Disproportionation of hydroxylamine by water-soluble iron(III) porphyrinate compounds.

Science.gov (United States)

Bari, Sara E; Amorebieta, Valentín T; Gutiérrez, María M; Olabe, José A; Doctorovich, Fabio

2010-01-01

The reactions of hydroxylamine (HA) with several water-soluble iron(III) porphyrinate compounds, namely iron(III) meso-tetrakis-(N-ethylpyridinium-2yl)-porphyrinate ([Fe(III)(TEPyP)](5+)), iron(III) meso-tetrakis-(4-sulphonatophenyl)-porphyrinate ([Fe(III)(TPPS)](3-)), and microperoxidase 11 ([Fe(III)(MP11)]) were studied for different [Fe(III)(Porph)]/[HA] ratios, under anaerobic conditions at neutral pH. Efficient catalytic processes leading to the disproportionation of HA by these iron(III) porphyrinates were evidenced for the first time. As a common feature, only N(2) and N(2)O were found as gaseous, nitrogen-containing oxidation products, while NH(3) was the unique reduced species detected. Different N(2)/N(2)O ratios obtained with these three porphyrinates strongly suggest distinctive mechanistic scenarios: while [Fe(III)(TEPyP)](5+) and [Fe(III)(MP11)] formed unknown steady-state porphyrinic intermediates in the presence of HA, [Fe(III)(TPPS)](3-) led to the well characterized soluble intermediate, [Fe(II)(TPPS)NO](4-). Free-radical formation was only evidenced for [Fe(III)(TEPyP)](5+), as a consequence of a metal centered reduction. We discuss the catalytic pathways of HA disproportionation on the basis of the distribution of gaseous products, free radicals formation, the nature of porphyrinic intermediates, the Fe(II)/Fe(III) redox potential, the coordinating capabilities of each complex, and the kinetic analysis. The absence of NO(2)(-) revealed either that no HAO-like activity was operative under our reaction conditions, or that NO(2)(-), if formed, was consumed in the reaction milieu.

Interaction of Cu(II)-meso-tetrakis(n-N-methylpyridiniumyl)porphyrin (n = 2,3,4) with Native and Synthetic Polynucleotides Probed by Polarized Spectroscopy

International Nuclear Information System (INIS)

Lee, Mi Jin; Kim, Seog K.; Kim, Jong Moon; Lee, Dong Jin; Lee, Gil Jun

2005-01-01

The interactions of Cu(II)-meso-Tetrakis(n-N-methylpyridiniumyl)porphyrin (n = 2,3,4), respectively referred to as o-, m- and p-CuTMPyP, and DNA, poly[d(A-T) 2 ] and poly[d(G-C) 2 ] were investigated by circular and linear dichroism (CD and LD). In the o-CuTMPyP case, in which the rotation of the pyridinium ring is prevented, the shape of the CD spectrum when associated to DNA and poly[d(A-T) 2 ] resembles and is characterized by a positive band at a low drug to DNA concentration ratio (R ratio) and is bisignate at a high R ratio. The former CD spectrum shape has been attributed to porphyrin that is bound monomerically outside of DNA while the latter can be attributed to those that are stacked. When o-CuTMPyP is bound to poly[d(G-C) 2 ], the excitonic CD appeared at a relatively high R ratio. In contrast, a characteristic negative CD band in the Soret region was apparent for both m- and p-CuTMPyP when bound to DNA and poly[d(G-C) 2 ] at the low R ratios, indicating that the porphyrin molecule intercalates. However, the DNA is bent near the intercalation site and the plane of the porphyrin molecule tilts relative to the DNA helix axis, as judged by the magnitude of the reduced LD. Various stacking patterns were identified by the shape of the CD spectrum for m- and p-CuTMPyP when bound to poly[d(A-T) 2 ]. Three species for the former complex and two for the latter complex were found which may reflect the extent of the stacking

Bis-Porphyrin Racks with Space-Separated Co-Planar Porphyrin Rings

Directory of Open Access Journals (Sweden)

Martin R. Johnston

2001-03-01

Full Text Available A porphyrin appended norbornenyl building block 8 has been isolated and coupled, using a 1,3-dipolar ACE reaction, to yield bis-porphyrin compounds in which the porphyrin moietes are angled upward relative to the norbornane backbone.

Photoconductivity in DNA-Porphyrin Complexes

Science.gov (United States)

Myint, Peco; Oxford, Emma; Nyazenga, Collence; Smith, Walter; Qi, Zhengqing; Johnson, A. T.

2015-03-01

We have measured the photoconductivity of λ - DNA that is modified by intercalating a porphyrin compound, meso-tetrakis(N-methyl-4-pyridiniumyl)porphyrin (TMPyP), into its base stacks. Intercalation was verified by a red shift and hypochromism of the Soret absorption peak. The DNA/porphyrin strands were then deposited onto oxidized silicon substrates which had been patterned with interdigitated electrodes, and blown dry. Electrical measurements were carried out under nitrogen, using illumination from a 445 nm laser; this wavelength falls within the absorption peak of the DNA/porphyrin complexes. When initially measured under dry nitrogen, the complexes show no photoconductivity or dark conductivity. However, at relative humidities of 30% and above, we do observe dark conductivity, and also photoconductivity that grows with time. Photoconductivity gets larger at higher relative humidity. Remarkably, when the humidity is lowered again, some photoconductivity is now observed, indicating a change that persists for more than 24 hours. It may be that the humidity alters the structure of the DNA, perhaps allowing for better alignment of the bases. This work was supported by NSF Grant BMAT-1306170.

Push-pull quinoidal porphyrins.

Science.gov (United States)

Smith, Martin J; Blake, Iain M; Clegg, William; Anderson, Harry L

2018-05-01

A family of push-pull quinoidal porphyrin monomers has been prepared from a meso-formyl porphyrin by bromination, thioacetal formation, palladium-catalyzed coupling with malononitrile and oxidation with DDQ. Attempts at extending this synthesis to a push-pull quinoidal/cumulenic porphyrin dimer were not successful. The crystal structures of the quinoidal porphyrins indicate that there is no significant contribution from singlet biradical or zwitterionic resonance forms. The crystal structure of an ethyne-linked porphyrin dimer shows that the torsion angle between the porphyrin units is only about 3°, in keeping with crystallographic results on related compounds, but contrasting with the torsion angle of about 35° predicted by computational studies. The free-base quinoidal porphyrin monomers form tightly π-stacked layer structures, despite their curved geometries and bulky aryl substituents.

Inverted porphyrins and expanded porphyrins: An overview

Indian Academy of Sciences (India)

Unknown

More recently, synthetic porphyrins and porphyrin-like macrocycles have ... one of the meso carbons resulting in the formation of corroles; – (d) Isomeric ... spectroscopic, chemical and physical properties, which can find applications in ..... diol 55 under TFA catalysis yielding 20–28% yield of expected rubyrins 85 and 86 as.

Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl.

Science.gov (United States)

Lai, Ya-Yuan; Chang, Yu-Chang; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

2016-03-21

The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT). The free energy of activation at the coalescence temperature Tc for the exchange of phenyl ortho protons o-H (26) with o-H (22) in 3 in a CDCl3 solvent is found to be ΔG = 61.4 kJ mol(-1) through (1)H NMR temperature-dependent measurements. The axial zero-field splitting parameter |D| was found to vary from 35.6 cm(-1) in 7 (or 30.7 cm(-1) in 8) to 42.0 cm(-1) in 9 and 46.9 cm(-1) in 10 through paramagnetic susceptibility measurements. The magnitude of |D| can be related to the coordination sphere at the cobalt sites.

N-Annulated perylene-substituted and fused porphyrin dimers with intense near-infrared one-photon and two-photon absorption

KAUST Repository

Luo, Jie

2015-01-21

Fusion of two N-annulated perylene (NP) units with a fused porphyrin dimer along the S0-S1 electronic transition moment axis has resulted in new near-infrared (NIR) dyes 1a/1b with very intense absorption (ε>1.3×105M-1cm-1) beyond 1250nm. Both compounds displayed moderate NIR fluorescence with fluorescence quantum yields of 4.4×10-6 and 6.0×10-6 for 1a and 1b, respectively. The NP-substituted porphyrin dimers 2a/2b have also been obtained by controlled oxidative coupling and cyclodehydrogenation, and they showed superimposed absorptions of the fused porphyrin dimer and the NP chromophore. The excited-state dynamics of all of these compounds have been studied by femtosecond transient absorption measurements, which revealed porphyrin dimer-like behaviour. These new chromophores also exhibited good nonlinear optical susceptibility with large two-photon absorption cross-sections in the NIR region due to extended π-conjugation. Time-dependent density functional theory calculations have been performed to aid our understanding of their electronic structures and absorption spectra.

Novel polar sedimentary porphyrins

Science.gov (United States)

Prowse, W. G.; Maxwell, J. R.

1989-11-01

Two polar nickel porphyrins in Messel oil shale are shown to be the C 32 and C 30 components IIIa,b. In the sample examined, component IIIa is by far the major porphyrin alcohol and is present in an abundance similar to that of the major nickel alkyl porphyrin. These primary alcohols, which do not appear to be artifacts, are structurally related to alkyl porphyrins reported previously in Serpiano oil shale.

New porphyrins bearing positively charged peripheral groups linked by a sulfonamide group to meso-tetraphenylporphyrin: interactions with calf thymus DNA.

