, although the patient had finished working with vibrating tools. The cold water provocation test confirmed the deterioration. At this time, the patient had inflamed swellings of some joints caused by rheumatoid arthritis. The differential diagnosis of a Raynaud's phenomenon should include occupational causes. Occupational history is diagnostically indicative. If an occupational disease is assumed, a report must be filed. With respect to German social law, the deterioration of the Raynaud's phenomenon was caused by the rheumatoid arthritis, which is regarded as independent from the job. © Georg Thieme Verlag KG Stuttgart · New York.

  2. Systemic lupus erythematosus and Raynaud's phenomenon*

    PubMed Central

    Heimovski, Flavia Emilie; Simioni, Juliana A.; Skare, Thelma Larocca

    2015-01-01

    BACKGROUND Patients with systemic lupus erythematosus seem to belong to different serological and clinical subgroups of the disease. Genetic background can cause the appearance of these subgroups. OBJECTIVE To determine whether Brazilian patients who have systemic lupus erythematosus and Raynaud's phenomenon differ from those who do not. METHODS Retrospective analysis of 373 medical records of systemic lupus erythematosus patients studied for demographic, clinical and serological data. A comparative analysis was performed of individuals with and without RP. RESULTS There was a positive association between Raynaud's phenomenon and age at diagnosis (p=0.02), presence of anti-Sm (p=0.01) antibodies and anti-RNP (p<0.0001). Furthermore, a negative association was found between Raynaud's phenomenon and hemolysis (p=0.01), serositis (p=0.01), glomerulonephritis (p=0.0004) and IgM aCL (p=0.004) antibodies. CONCLUSION Raynaud's phenomenon patients appear to belong to a systemic lupus erythematosus subset with a spectrum of clinical manifestations located in a more benign pole of the disease. PMID:26734864

  3. Magnetic properties of the layered III-VI diluted magnetic semiconductor Ga{sub 1−x}Fe{sub x}Te

    SciTech Connect

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

    2016-05-15

    Magnetic properties of single crystalline Ga{sub 1−x}Fe{sub x}Te (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 Ga{sub 1−x}Mn{sub x}Se and Ga{sub 1−x}Mn{sub x}S and reaches a maximum of 0.68 emu/g at 2 K in 7 T. The magnetization of Ga{sub 1−x}Fe{sub x}Te 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 Ga{sub 1−x}Fe{sub x}Se. Neither the broad thermal hysteresis observed from 100-300 K in In{sub 1−x}Mn{sub x}Se nor the spin-glass behavior observed around 10.9 K in Ga{sub 1−x}Mn{sub x}S are observed in Ga{sub 1−x}Fe{sub x}Te. 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 Å{sup 3}.

  4. 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

  5. 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.

  6. 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.

  7. Endoscopic thoracic sympathicotomy for Raynaud's phenomenon.

    PubMed

    Matsumoto, Yasushi; Ueyama, Takeshi; Endo, Masamitsu; Sasaki, Hisao; Kasashima, Fuminori; Abe, Yoshinobu; Kosugi, Ikuko

    2002-07-01

    For many years, thoracic sympathectomy via open surgery was not used to treat Raynaud's phenomenon because of the invasiveness of this procedure and the poor long-term outcomes associated with it. However, with the introduction of endoscopic surgery, thoracic sympathectomy (or sympathicotomy) has been performed by some surgeons as a less invasive surgical option for patients with Raynaud's phenomenon. The less invasive procedure has the possibility of emphasizing merits of sympathectomy. The purpose of this study was to reevaluate the efficacy of sympathicotomy for Raynaud's phenomenon with endoscopic technique and its range of applicability. Between December 1992 and August 2001, endoscopic thoracic sympathicotomy (ETS) was performed in 28 patients with Raynaud's phenomenon (of a total of 502 patients with autonomic disorders who underwent ETS) at National Kanazawa Hospital. We considered indications for surgical treatment of Raynaud's phenomenon to include severe chronic symptoms or nonhealing digital ulceration refractory to intensive medical therapy. All patients were mailed a self-assessment questionnaire after surgery to determine the immediate and long-term results of the procedure. Data from both initial and long-term follow-up examinations were obtained. Fifty-four ETS procedures were performed in 28 patients. No operative mortality was seen, and no occurrence of major complications necessitated open surgery. Initial resolution or improvement of symptoms was achieved in 26 of 28 patients (92.9%). However, later in the postoperative period, symptoms recurred in 23 of 28 patients (82.1%), although no recurrence of digital ulceration was seen throughout our observation. At the final follow-up examination (median follow-up period, 62.5 months), 25 patients (89.3%) reported overall improvement of the frequency and severity of their symptoms. Despite the high rate of recurrence, ETS clearly produced a high rate of initial relief. ETS did indeed promote healing

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Lorentz Symmetry as AN Emergent Phenomenon

    NASA Astrophysics Data System (ADS)

    Consoli, M.