Science.gov (United States)

Manono, Janet; Marzilli, Patricia A; Marzilli, Luigi G

2009-07-06

New water-soluble cationic meso-tetraarylporphyrins (TArP, Ar = 4-C(6)H(4)) and some metal derivatives have been synthesized and characterized. One main goal was to assess if N-methylpyridinium (N-Mepy) groups must be directly attached to the porphyrin core for intercalative binding of porphyrins to DNA. The new porphyrins have the general formula, [T(R(2)R(1)NSO(2)Ar)P]X(4/8) (R(1) = CH(3) or H and R(2) = N-Mepy-n-CH(2) with n = 2, 3, or 4; or R(1) = R(2) = Et(3)NCH(2)CH(2)). Interactions of selected porphyrins and metalloporphyrins (Cu(II), Zn(II)) with calf thymus DNA were investigated by visible circular dichroism (CD), absorption, and fluorescence spectroscopies. The DNA-induced changes in the porphyrin Soret region (a positive induced CD feature and, at high DNA concentration, increases in the Soret band and fluorescence intensities) indicate that the new porphyrins interact with DNA in an outside, non-self-stacking binding mode. Several new metalloporphyrins did not increase DNA solution viscosity and thus do not intercalate, confirming the conclusion drawn from spectroscopic studies. Porphyrins known to intercalate typically bear two or more N-Mepy groups directly attached to the porphyrin ring, such as the prototypical meso-tetra(N-Mepy)porphyrin tetracation (TMpyP(4)). The distances between the nitrogens of the N-Mepy group are estimated to be approximately 11 A (cis) and 16 A (trans) for the relatively rigid TMpyP(4). For the new flexible porphyrin, [T(N-Mepy-4-CH(2)(CH(3))NSO(2)Ar)P]Cl(4), the distances between the nitrogens are estimated to be able to span the range from approximately 9 to approximately 25 A. Thus, the N-Mepy groups in the new porphyrins can adopt the same spacing as in known intercalators such as TMpyP(4). The absence of intercalation by the new porphyrins indicates that the propensity for the N-Mepy group to facilitate DNA intercalation of cationic porphyrins requires direct attachment of N-Mepy groups to the porphyrin core.

HAEM SYNTHASE AND COBALT PORPHYRIN SYNTHASE IN VARIOUS MICRO-ORGANISMS.

Science.gov (United States)

PORRA, R J; ROSS, B D

1965-03-01

1. The preparation of a crude extract of Clostridium tetanomorphum containing cobalt porphyrin synthase but little haem-synthase activity is described. 2. The properties of cobalt porphyrin synthase in the clostridial extracts is compared with the properties of a haem synthase present in crude extracts of the yeast Torulopsis utilis. 3. Cobalt porphyrin synthase in extracts of C. tetanomorphum inserts Co(2+) ions into the following dicarboxylic porphyrins in descending order of rate of insertion: meso-, deutero- and proto-porphyrins. Esterification renders meso- and deutero-porphyrins inactive as substrates. Neither the tetracarboxylic (coproporphyrin III) nor the octacarboxylic (uroporphyrin III) compounds are converted into cobalt porphyrins by the extract, but the non-enzymic incorporation of Co(2+) ions into these two porphyrins is rapid. These extracts are unable to insert Mn(2+), Zn(2+), Mg(2+) or Cu(2+) ions into mesoporphyrin. 4. Crude extracts of T. utilis readily insert both Co(2+) and Fe(2+) ions into deutero-, meso, and proto-porphyrins. Unlike the extracts of C. tetanomorphum, these preparations catalyse the insertion of Co(2+) ions into deuteroporphyrin more rapidly than into mesoporphyrin. This parallels the formation of haems by the T. utilis extract. 5. Cobalt porphyrin synthase is present in the particulate fraction of the extracts of C. tetanomorphum but requires a heat-stable factor present in the soluble fraction. This soluble factor can be replaced by GSH. 6. Cobalt porphyrin synthase in the clostridial extract is inhibited by iodoacetamide and to a smaller extent by p-chloromercuribenzoate and N-ethylmaleimide. The haem synthases of T. utilis and Micrococcus denitrificans are also inhibited by various thiol reagents.

Supramolecular assemblies of pyridyl porphyrin and diazadithia phthalocyanine

Directory of Open Access Journals (Sweden)

OZER BEKAROGLU

1999-08-01

Full Text Available In this paper we report for the first time on a mixed complex between the cationic porphyrin 5, 10, 15, 20-tetra-N- -methyl-pyrydinium-p-il porphyrin (TMPyP and a new metal phthalocyanine with four 16-membered diazadithia macrocycles (denoted here as Pc16, in order to obtain an active complex with an intense absorption on the lower energy side of the visible spectrum and with a higher sensitivity in photodynamic therapy of cancer. The dimerization constant for Pc16 and also the ratio between the oscillator strengths for monomeric and dimeric forms of this compound, were evaluated. The ratio between these oscillator strengths was 2.01 showing a certain dimerization process. The Job mathematical method allowed the establishment of the stoichiometry and the formation constants for the heteroaggregates between the porphyrin and the phthalocy- anine (a diad between one phthalocyanine molecule and one porphyrin molecule and a triad between two phthalocyanine molecules and only one porphyrin molecule. The coulombic attraction resulting from the p-p interaction of the two highly conjugated macrocycles and from the interaction between the substituents, favors a face-to-face geometry.

Photodynamic inactivation of Candida albicans sensitized by tri- and tetra-cationic porphyrin derivatives.

Science.gov (United States)

Cormick, M Paula; Alvarez, M Gabriela; Rovera, Marisa; Durantini, Edgardo N

2009-04-01

The photodynamic action of 5-(4-trifluorophenyl)-10,15,20-tris(4-trimethylammoniumphenyl)porphyrin iodide (TFAP(3+)) and 5,10,15,20-tetra(4-N,N,N-trimethylammonium phenyl)porphyrin p-tosylate (TMAP(4+)) has been studied in vitro on Candida albicans. The results of these cationic porphyrins were compared with those of 5,10,15,20-tetra(4-sulphonatophenyl)porphyrin (TPPS(4-)), which characterizes an anionic sensitizer. In vitro investigations show that these cationic porphyrins are rapidly bound to C. albicans cells, reaching a value of approximately 1.4 nmol/10(6) cells, when the cellular suspensions were incubated with 5 microM sensitizer for 30 min. In contrast, TPPS(4-) is poorly uptaken by yeast cells. The fluorescence spectra of these sensitizers into the cells confirm this behaviour. The amount of porphyrin binds to cells is dependent on both sensitizer concentrations (1-5 microM) and cells densities (10(6)-10(8) cells/mL). Photosensitized inactivation of C. albicans cellular suspensions increases with sensitizer concentration, causing a approximately 5 log decrease of cell survival, when the cultures are treated with 5 microM of cationic porphyrin and irradiated for 30 min. However, the photocytotoxicity decreases with an increase in the cell density, according to its low binding to cells. Under these conditions, the photodynamic activity of TFAP(3+) is quite similar to that produced by TMAP(4+), whereas no important inactivation effect was found for TPPS(4)(-). The high photodynamic activity of cationic porphyrins was confirmed by growth delay experiments. Thus, C. albicans cell growth was not detected in the presence of 5 microM TFAP(3+). Photodynamic inactivation capacities of these sensitizers were also evaluated on C. albicans cells growing in colonies on agar surfaces. Cationic porphyrins produce a growth delay of C. albicans colonies and viability of cells was not observed after 3 h irradiation, indicating a complete inactivation of yeast cells

Mechanistic insight of the photodynamic effect induced by tri- and tetra-cationic porphyrins on Candida albicans cells.

Science.gov (United States)

Cormick, M Paula; Quiroga, Ezequiel D; Bertolotti, Sonia G; Alvarez, M Gabriela; Durantini, Edgardo N

2011-10-01

The photodynamic mechanism of action induced by 5-(4-trifluorophenyl)-10,15,20-tris(4-N,N,N-trimethylammoniumphenyl)porphyrin (TFAP(3+)), 5,10,15,20-tetrakis(4-N,N,N-trimethylammoniumphenyl)porphyrin (TMAP(4+)) and 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin (TMPyP(4+)) was investigated on Candida albicans cells. These cationic porphyrins are effective photosensitizers, producing a ~5 log decrease of cell survival when the cultures are incubated with 5 μM photosensitizer and irradiated for 30 min with visible light. Studies under anoxic conditions indicated that oxygen is necessary for the mechanism of action of photodynamic inactivation of this yeast. Furthermore, photoinactivation of C. albicans cells was negligible in the presence of 100 mM azide ion, whereas the photocytotoxicity induced by these porphyrins increased in D(2)O. In contrast, the addition of 100 mM mannitol produced a negligible effect on the cellular phototoxicity. On the other hand, in vitro direct observation of singlet molecular oxygen, O(2)((1)Δ(g)) phosphorescence at 1270 nm was analyzed using C. albicans in D(2)O. A shorter lifetime of O(2)((1)Δ(g)) was found in yeast cellular suspensions. These cationic porphyrins bind strongly to C. albicans cells and the O(2)((1)Δ(g)) generated inside the cells is rapidly quenched by the biomolecules of the cellular microenvironment. Therefore, the results indicate that these cationic porphyrins appear to act as photosensitizers mainly via the intermediacy of O(2)((1)Δ(g)). This journal is © The Royal Society of Chemistry and Owner Societies 2011

Mechanistic aspects of the photodynamic inactivation of Candida albicans induced by cationic porphyrin derivatives.

Science.gov (United States)

Quiroga, Ezequiel D; Cormick, M Paula; Pons, Patricia; Alvarez, M Gabriela; Durantini, Edgardo N

2012-12-01

Photodynamic inactivation of Candida albicans produced by 5-(4-trifluorophenyl)-10,15,20-tris(4-N,N,N-trimethylammoniumphenyl)porphyrin (TFAP(3+)), 5,10,15,20-tetrakis(4-N,N,N-trimethylammoniumphenyl)porphyrin (TMAP(4+)) and 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin (TMPyP(4+)) was investigated to obtain insight about the mechanism of cellular damage. In solution, absorption spectroscopic studies showed that these cationic porphyrins interact strongly with calf thymus DNA. The electrophoretic analysis indicated that photocleavage of DNA induced by TFAP(3+) took place after long irradiation periods (>5 h). In contrast, TMAP(4+) produced a marked reduction in DNA band after 1 h irradiation. In C. albicans, these cationic porphyrins produced a ∼3.5 log decrease in survival when the cell suspensions (10(7) cells/mL) were incubated with 5 μM photosensitizer and irradiated for 30 min with visible light (fluence 162 J/cm(2)). After this treatment, modifications of genomic DNA isolated from C. albicans cells were not found by electrophoresis. Furthermore, transmission electron microscopy showed structural changes with appearance of low density areas into the cells and irregularities in cell barriers. However, the photodamage to the cell envelope was insufficient to cause the release of intracellular biopolymers. Therefore, modifications in the cytoplasmic biomolecules and alteration in the cell barriers could be mainly involved in C. albicans photoinactivation. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

Interaction of cationic porphyrins with DNA: Importance of the number and position of the charges and minimum structural requirements for intercalation

International Nuclear Information System (INIS)

Sari, M.A.; Battioni, J.P.; Dupre, D.; Mansuy, D.; Le Pecq, J.B.

1990-01-01

Thirty-three porphyrins or metalloporphyrins corresponding to the general formula [meso-[N-methyl-4(or 3 or 2)-pyridiniumyl] n (aryl) 4-n porphyrin]M (M = H 2 , Cu II , or ClFe III ), with n = 2-4, have been synthesized and characterized by UV-visible and 1 H NMR spectroscopy and mass spectrometry. These porphyrins differ not only in the number (2-4) and position of their cationic charges but also in the steric requirements to reach even temporarily a completely planar geometry. Interaction of these porphyrins or metalloporphyrins with calf thymus DNA has been studied and their apparent affinity binding constants have been determined by use of a competition method with ethidium bromide which was applicable not only for all the free base porphyrins but also for their copper (II) or iron (III) complexes. Whatever their mode of binding may be, their apparent affinity binding constants were relatively high and a linear decrease of log K app with the number of porphyrin charges was observed. Studies of porphyrin-DNA interactions by UV and fluorescence spectroscopy, viscosimetry, and fluorescence energy transfer experiments showed that not only the tetracationic meso-tetrakis[N-methyl-4(or 3)-pyridiniumyl]porphyrins, which both involved four freely rotating meso-aryl groups, but also the corresponding tri- and dicationic porphyrins were able to intercalate into calf thymus DNA. These results show that only half of the porphyrin ring is necessary for intercalation to occur

Synthesis of borylated porphyrin and bromo- porphyrin as building blocks for light harvesting antenna molecule

Science.gov (United States)

Radzuan, Nuur Haziqah Mohd; Hassan, Nurul Izzaty; Bakar, Muntaz Abu

2018-04-01

The building blocks for synthesis of light harvesting antenna which are 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-10,20-diphenylporphyrin, 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-10,20-dihexylporphyrin and 5,10,15,20-tetra-(bromophenyl)porphyrin were synthesized. Borylated porphyrin was synthesized by Suzuki coupling reaction between A2BC bromo-porphyrin and pinacolborane. Whereas 5,10,15,20-tetra-(bromophenyl) porphyrin was synthesized by Lindsey condensation reaction between pyrrole and 4-bromobenzaldehyde. 1H-NMR, 13C-NMR spectroscopy and UV-visible spectroscopy confirmed the successful formation of all compounds.

Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons

KAUST Repository

Diev, Vyacheslav V.; Schlenker, Cody W.; Hanson, Kenneth; Zhong, Qiwen; Zimmerman, Jeramy D.; Forrest, Stephen R.; Thompson, Mark E.

2012-01-01

A systematic study of the preparation of porphyrins with extended conjugation by meso,β-fusion with polycyclic aromatic hydrocarbons (PAHs) is reported. The meso-positions of 5,15-unsubstituted porphyrins were readily functionalized with PAHs. Ring fusion using standard Scholl reaction conditions (FeCl 3, dichloromethane) occurs for perylene-substituted porphyrins to give a porphyrin β,meso annulated with perylene rings (0.7:1 ratio of syn and anti isomers). The naphthalene, pyrene, and coronene derivatives do not react under Scholl conditions but are fused using thermal cyclodehydrogenation at high temperatures, giving mixtures of syn and anti isomers of the meso,β-fused porphyrins. For pyrenyl-substituted porphyrins, a thermal method gives synthetically acceptable yields (>30%). Absorption spectra of the fused porphyrins undergo a progressive bathochromic shift in a series of naphthyl (λ max = 730 nm), coronenyl (λ max = 780 nm), pyrenyl (λ max = 815 nm), and perylenyl (λ max = 900 nm) annulated porphyrins. Despite being conjugated with unsubstituted fused PAHs, the β,meso-fused porphyrins are more soluble and processable than the parent nonfused precursors. Pyrenyl-fused porphyrins exhibit strong fluorescence in the near-infrared (NIR) spectral region, with a progressive improvement in luminescent efficiency (up to 13% with λ max = 829 nm) with increasing degree of fusion. Fused pyrenyl-porphyrins have been used as broadband absorption donor materials in photovoltaic cells, leading to devices that show comparatively high photovoltaic efficiencies. © 2011 American Chemical Society.

Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons

KAUST Repository

Diev, Vyacheslav V.

2012-01-06

A systematic study of the preparation of porphyrins with extended conjugation by meso,β-fusion with polycyclic aromatic hydrocarbons (PAHs) is reported. The meso-positions of 5,15-unsubstituted porphyrins were readily functionalized with PAHs. Ring fusion using standard Scholl reaction conditions (FeCl 3, dichloromethane) occurs for perylene-substituted porphyrins to give a porphyrin β,meso annulated with perylene rings (0.7:1 ratio of syn and anti isomers). The naphthalene, pyrene, and coronene derivatives do not react under Scholl conditions but are fused using thermal cyclodehydrogenation at high temperatures, giving mixtures of syn and anti isomers of the meso,β-fused porphyrins. For pyrenyl-substituted porphyrins, a thermal method gives synthetically acceptable yields (>30%). Absorption spectra of the fused porphyrins undergo a progressive bathochromic shift in a series of naphthyl (λ max = 730 nm), coronenyl (λ max = 780 nm), pyrenyl (λ max = 815 nm), and perylenyl (λ max = 900 nm) annulated porphyrins. Despite being conjugated with unsubstituted fused PAHs, the β,meso-fused porphyrins are more soluble and processable than the parent nonfused precursors. Pyrenyl-fused porphyrins exhibit strong fluorescence in the near-infrared (NIR) spectral region, with a progressive improvement in luminescent efficiency (up to 13% with λ max = 829 nm) with increasing degree of fusion. Fused pyrenyl-porphyrins have been used as broadband absorption donor materials in photovoltaic cells, leading to devices that show comparatively high photovoltaic efficiencies. © 2011 American Chemical Society.

Excited-state absorption in tetrapyridyl porphyrins: comparing real-time and quadratic-response time-dependent density functional theory

Energy Technology Data Exchange (ETDEWEB)

Bowman, David N. [Department of Chemistry; Supercomputing Institute and Chemical Theory Center; University of Minnesota; Minneapolis; USA; Asher, Jason C. [Department of Chemistry; Supercomputing Institute and Chemical Theory Center; University of Minnesota; Minneapolis; USA; Fischer, Sean A. [William R. Wiley Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; P.O. Box 999; Richland; USA; Cramer, Christopher J. [Department of Chemistry; Supercomputing Institute and Chemical Theory Center; University of Minnesota; Minneapolis; USA; Govind, Niranjan [William R. Wiley Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; P.O. Box 999; Richland; USA

2017-01-01

Threemeso-substituted tetrapyridyl porphyrins (free base, Ni(ii), and Cu(ii)) were investigated for their optical limiting (OL) capabilities using real-time (RT-), linear-response (LR-), and quadratic-response (QR-) time-dependent density functional theory (TDDFT) methods.