    2015-01-01

    The vacuum of quantum gravity is believed to be a form of `space-time foam' which resembles a turbulent fluid. In this perspective, it is conceivable that Lorentz symmetry might be an emergent phenomenon. However, this idea of an underlying turbulent ether is not strictly peculiar of quantum gravity. This general picture suggests an alternative interpretation of the stochastic signal observed in the present ether-drift experiments with potentially important implications for both relativity and gravity.

  15. 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

  16. Glomus Tumor Presenting as Raynaud's Phenomenon

    PubMed Central

    Abdelrahman, M. H.; Hammoudeh, M.

    2012-01-01

    Glomus tumors are rare tumors that often include hands and feet; they present characteristically with paroxysmal pain, exquisite point tenderness, and cold sensitivity. Such diagnosis needs to be confirmed by imaging like ultrasound and magnetic resonance imaging (MRI). Surgical excision is the treatment of choice for glomus tumors. There are only few case reports of glomus tumors in association with Raynaud's phenomenon; this is considered to be the 4th case. PMID:22811722

  17. The feedback phenomenon applied to underwater acoustics

    NASA Astrophysics Data System (ADS)

    Roux, Philippe; Jordan, Jason E.; Kuperman, W. A.

    2002-11-01

    People are familiar with the feedback phenomenon that results in the loud sound heard when a musician plays an electric instrument directly into a speaker. Feedback occurs when a source and a receiver are connected both acoustically through the propagation medium and electrically through an amplifier in such way that the received signal is simultaneously and continuously added to the emitted signal. A resonance is then obtained when the emitter and the receiver are in phase. The resonant frequency appears to be highly sensitive to fluctuations of the propagation medium. The feedback phenomenon has been experimentally demonstrated as a means to monitor the temperature fluctuation of a shallow water environment [''Acoustic monitoring of the sea medium variability: experimental testing of new methods,'' by A. V. Furduev, Acoust. Phys. 47, No. 3, 361-368 (2001)]. The goal of our work is to reproduce the feedback experiment using an alternative method that decomposes the feedback phenomenon into an iterative process. Successful reproduction of the feedback is accomplished using a step-by-step algorithm which details the evolution of the system from the initial signal to its steady-state form. These experimental and numerical results illustrate the potential of the feedback process for use in narrow-band acoustical tomography.

  18. The Tullio phenomenon: a neurologically neglected presentation.

    PubMed

    Kaski, Diego; Davies, R; Luxon, L; Bronstein, A M; Rudge, P

    2012-01-01

    The Tullio phenomenon refers to sound-induced disequilibrium or oscillopsia. Patients with this condition frequently present to neurologists, many of whom are unfamiliar with the condition and its diagnostic criteria. Indeed, due to the unusual nature of the symptoms patients are often misdiagnosed as having psychiatric disturbances. Tullio patients describe disequilibrium, auditory and visual symptoms, which are recurrent, brief, and often triggered by loud noises or middle ear pressure changes, e.g. the Valsalva manoeuvre. Many cases are associated with superior semicircular canal dehiscence (SCCD). Early work suggested that the presence of sound-induced torsional eye movements and visual field tilts were consequent upon a utricular-mediated ocular tilt reaction. However, more recent evidence from imaging and oculographic research, as well as data from our patient series indicates that these ocular abnormalities are usually the result of superior semicircular canal stimulation. The clinical history and a focussed examination are often sufficient to make the diagnosis, which can be confirmed with high resolution CT imaging of the temporal bones. In some patients, surgical occlusion or resurfacing of the affected canal can ameliorate symptoms and signs. The aim of this paper is two-fold: Firstly, to review the clinical features of the Tullio phenomenon, and secondly, to highlight our own observations in three cases with a new clinical syndrome consisting of Tullio's phenomenon with bilateral vestibular failure, a pure horizontal nystagmus in response to sound, and no evidence of canal dehiscence.

  19. A theoretical study on the injection, transport, absorption and phosphorescence properties of heteroleptic iridium(III) complexes with different ancillary ligands.