N-Annulated perylene substituted zinc–porphyrins with different linking modes and electron acceptors for dye sensitized solar cells

KAUST Repository

Luo, Jie

2016-05-03

Three new N-annulated perylene (NP) substituted porphyrin dyes WW-7-WW-9 with different linking modes and accepting groups were synthesized and applied in Co(ii)/(iii) based dye sensitized solar cells (DSCs). The bay-linked porphyrins WW-7 and WW-8 exhibited moderate power conversion efficiency (PCE = 4.4% and 4.8%, respectively), while the peri-linked porphyrin dye WW-9 showed a PCE up to 9.2% which is slightly lower than that of our reference dye WW-6. Detailed physical measurements (optical and electrochemical), DFT calculations, and photovoltaic characterizations were performed to understand how the structural changes affect their light-harvesting ability, molecular orbital profile, energy level alignment, and eventually the photovoltaic performance. It turned out that the lower efficiencies of the cells based on WW-7 and WW-8 could be ascribed to the weak π-conjugation between the bay-substituted NP and phenylethynyl substituted porphyrin unit. The introduction of a benzothiadiazole acceptor at the anchoring group has induced a significant red shift of the IPCE action spectra of WW-8 and WW-9, by about 90 nm and 50 nm as compared to that of WW-7 and WW-6, respectively. However, less efficient electron injection was observed. Our studies gave some insight into the important role of electronic interactions between different components when one designs a dye for high-efficiency DSCs. © The Royal Society of Chemistry 2016.

N-Annulated perylene substituted zinc–porphyrins with different linking modes and electron acceptors for dye sensitized solar cells

KAUST Repository

Luo, Jie; Zhang, Jing; Huang, Kuo-Wei; Qi, Qingbiao; Dong, Shaoqiang; Zhang, Jie; Wang, Peng; Wu, Jishan

2016-01-01

Three new N-annulated perylene (NP) substituted porphyrin dyes WW-7-WW-9 with different linking modes and accepting groups were synthesized and applied in Co(ii)/(iii) based dye sensitized solar cells (DSCs). The bay-linked porphyrins WW-7 and WW-8 exhibited moderate power conversion efficiency (PCE = 4.4% and 4.8%, respectively), while the peri-linked porphyrin dye WW-9 showed a PCE up to 9.2% which is slightly lower than that of our reference dye WW-6. Detailed physical measurements (optical and electrochemical), DFT calculations, and photovoltaic characterizations were performed to understand how the structural changes affect their light-harvesting ability, molecular orbital profile, energy level alignment, and eventually the photovoltaic performance. It turned out that the lower efficiencies of the cells based on WW-7 and WW-8 could be ascribed to the weak π-conjugation between the bay-substituted NP and phenylethynyl substituted porphyrin unit. The introduction of a benzothiadiazole acceptor at the anchoring group has induced a significant red shift of the IPCE action spectra of WW-8 and WW-9, by about 90 nm and 50 nm as compared to that of WW-7 and WW-6, respectively. However, less efficient electron injection was observed. Our studies gave some insight into the important role of electronic interactions between different components when one designs a dye for high-efficiency DSCs. © The Royal Society of Chemistry 2016.

Electron Transport through Porphyrin Molecular Junctions

Science.gov (United States)

Zhou, Qi

The goal of this work is to study the properties that would affect the electron transport through a porphyrin molecular junction. This work contributes to the field of electron transport in molecular junctions in the following 3 aspects. First of all, by carrying out experiments comparing the conductance of the iron (III) porphyrin (protected) and the free base porphyrin (protected), it is confirmed that the molecular energy level broadening and shifting occurs for porphyrin molecules when coupled with the metal electrodes, and this level broadening and shifting plays an important role in the electron transport through molecular junctions. Secondly, by carrying out an in-situ deprotection of the acetyl-protected free base porphyrin molecules, it is found out that the presence of acetyl groups reduces the conductance. Thirdly, by incorporating the Matrix-assisted laser desorption/ionization (MALDI) spectrum and the in-situ deprotection prior to formation of molecular junctions, it allows a more precise understanding of the molecules involved in the formation of molecular junctions, and therefore allows an accurate analysis of the conductance histogram. The molecules are prepared by self-assembly and the junctions are formed using a Scanning Tunneling Microscopy (STM) molecular break junction technique. The porphyrin molecules are characterized by MALDI in solution before self-assembly to a gold/mica substrate. The self-assembled monolayers (SAMs) of porphyrins on gold are characterized by Ultraviolet-visible (UV-Vis) reflection spectroscopy to confirm that the molecules are attached to the substrate. The SAMs are then characterized by Angle-Resolved X-ray photoelectron spectroscopy (ARXPS) to determine the thickness and the average molecular orientation of the molecular layer. The electron transport is measured by conductance-displacement (G-S) experiments under a given bias (-0.4V). The conductance value of a single molecule is identified by a statistical analysis

Synthesis and characterization of a novel meso-porphyrin and its metallo derivatives

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Paulo Cesar Bega

2014-02-01

Full Text Available There has been a growing interest in the properties of substituted meso-tetraarylporphyrins and metallo porphyrins as catalysts for oxidation of hydrocarbons, oxygen detection, among others. This work describes the synthesis of a new porphyrin, 5,10,15,20-tetrakis(4-butoxy-3-methoxyphenylporphyrin, and its metallo complexes. Herein it was used a readily available reactant, vanillin, as starting material which was submitted to alkylation with n-bromobutane affording the synthetic precursor. The desired porphyrin was obtained by reacting the O-alkylated aldehyde with pyrrole in the presence of propionic acid (Alder-Longo method. The purified porphyrin was then subjected to the metallation process using iron (II and manganese (II salts. The synthesized compounds were characterized by IR, UV-Vis, NMR and EPR spectroscopy.

Iron(II) porphyrins induced conversion of nitrite into nitric oxide: A computational study.

Science.gov (United States)

Zhang, Ting Ting; Liu, Yong Dong; Zhong, Ru Gang

2015-09-01

Nitrite reduction to nitric oxide by heme proteins was reported as a protective mechanism to hypoxic injury in mammalian physiology. In this study, the pathways of nitrite reduction to nitric oxide mediated by iron(II) porphyrin (P) complexes, which were generally recognized as models for heme proteins, were investigated by using density functional theory (DFT). In view of two type isomers of combination of nitrite and Fe(II)(P), N-nitro- and O-nitrito-Fe(II)-porphyrin complexes, and two binding sites of proton to the different O atoms of nitrite moiety, four main pathways for the conversion of nitrite into nitric oxide mediated by iron(II) porphyrins were proposed. The results indicate that the pathway of N-bound Fe(II)(P)(NO2) isomer into Fe(III)(P)(NO) and water is similar to that of O-bound isomer into nitric oxide and Fe(III)(P)(OH) in both thermodynamical and dynamical aspects. Based on the initial computational studies of five-coordinate nitrite complexes, the conversion of nitrite into NO mediated by Fe(II)(P)(L) complexes with 14 kinds of proximal ligands was also investigated. Generally, the same conclusion that the pathways of N-bound isomers are similar to those of O-bound isomer was obtained for iron(II) porphyrin with ligands. Different effects of ligands on the reduction reactions were also found. It is notable that the negative proximal ligands can improve reactive abilities of N-nitro-iron(II) porphyrins in the conversion of nitrite into nitric oxide compared to neutral ligands. The findings will be helpful to expand our understanding of the mechanism of nitrite reduction to nitric oxide by iron(II) porphyrins. Copyright © 2015 Elsevier Inc. All rights reserved.

Proof of concept for molecular velcro based on the attractive interaction between porphyrin and pyridine containing copolymers

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M. Sievers

2018-06-01

Full Text Available In this short communication, we investigated the synthesis and mixing of porphyrin and pyridine functionalized copolymers as a proof of concept for a velcro-like interaction. A functionalized porphyrin monomer with one polymerizable side chain was synthesized following a rational synthetic pathway. Subsequent copolymerization and careful removal of residual free porphyrin led to poly(n-butyl acrylate-co-5,10,15-triphenyl-20-(3-vinylphenylporphyrin. The immobilized porphyrin was transformed into the corresponding zinc(II complex, which is capable of the coordinative binding of one pyridine moiety. Complete metallation was proven by absorption spectroscopy. 4-Vinylpyridine was immobilized by copolymerization with n-butyl acrylate, too. Via controlled radical polymerization conditions, the molecular weight of poly(n-butyl acrylate-co-4-vinylpyridine was limited to one tenth of the molecular weight of the porphyrin containing copolymer. This large difference in the molecular weight easily allowed identifying the polymers in the mixture of both. With the help of diffusion ordered nuclear magnetic resonance spectroscopy, the complete and temperature-stable precipitation of the porphyrin containing copolymer was observed, proving the expected attractive interaction and supramolecular network formation.

Porphyrin coordination polymer nanospheres and nanorods

Science.gov (United States)

Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

2012-12-04

A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

RAFT Synthesis and Self-Assembly of Free-Base Porphyrin Cored Star Polymers

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Lin Wu

2011-01-01

Full Text Available Reversible addition fragmentation chain transfer (RAFT synthesis and self-assembly of free-base porphyrin cored star polymers are reported. The polymerization, in the presence of a free-base porphyrin cored chain transfer agent (CTA-FBP, produced porphyrin star polymers with controlled molecular weights and narrow polydispersities for a number of monomers including N, N-dimethylacrylamide (DMA and styrene (St. Well-defined amphiphilic star block copolymers, P-(PS-PDMA4 and P-(PDMA-PS4 (P: porphyrin, were also prepared and used for self-assembly studies. In methanol, a selective solvent for PDMA, spherical micelles were observed for both block copolymers as characterized by TEM. UV-vis studies suggested star-like micelles were formed from P-(PS-PDMA4, while P-(PDMA-PS4 aggregated into flower-like micelles. Spectrophotometric titrations indicated that the optical response of these two micelles to external ions was a function of micellar structures. These structure-related properties will be used for micelle studies and functional material development in the future.