    PubMed

    Shang, Xiaohong; Wan, Ning; Han, Deming; Zhang, Gang

    2014-03-01

    We have reported a theoretical analysis of a series of heteroleptic iridium(III) complexes (mpmi)2Ir(fppi) [mpmi = 1-(4-tolyl)-3-methyl-imidazole, fppi = 4-fluoro-2-(pyrrol-2-yl)-pyridine] (1a), (mpmi)2Ir(dfpi) [dfpi = 4-fluoro-2-(3-fluoro-pyrrol-2-yl)-pyridine] (1b), (mpmi)2Ir(tfpi) [tfpi = 2-(pyrrol-2-yl)-4-trifluoromethyl-pyridine] (1c), (mpmi)2Ir(priq) [priq = 1-(pyrrol-2-yl)isoquinoline] (2a), (mpmi)2Ir(isql) [isql = 1-(indol-2-yl)-isoquinoline] (2b), and (mpmi)2Ir(biql) [biql = 1-(benzoimidazol-2-yl)-isoquinoline] (2c) by using the density functional theory (DFT) method to investigate their electronic structures, photophysical properties, and the phosphorescent efficiency mechanism. The results reveal that the nature of the ancillary ligands can affect the electron density distributions and energies of frontier molecular orbitals, resulting in changes of charge transfer performances and emission color. It is found that the studied complex 1c with the -CF3 substituent at the pyridine moiety results in the lower HOMO-LUMO energy gap and LUMO energy level, which will lead to a rich electron injection ability compared with that of 1a. For each complex studied (except 2b), the hole-transporting performance is better than the electron-transporting performance. In addition, for complexes 2a and 2b, the differences between reorganization energies for hole transport (λ(ih)) and reorganization energies for electron transport (λ(ie)) are relatively smaller, indicating that the hole and electron transfer balance could be achieved more easily in the emitting layer. It is believed that the largest metal to ligand charge transfer (MLCT) character, the higher μ(S1) and E(T1) values, as well as the smallest ΔE(S1-T1) value could result in higher phosphorescent quantum efficiency for 1b than those of other complexes.

  20. 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

  1. 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.

  2. 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 [

  3. 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

  4. The phenomenon of wetting at solid/solid interface

    NASA Astrophysics Data System (ADS)

    Haber, J.; Machej, T.; Czeppe, T.

    1985-03-01

    When a V 2O 5 crystallite is placed on an anatase pellet and heated at 823-923 K, vanadium ions migrate over the surface of anatase grains enveloping them in a thin overlayer. XPS, X-ray and EPR studies show that at 823 K a very thin layer is formed, its properties being strongly modified by interaction with the anatase support. At 923 K, on top of this inner layer an outer layer migrates, whose properties are similar to V 2O 5. As in the same conditions no migration is observed on rutile, it is concluded that this phenomenon is a manifestation of wetting of one oxide by another oxide, the difference in the surface free energy being the driving force of the migration.

  5. 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.

  6. Single-layer group IV-V and group V-IV-III-VI semiconductors: Structural stability, electronic structures, optical properties, and photocatalysis

    NASA Astrophysics Data System (ADS)

    Lin, Jia-He; Zhang, Hong; Cheng, Xin-Lu; Miyamoto, Yoshiyuki

    2017-07-01

    Recently, single-layer group III monochalcogenides have attracted both theoretical and experimental interest at their potential applications in photonic devices, electronic devices, and solar energy conversion. Excited by this, we theoretically design two kinds of highly stable single-layer group IV-V (IV =Si ,Ge , and Sn; V =N and P) and group V-IV-III-VI (IV =Si ,Ge , and Sn; V =N and P; III =Al ,Ga , and In; VI =O and S) compounds with the same structures with single-layer group III monochalcogenides via first-principles simulations. By using accurate hybrid functional and quasiparticle methods, we show the single-layer group IV-V and group V-IV-III-VI are indirect bandgap semiconductors with their bandgaps and band edge positions conforming to the criteria of photocatalysts for water splitting. By applying a biaxial strain on single-layer group IV-V, single-layer group IV nitrides show a potential on mechanical sensors due to their bandgaps showing an almost linear response for strain. Furthermore, our calculations show that both single-layer group IV-V and group V-IV-III-VI have absorption from the visible light region to far-ultraviolet region, especially for single-layer SiN-AlO and SnN-InO, which have strong absorption in the visible light region, resulting in excellent potential for solar energy conversion and visible light photocatalytic water splitting. Our research provides valuable insight for finding more potential functional two-dimensional semiconductors applied in optoelectronics, solar energy conversion, and photocatalytic water splitting.

  7. 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.

  8. 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.

  9. 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.

  10. Stochastic mirage phenomenon in a random medium.

    PubMed

    McDaniel, Austin; Mahalov, Alex

    2017-05-15

    In the framework of geometric optics, we consider the problem of characterizing the ray trajectory in a random medium with a mean refractive index gradient. Such a gradient results in the mirage phenomenon where an object's observed location is displaced from its actual location. We derive formulas for the mean ray path in both the situation of isotropic stochastic fluctuations and an important anisotropic case. For the isotropic model, the mean squared displacement is also given by a simple formula. Our results could be useful for applications involving the propagation of electromagnetic waves through the atmosphere, where larger-scale mean gradients and smaller-scale stochastic fluctuations are both present.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. A Comparative Test of the Interval-Scale Properties of Magnitude Estimation and Case III Scaling and Recommendations for Equal-Interval Frequency Response Anchors.

    ERIC Educational Resources Information Center

    Schriesheim, Chester A.; Novelli, Luke, Jr.

    1989-01-01

    Differences between recommended sets of equal-interval response anchors derived from scaling techniques using magnitude estimations and Thurstone Case III pair-comparison treatment of complete ranks were compared. Differences in results for 205 undergraduates reflected differences in the samples as well as in the tasks and computational…

  17. 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.

  18. 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.

  19. 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.

  20. 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