Interacción familiar y desarrollo emocional en niños y niñas

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Gloria Cecilia Henao López

2009-01-01

Full Text Available En la presente investigación se tuvo como objetivo principal abordar los estilos de interacción de padres y madres de niños y niñas preescolares y su relación con el desarrollo emocional de sus hijos e hijas (235 niños y 169 niñas entre cinco y seis años de edad. Las dimensiones que se consideraron para evaluar el nivel emocional de los niños y niñas fueron: autorregulación, comprensión emocional, y empatía. Como primer aspecto describimos los tipos de interacción con sus hijos e hijas y el desarrollo emocional de los niños y niñas evaluados. Un segundo aspecto que se abordó, es el de explorar las asociaciones entre el estilo de interacción familiar y el desarrollo emocional infantil. El instrumento utilizado dirigido a los padres y madres fue la Escala de Identificación de Prácticas Educativas Familiares (PEF, versión española realizada por Alonso y Román; a los niños y niñas les aplicamos la evaluación del desempeño emocional (EDEI, que se construye como parte de esta investigación. Se trabajó con una muestra de 404 niños y niñas, y sus respectivos padres y madres. Los resultados obtenidos en esta investigación resaltan el estilo equilibrado como generador de conductas adecuadas y adaptativas en el niño o niña, al igual que rescata este estilo como el que más posibilita el nivel de comprensión emocional en los niños y niñas de nuestro estudio.

Enhancement of oxygen reduction at Fe tetrapyridyl porphyrin by pyridyl-N coordination to transition metal ions

International Nuclear Information System (INIS)

Maruyama, Jun; Baier, Claudia; Wolfschmidt, Holger; Bele, Petra; Stimming, Ulrich

2012-01-01

One of the promising candidates as noble-metal-free electrode catalysts for polymer electrolyte fuel cells (PEFCs) is a carbon material with nitrogen atoms coordinating iron ions embedded on the surface (Fe-N x moiety) as the active site, although the activity is insufficient compared to conventional platinum-based electrocatalysts. In order to obtain fundamental information on the activity enhancement, a simple model of the Fe-N x active site was formed by adsorbing 5,10,15,20-Tetrakis(4-pyridyl)-21H,23H-porphine iron(III) chloride (FeTPyPCl) on the basal plane of highly oriented pyrolytic graphite (HOPG), and cathodic oxygen reduction was investigated on the surface in 0.1 M HClO 4 . The catalytic activity for oxygen reduction was enhanced by loading transition metal ions (Co 2+ , Ni 2+ , Cu 2+ ) together with FeTPyPCl. The X-ray photoelectron spectrum of the surface suggested that the metal was coordinated by the pyridine-N. The enhancement effect of the transition metals was supported by two different measurements: oxygen reduction at HOPG in 0.1 M HClO 4 dissolving FeTPyPCl and the metal ions; oxygen reduction in 0.1 M HClO 4 at the subsequently well-rinsed and dried HOPG. The ultraviolet–visible spectrum for the solution also suggested the coordination between the pyridyl-N and the metal ions. The oxygen reduction enhancement was attributed to the electronic interaction between the additional transition metal and the Fe center of the porphyrin through the coordination bonds. These results implied that the improvement of the activity of the noble-metal-free catalyst would be possible by the proper introduction of the transition metal ions around the active site.

Acid-base and coordination properties of Meso-substituted porphyrins in nonaqueous solutions

Science.gov (United States)

Pukhovskaya, S. G.; Nam, Dao Tkhe; Fien, Chan Ding; Domanina, E. N.; Ivanova, Yu. B.; Semeikin, A. S.

2017-09-01

Acid-base and coordination properties of alkyl and aryl meso-substituted porphyrins are studied spectrophotometrically in nonaqueous solutions. It is found that the nature of the substituent greatly affects the basicity of ligands for porphyrins characterized by a flat structure of macrocycle. The electronic effects of substituents have a much weaker influence on the kinetics of complexing. These effects could be due to the opposite orientation of some factors: an increase in the basicity and stability of the N-H bonds of porphyrin reaction centers. Dissociation constants p K b of the cationic forms of meso-substituted derivatives of porphyrin are measured. The values of p K b are in good agreement with classic concepts of the nature of substituents, particularly those indirectly included in the macrocycle through phenyl buffer rings.

Niños y niñas frente a la televisión: entretención y educación

OpenAIRE

Carmona Escobar, Sandra; Horta Burbano, Nubia

2017-01-01

La presente investigación se ha desarrollado teniendo en cuenta que la televisión, puede ser una de las herramientas más significativas en la formación de los niños y niñas, debido al contacto e influencia que este medio tiene con la sociedad actual. Por esta razón se considera necesario realizar un acercamiento desde el campo de la comunicación educativa, permitiendo describir la manera en la cual la televisión entra a los hogares, centrándose en la recepción que realizan los niños de los pr...

Synthesis and characterization of n-type NiO:Al thin films for fabrication of p-n NiO homojunctions

Science.gov (United States)

Sun, Hui; Liao, Ming-Han; Chen, Sheng-Chi; Li, Zhi-Yue; Lin, Po-Chun; Song, Shu-Mei

2018-03-01

n-type NiO:Al thin films were deposited by RF magnetron sputtering. Their optoelectronic properties versus Al target power was investigated. The results show that with increasing Al target power, the conduction type of NiO films changes from p-type to n-type. The variation of the film’s electrical and optical properties depends on Al amount in the film. When Al target power is relatively low, Al3+ cations tend to enter nickel vacancy sites, which makes the lattice structure of NiO more complete. This improves the carrier mobility and film’s transmittance. However, when Al target power exceeds 40 W, Al atoms begin to enter into interstitial sites and form an Al cluster in the NiO film. This behavior is beneficial for improving the film’s n-type conductivity but degrades the film’s transmittance. Finally, Al/(p-type NiO)/(n-type NiO:Al)/ITO homojunctions were fabricated. Their performance was compared with Al/(p-type NiO)/ITO heterojunctions without an n-type NiO layer. Thanks to the better interface quality between the two NiO layers, the homojunctions present better performance.

The photodynamic and non-photodynamic actions of porphyrins

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S.G. Afonso

1999-03-01

Full Text Available Porphyrias are a family of inherited diseases, each associated with a partial defect in one of the enzymes of the heme biosynthetic pathway. In six of the eight porphyrias described, the main clinical manifestation is skin photosensitivity brought about by the action of light on porphyrins, which are deposited in the upper epidermal layer of the skin. Porphyrins absorb light energy intensively in the UV region, and to a lesser extent in the long visible bands, resulting in transitions to excited electronic states. The excited porphyrin may react directly with biological structures (type I reactions or with molecular oxygen, generating excited singlet oxygen (type II reactions. Besides this well-known photodynamic action of porphyrins, a novel light-independent effect of porphyrins has been described. Irradiation of enzymes in the presence of porphyrins mainly induces type I reactions, although type II reactions could also occur, further increasing the direct non-photodynamic effect of porphyrins on proteins and macromolecules. Conformational changes of protein structure are induced by porphyrins in the dark or under UV light, resulting in reduced enzyme activity and increased proteolytic susceptibility. The effect of porphyrins depends not only on their physico-chemical properties but also on the specific site on the protein on which they act. Porphyrin action alters the functionality of the enzymes of the heme biosynthetic pathway exacerbating the metabolic deficiencies in porphyrias. Light energy absorption by porphyrins results in the generation of oxygen reactive species, overcoming the protective cellular mechanisms and leading to molecular, cell and tissue damage, thus amplifying the porphyric picture.

[Study on the aggregation behavior of cationic porphyrins and their interaction with ctDNA].

Science.gov (United States)

Ma, Hong-Min; Chen, Xin; Sun, Shu-Ting; Zhang, Li-Na; Wu, Dan; Zhu, Pei-Hua; Li, Yan; Du, Bin; Wei, Qin

2009-02-01

Interest in the interaction between cationic porphyrins, particularly derivatives of meso-tetra(N-methylpyridinium-4-yl) porphyrin(TMPyP), and DNA abounds because they are versatile DNA-binding agents that could find application in photodynamic therapy, cancer detection, artificial nucleases, virus inhibition and so on. The interaction of two water-soluble cationic porphyrins, meso-tetrakis(4-N, N, N-trimethylanilinium) porphyrin (TMAP) and 5-phenyl-10,15,20-tris[4-(N-methyl) pyridinium]porphyrin (TriMPyP), with calf thymus DNA (ctDNA) was studied by UV-Vis absorption spectroscopy, fluorescence spectroscopy and resonance light scattering technique. TriMPyP forms aggregate in water due to the molecular asymmetry while TMAP exists as monomers. At lower concentrations of ctDNA (R > 1, R = c(TMAP)/c(DNA) base pair), the interaction of TMAP with DNA leads to significant hypochromicity and bathochromic shift of absorption spectra. And the fluorescence of TMAP was quenched while it showed enhanced resonance light scattering signals. But the extent of enhancement of resonance light scattering signals is very small, so the aggregate of TMAP is not very high. These observations indicate the self-stacking of TMAP along the DNA surface. At higher concentrations of ctDNA (R TMAP association with DNA is via outside binding which is accompanied with hyperchromic effect and fluorescence enhancement while the resonance light scattering signals is reduced. DNA addition decreases the fluorescence intensity of TriMPyP and it shifts the peak to the higher wavelengths (red shift). The interaction with DNA promotes the aggregation of TriMPyP and no simple outside binding is observed even at higher concentrations of ctDNA. The steric effect of molecular distortion constrains the intercalation or further binding to DNA. The effect of ionic strength on the interaction was investigated at two DNA concentrations, 1.2 and 24.0 micromol x L(-1), for TMAP. The Interactions of both porphyrins

Adsorption characteristics of a cationic porphyrin on nanoclay at various pH.

Science.gov (United States)

Rice, Zachary; Bergkvist, Magnus

2009-07-15

Natural and synthetic porphyrin derivatives offer a range of applications including enzymatic catalysis, photosensitizers for light harvesting and chemical reactions, and molecular electronics. They exhibit unique optical spectra dominated by the presence of Soret and Q-band structures whose position and shape offer a straightforward method to characterize porphyrins in various surroundings. In many applications it is often beneficial to have porphyrins adsorbed onto a solid matrix. Applications of porphyrin-clay complexes extend to numerous biological applications including pharmaceutical drug delivery, cosmetics, and agricultural applications and thus a full understanding of porphyrin-clay surface interactions are essential. Here we investigated the adsorption behavior of meso-tetra(4-N,N,N-trimethylanilinium) porphine (TMAP) onto sodium containing, natural montmorillonite clay (Cloisite Na(+)) in characteristic biological buffers over a range of pHs (approximately 2-9). Spectroscopic analyses show a linear absorption response at acidic and basic pHs but a slight deviation at intermediate pHs. Absorption spectra for TMAP on clay showed distinct red shifts of the Soret and Q-bands compared to free TMAP for all buffer conditions indicating core pi-electron delocalization into the substituent rings. At intermediate pHs, a gradual transition between protonated/deprotonated states were seen, presumably due to higher H(+) concentration at the surface than in bulk. Results indicate TMAP adsorption to clay occurs in a monolayer fashion at low/high pH while slightly acidic/neutral pH possibly rearrange on the surface and/or form aggregates. AFM images of clay saturated with TMAP are reported and show single isolated clay sheets without aggregation, similar to clay without TMAP.

Tradução e adaptação cultural da escala de confusão de NEECHAM Traducción y adaptación cultural de la escala de confusión de NEECHAM Translation and cultural adaption of the NEECHAM confusion scales

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Hugo Neves

2011-03-01

Full Text Available Apesar dos problemas e dos riscos associados à Confusão Aguda (CA, a literatura sugere grandes dificuldades no seu diagnóstico, por parte dos profissionais de saúde, nomeadamente, pelos enfermeiros. O uso de instrumentos de avaliação que, através da aplicação de critérios, permitam uma avaliação rigorosa sistematizada e que conduza a níveis de detecção mais eficazes, torna-se necessário. Com este estudo pretendeu-se traduzir e validar uma escala capaz de diagnosticar a CA de forma a promover a saúde e segurança do doente confuso. Após uma revisão sistemática da literatura optou-se pelo uso da escala NEECHAM Confusion Scale. O processo de tradução utilizado baseou-se no método recomendado pela International Society for Pharmacoeconomics and Outcomes Research (ISPOR. Após a utilização da NEECHAM Confusion Scale observou-se uma elevada consistência interna (Alpha Cronbach=0,913, uma boa correlação com os scores da Escala de Glasgow (r=0,866 p=0,000 e divisão da escala em duas dimensões pela análise das cargas factoriais e pela análise da rotação varimax. Sugerimos e defendemos a importância da utilização da NEECHAM, associada a formação sobre o fenómeno, o que permitirá produzir melhores índices de reconhecimento, ao mesmo tempo que permitirá a validação de intervenções adequadas ao doente confuso.A pesar de los problemas y de los riesgos asociados a la Confusión Aguda (CA, la literatura sugiere grandes dificultades en su diagnóstico, por parte de los profesionales de salud, en particular por parte de los enfermeros. El uso de instrumentos de evaluación que, mediante la aplicación de criterios, permitan una evaluación rigurosa sistematizada y que conduzca a niveles de detección más eficaces es una necesidad. Con este estudio se pretendió traducir y validar una escala capaz de diagnosticar la CA de forma a promover la salud y la seguridad del enfermo con delirium. Tras una revisión sistem

Comparison of electron ionization and fast atom bombardment-mass spectrometry for the determination of nickel, vanadyl and free-base porphyrins

Energy Technology Data Exchange (ETDEWEB)

Castro, A.J.; Van Berkel, G.J.; Doolittle, F.G.; Filby, R.H. (Washington State Univ., Pullman (USA))

1989-01-01

Fast Atom Bombardment-Mass Spectrometry (FAB-MS) and Electron Ionization-Mass Spectrometry (EI-MS) at 12 and 70 eV, were used to obtain mass spectra of mesoporphyrin IX dimethylester (DME), tetraphenylporphyrin (TPP), octaethylporphyrin (OEP), and the metal-loporphyrins, Ni(DME), Ni(TPP), Ni(OEP), VO(TPP), VO(OEP), as well as a VO(II) porphyrin concentrate obtained from the New Albany oil shale bitumen (Mississippian-Devonian). A mixture of dithiothreitol/dithioerythritol (Magic Bullet) was used as the FAB matrix. Greater fragmentation of free-base and metalloporphyrins was observed in FAB mass spectra compared to the EI mass spectra. Adduct ions formed by addition of sulfur and a matrix molecule to the porphyrins were observed. In FAB spectra of the VO(II) complexes, loss of oxygen was noted. The FAB mass spectra of mixtures of VO(II) geoporphyrins are much more complex than corresponding EI mass spectra because of the greater fragmentation and the multiplicity of ions (M{sup +}, M + H, M + 2H, etc.) observed in the FAB mode. Using the matrices investigated, FAB is less suitable for EI for the mass spectrometric analysis of the geoporphyrins.

A Study of Porphyrins in Petroleum Source Rocks

Energy Technology Data Exchange (ETDEWEB)

Huseby, Berit

1997-12-31

This thesis discusses several aspects of porphyrin geochemistry. Degradation experiments have been performed on the Messel oil shale (Eocene, Germany) to obtain information on porphyrins bound or incorporated into macromolecular structures. Thermal heating of the preextracted kerogen by hydrous pyrolysis was used to study the release of porphyrins and their temperature dependent changes during simulated diagenesis and catagenesis. Selective chemical degradation experiments were performed on the preextracted sediment to get more detailed information about porphyrins that are specifically bound to the macromolecular structures via ester bonds. From the heating experiments, in a separate study, the porphyrin nitrogen content in the generated bitumens was compared to the bulk of organic nitrogen compounds in the fraction. The bulk nitrogen contents in the generated bitumens, the water phase and the residual organic matter was recorded to establish the distribution of nitrogen between the kerogen and product phases. Porphyrins as biomarkers were examined in naturally matured Kimmeridge clay source rocks (Upper Jurassic, Norway), and the use of porphyrins as general indicators of maturity was evaluated. Underlying maturity trends in the biomarker data was investigated by Partial Least Squares analysis. Porphyrin as indicators of depositional conditions was also addressed, where the correlations between the (amounts) abundance of nickel and vanadyl porphyrins were mapped together with other descriptors that are assumed to be indicative of redox depositional conditions. 252 refs., 28 figs., 4 tabs.

A Study of Porphyrins in Petroleum Source Rocks

Energy Technology Data Exchange (ETDEWEB)

Huseby, Berit

1996-12-31

This thesis discusses several aspects of porphyrin geochemistry. Degradation experiments have been performed on the Messel oil shale (Eocene, Germany) to obtain information on porphyrins bound or incorporated into macromolecular structures. Thermal heating of the preextracted kerogen by hydrous pyrolysis was used to study the release of porphyrins and their temperature dependent changes during simulated diagenesis and catagenesis. Selective chemical degradation experiments were performed on the preextracted sediment to get more detailed information about porphyrins that are specifically bound to the macromolecular structures via ester bonds. From the heating experiments, in a separate study, the porphyrin nitrogen content in the generated bitumens was compared to the bulk of organic nitrogen compounds in the fraction. The bulk nitrogen contents in the generated bitumens, the water phase and the residual organic matter was recorded to establish the distribution of nitrogen between the kerogen and product phases. Porphyrins as biomarkers were examined in naturally matured Kimmeridge clay source rocks (Upper Jurassic, Norway), and the use of porphyrins as general indicators of maturity was evaluated. Underlying maturity trends in the biomarker data was investigated by Partial Least Squares analysis. Porphyrin as indicators of depositional conditions was also addressed, where the correlations between the (amounts) abundance of nickel and vanadyl porphyrins were mapped together with other descriptors that are assumed to be indicative of redox depositional conditions. 252 refs., 28 figs., 4 tabs.

Dualism of Sensitivity and Selectivity of Porphyrin Dimers in Electroanalysis.

Science.gov (United States)

Lisak, Grzegorz; Tamaki, Takashi; Ogawa, Takuji

2017-04-04

This work uncovers the application of porphyrin dimers for the use in electroanalysis, such as potentiometric determination of ions. It also puts in question a current perception of an occurrence of the super-Nernstian response, as a result of the possible dimerization of single porphyrins within an ion-selective membrane. To study that, four various porphyrin dimers were used as ionophores, namely, freebase-freebase, Zn-Zn, Zn-freebase, and freebase-Zn. Since the Zn-freebase and freebase-Zn porphyrin dimers carried both anion- and cation-sensitive porphyrin units, their application in ISEs was utilized in both anion- and cation-sensitive sensors. With respect to the lipophilic salt added, both porphyrins dimers were found anion- and cation-sensitive. This allowed using a single molecule as novel type of versatile ionophore (anion- and cation-selective), simply by varying the membrane composition. All anion-sensitive sensors were perchlorate-sensitive, while the cation-selective sensors were silver-sensitive. The selectivity of the sensors depended primarily on the porphyrin dimers in the ion-selective membrane. Furthermore, the selectivity of cation-sensitive dimer based sensors was found significantly superior to the ones measured for the single porphyrin unit based sensors (precursors of the porphyrin dimers). Thus, the dimerization of single porphyrins may actually be a factor to increase or modulate porphyrin selectivity. Moreover, in the case of cation-sensitive sensors, the selectivity vastly depended on the order of porphyrin units in the dimer. This opens a new approach of regulating and adjusting sensitivity and selectivity of the sensor through the application of complex porphyrin systems with more than one porphyrin units with mix sensitive porphyrins.

Reduction reactions of water soluble cyano-cobalt(III)-porphyrins: Metal versus ligand centered processes

International Nuclear Information System (INIS)

Mosseri, S.; Neta, P.; Harriman, A.; Hambright, P.

1990-01-01

Reduction reactions of dicyano-cobalt(III)-porphyrins [potential in vivo cyanide scavenger drugs] were studied by radiolytic and electrochemical methods using the water soluble tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and tetrakis(N-methyl-4-pyridyl)porphyrin (TMPyP). For [(CN)2CoIIITPPS]-, reduction occurs stepwise to the CoII, CoI, and finally to the phlorin anion. This behavior is similar to that of the cobalt porphyrins in the absence of cyanide, except that the cyanide ligand shifts the reduction potentials to much more negative values. On the other hand, under radiolytic conditions, [(CN)2CoIIITMPyP]- is reduced on the porphyrin macrocycle by one electron to give the CoIII pi-radical anion, which disproportionates into the initial complex and the two-electron ring reduced CoIII phlorin. The radical anion is also formed by intramolecular electron transfer subsequent to the reaction of CoIITMPyP and cyanide. The results are compared with the chemistry of Vitamin B-12

Synthesis and biological evaluation of porphyrin-polyamine conjugates as potential agents in photodynamic therapy

International Nuclear Information System (INIS)

Lamarche, Francois

2004-01-01

The synthesis of photosensitizers that specifically recognize tumoral cells constitutes a challenging step in the field of photodynamic therapy. To this end, we designed a new class of porphyrins linked to natural polyamines (spermidine, spermine). As a first step, we synthesized para and ortho-carboxy-propyl-oxy-phenyl-tritolyl-porphyrins bearing spermidine or spermine. Then, we designed two precursors, N4-aminobutyl-spermidine-Boc2 and N4-aminobutyl-spermine-Boc3. These derivatives have been fixed on carboxy-porphyrins, protoporphyrin IX and chlorin e6. These new compounds have been characterized by MALDI spectrometry, UV-Visible and 1 H NMR spectroscopy. They have been found to produce singlet oxygen. Biological activity study of these photosensitizers has been realized on K562 cell line, irradiated with fluorescent bulbs. In vitro tests of these porphyrins have shown their photo-cytotoxic activity and protoporphyrins-polyamines have been able to trigger early apoptotic events. Finally, preliminary results obtained with chlorin e6-polyamines, irradiated with red light, seem to show that these structures are good candidates for an application in PDT. (author) [fr

Thin porphyrin composite membranes with enhanced organic solvent transport

KAUST Repository

Phuoc, Duong

2018-05-01

Extending the stability of polymeric membranes in organic solvents is important for applications in chemical and pharmaceutical industry. Thin-film composite membranes with enhanced solvent permeance are proposed, using porphyrin as a building block. Hybrid polyamide films are formed by interfacial polymerization of 5,10,15,20-(tetra-4-aminophenyl)porphyrin/m-phenylene diamine (MPD) mixtures with trimesoyl chloride. Porphyrin is a non-planar molecule, containing a heterocyclic tetrapyrrole unit. Its incorporation into a polyamide film leads to higher free volume than that of a standard polyamide film. Polyamide films derived from porphyrin and MPD amines with a fixed total amine concentration of 1wt% and various porphyrin/MPD ratios were fabricated and characterized. The porphyrin/MPD polyamide film was complexed with Cu(II), due to the binding capacity of porphyrin to metal ions. By coupling scanning transmission electron microscopy (STEM) with electron energy-loss spectroscopy (EELS), Cu mapping was obtained, revealing the distribution of porphyrin in the interfacial polymerized layer. By using porphyrin as amine-functionalized monomer a membrane with thin selective skin and enhanced solvent transport is obtained, with good dye selectivity in the nanofiltration range. For instance, an ultra-fast hexane permeance, 40-fold increased, was confirmed when using 0.5/0.5 porphyrin/MPD mixtures, instead of only MPD as amine monomer. A rejection of 94.2% Brilliant Blue R (826g/mol) in methanol was measured.

Remarkable fluorescence enhancement versus complex formation of cationic porphyrins on the surface of ZnO nanoparticles

KAUST Repository

Aly, Shawkat Mohammede

2014-06-12

Fluorescence enhancement of organic fluorophores shows tremendous potential to improve image contrast in fluorescence-based bioimaging. Here, we present an experimental study of the interaction of two cationic porphyrins, meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride (TMPyP) and meso-tetrakis(4-N,N,N-trimethylanilinium)porphyrin chloride (TMAP), with cationic surfactant-stabilized zinc oxide nanoparticles (ZnO NPs) based on several steady-state and time-resolved techniques. We show the first experimental measurements demonstrating a clear transition from pronounced fluorescence enhancement to charge transfer (CT) complex formation by simply changing the nature and location of the positive charge of the meso substituent of the cationic porphyrins. For TMPyP, we observe a sixfold increase in the fluorescence intensity of TMPyP upon addition of ZnO NPs. Our experimental results indicate that the electrostatic binding of TMPyP with the surface of ZnO NPs increases the symmetry of the porphyrin macrocycle. This electronic communication hinders the rotational relaxation of the meso unit and/or decreases the intramolecular CT character between the cavity and the meso substituent of the porphyrin, resulting in the enhancement of the intensity of the fluorescence. For TMAP, on the other hand, the different type and nature of the positive charge resulting in the development of the CT band arise from the interaction with the surface of ZnO NPs. This observation is confirmed by the femtosecond transient absorption spectroscopy, which provides clear spectroscopic signatures of photoinduced electron transfer from TMAP to ZnO NPs. © 2014 American Chemical Society.

The cross section measurement for the reactions of 48,46Ti(n,p) 48,46Sc, 50Ti(n, α)47Ca and 58Ni (n, 2n)57Ni, 58Ni(n,p)58m+gCo

International Nuclear Information System (INIS)

Yuan Junqian; Wang Yongchang; Kong Xiangzhong; Yang Jingkang

1992-01-01

The cross sections for the 50 Ti(n, α) 47 Ca, 46 Ti(n, p) 46 Sc, 48 Ti(n, p) 48 Sc and 58 Ni(n, 2n) 57 Ni, 58 Ni(n, p) 58m+g Co reactions have been measured by using the activation method relative to the cross sections of the 27 Al(n, α) 24 Na reaction in the neutron energy range of 13.50-14.81 MeV. The neutron energies were determined by the cross section ratios of the 90 Zr(n, 2n) 89m+g Zr and 93 Nb(n, 2n) 92m Nb reactions. The results obtained are compared with the published and to be published data of several authors

Conformational switching of ethano-bridged Cu,H2-bis-porphyrin induced by aromatic amines.

Science.gov (United States)

Bettini, Simona; Maglie, Emanuela; Pagano, Rosanna; Borovkov, Victor; Inoue, Yoshihisa; Valli, Ludovico; Giancane, Gabriele

2015-01-01

Cu,H2-bis-porphyrin (Cu,H2-Por2), in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir-Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase) to a surface plasmon resonance (SPR) substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

Conformational switching of ethano-bridged Cu,H2-bis-porphyrin induced by aromatic amines

Directory of Open Access Journals (Sweden)

Simona Bettini

2015-11-01

Full Text Available Cu,H2-bis-porphyrin (Cu,H2-Por2, in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir–Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase to a surface plasmon resonance (SPR substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

Substituted group and side chain effects for the porphyrin and zinc(II)–porphyrin derivatives: A DFT and TD-DFT study

International Nuclear Information System (INIS)

Tai, Chin-Kuen; Chuang, Wen-Hua; Wang, Bo-Cheng

2013-01-01

The DFT/B3LYP/LANL2DZ and TD-DFT calculations have been performed to generate the optimized structures, electronic and photo-physical properties for the porphyrin and zinc(II)–porphyrin (metalloporphyrin) derivatives. The substituted group and side chain effects for these derivatives are discussed in this study. According to the calculation results, the side chain moiety extends the π-delocalization length from the porphyrin core to the side chain moiety. The substituted group with a stronger electron-donating ability increases the energy level of highest occupied molecular orbital (E HOMO ). The side chain moiety with a lower resonance energy decreases E HOMO , the energy level of the lowest unoccupied molecular orbital (E LUMO ), and the energy gap (E g ) between HOMO and LUMO in the porphyrin and zinc(II)–porphyrin derivatives. The natural bonding orbital (NBO) analysis determines the possible electron transfer mechanism from the electron-donating to -withdrawing groups (the side chain moiety) in these porphyrin derivatives. The projected density of state (PDOS) analysis shows that the electron-donating group affects the electron density distribution in both HOMO and LUMO, and the side chain moiety influence the electron density distribution in LUMO. The calculated photo-physical properties (absorption wavelengths and the related oscillator strength, f) in dichloromethane environment for porphyrin and zinc(II)–porphyrin derivatives have been simulated by using the TD-DFT method within the Polarizable Continuum Model (PCM). The present of both of the substituted group and the side chain moiety in these derivatives results in a red shift and broadening of the range of the absorption peaks of the Q/Soret band as compared to porphin. -- Highlights: • Side chain moiety extends the π-delocalization for the porphyrins. • Substituted group increases the energy of highest occupied molecular orbital. • Side chain moiety influences the Q/Soret band of

Spectroscopic studies on the interaction of a water-soluble cationic porphyrin with proteins

Science.gov (United States)

Ma, Hong-Min; Chen, Xin; Zhang, Nuo; Han, Yan-Yan; Wu, Dan; Du, Bin; Wei, Qin

2009-04-01

The interaction of a water-soluble cationic porphyrin, meso-tetrakis (4- N, N, N-trimethylanilinium) porphyrin (TMAP), with two proteins, bovine serum albumin (BSA) and human serum albumin (HSA), was studied by UV-vis absorption spectroscopy, fluorescence spectroscopy, fluorescence anisotropy and synchronous fluorescence spectroscopy at neutral aqueous solutions. Free base TMAP bound to proteins as monomers and no aggregation was observed. The binding of TMAP quenched the fluorescence of the protein. On the contrary, the fluorescence of TMAP was enhanced and the fluorescence anisotropy increased due to the binding. The direct static binding mechanism could account for the quenching by TMAP and the binding constants were calculated. TMAP showed a higher quenching efficiency and binding constant of HSA than BSA. The binding of TMAP had no obvious effect on the molecular conformation of the protein. There was only one binding site for TMAP and it was located on the surface of the protein molecule. Electrostatic force played an important role in the binding due to the opposite charges on porphyrin and the proteins.

Characterization of functionalised porphyrin films using synchrotron radiation

International Nuclear Information System (INIS)

Arima, V.; Matino, F.; Thompson, J.; Del Sole, R.; Mele, G.; Vasapollo, G.; Cingolani, R.; Rinaldi, R.; Blyth, R.I.R.

2005-01-01

Porphyrins and C 60 are strategic materials for the fabrication of nanoscale molecular devices by virtue of their optical, photo-electro-chemical and chemical properties. We have developed procedures to immobilise cobalt tetra-butyl-phenyl porphyrins (CoTBPPs) on gold surfaces via ligation to self-assembled monolayers of aromatic aminothiophenols (4-ATP). We have used synchrotron radiation photoemission and near-edge X-ray absorption, NEXAFS, to characterise such films, both in their native state, and with ligated fulleropyrrolidines N-methyl-2-(p-pyridyl)-3,4-fulleropyrrolidine (Py-C 60 ), forming charge-separation complexes which may have applications in solar cells. While photoemission spectra appear dominated by the individual CoTBPP and Py-C 60 components, we observe an apparent signature of charge separation in fulleropyrrolidine NEXAFS spectra

A novel chlorine derivative of Meso-tris(pentafluorophenyl)-4-pyridyl porphyrin: synthesis, photophysics and photochemical properties

Energy Technology Data Exchange (ETDEWEB)

Maestrin, Ana Paula J.; Ribeiro, Anderson O.; Tedesco, Antonio Claudio; Neri, Claudio R.; Vinhado, Fabio S.; Serra, Osvaldo A.; Martins, Patricia R.; Iamamoto, Yassuko [Sao Paulo Univ., Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras. Inst. de Quimica]. E-mail: oaserra@ffclrp.usp.br; Silva, Ana Margarida G.; Tome, Augusto C.; Neves, Maria G.P.M.S.; Cavaleiro, Jose A.S. [Universidade de Aveiro (Portugal). Dept. de Quimica]. E-mail: jcavaleiro@dq.ua.pt

2004-12-01

Photodynamic therapy (PDT) is based on the accumulation of a photosensitizer, such as a porphyrin or a chlorine, in a malignant tissue after its administration. Chlorins exhibit photophysical properties similar to those of the porphyrin macrocycles, but with intensified and red-shifted Q bands, making chlorine-containing systems even better candidates for PDT. In this contribution, we report the synthesis of 5,10,15-tris(pentafluorophenyl)-20-(4-pyridyl)porphyrin, (2) and its transformation to the novel chlorine derivatives 4, (5,10,20-tris(pentafluorophenyl)-15-(4-pyridyl)-tetrahydro-1H- N-methyl-pyrrolo [3,4-b]porphyrin and 5, (5,10,15-tris(pentafluorophenyl)-20-(4-pyridyl)-tetrahydro-1H- N-methyl-pyrrolo[3,4-b]porphyrin) by 1,3-dipolar cycloaddition with an azomethine ylide. The new products have been characterized by UV-Vis, {sup 1}H NMR and FAB-MS. The photophysics, photochemical and photobleaching properties of chlorine 4 have been evaluated. Its quantum yield of photobleaching ({phi}{sub Pb}, mol Einstein{sup -1}) was 0.047{+-}0.014. In order to demonstrate the production of {sup 1}O{sub 2} when 4 is used as a photosensitizer, uric acid tests have been carried out. The results indicate that chlorine 4 can be considered a promising photosensitizer in PDT. (author)

A novel chlorine derivative of Meso-tris(pentafluorophenyl)-4-pyridyl porphyrin: synthesis, photophysics and photochemical properties

International Nuclear Information System (INIS)

Maestrin, Ana Paula J.; Ribeiro, Anderson O.; Tedesco, Antonio Claudio; Neri, Claudio R.; Vinhado, Fabio S.; Serra, Osvaldo A.; Martins, Patricia R.; Iamamoto, Yassuko; Silva, Ana Margarida G.; Tome, Augusto C.; Neves, Maria G.P.M.S.; Cavaleiro, Jose A.S.

2004-01-01

Photodynamic therapy (PDT) is based on the accumulation of a photosensitizer, such as a porphyrin or a chlorine, in a malignant tissue after its administration. Chlorins exhibit photophysical properties similar to those of the porphyrin macrocycles, but with intensified and red-shifted Q bands, making chlorine-containing systems even better candidates for PDT. In this contribution, we report the synthesis of 5,10,15-tris(pentafluorophenyl)-20-(4-pyridyl)porphyrin, (2) and its transformation to the novel chlorine derivatives 4, (5,10,20-tris(pentafluorophenyl)-15-(4-pyridyl)-tetrahydro-1H- N-methyl-pyrrolo [3,4-b]porphyrin and 5, (5,10,15-tris(pentafluorophenyl)-20-(4-pyridyl)-tetrahydro-1H- N-methyl-pyrrolo[3,4-b]porphyrin) by 1,3-dipolar cycloaddition with an azomethine ylide. The new products have been characterized by UV-Vis, 1 H NMR and FAB-MS. The photophysics, photochemical and photobleaching properties of chlorine 4 have been evaluated. Its quantum yield of photobleaching (φ Pb , mol Einstein -1 ) was 0.047±0.014. In order to demonstrate the production of 1 O 2 when 4 is used as a photosensitizer, uric acid tests have been carried out. The results indicate that chlorine 4 can be considered a promising photosensitizer in PDT. (author)

Thermochemical characteristics of La n+1Ni nO3n+1 oxides

International Nuclear Information System (INIS)

Bannikov, D.O.; Safronov, A.P.; Cherepanov, V.A.

2006-01-01

Lanthanum nickelates: La 2 NiO 4+δ , La 3 Ni 2 O 7-δ , La 4 Ni 3 O 10-δ and LaNiO 3-δ the members of Ruddlesden-Popper series La n+1 Ni n O 3n+1 were prepared using citrate route. Dissolution enthalpies of complex oxides as well as a number of subsidiary substances were measured by means of Calvet calorimeter in 1 M solution of hydrochloric acid at 25 deg. C. The dissolution scheme of complex oxides in hydrochloric acid was proposed and enthalpies of formation of the complex oxides from binary oxides were calculated considering oxygen nonstoichiometry of these substances. Enthalpies of step-by-step oxidation were evaluated. Partial enthalpy contribution of LaO layers was calculated endothermic equals to 30.9 J/mol while partial enthalpy contribution of perovskite LaNiO 3 layers was negative equals to -97.0 J/mol. Enthalpy of formation of any complex oxide of Ruddlesden-Popper series fits very well to the linear regression based on these values

Porphyrin and fullerene-based artificial photosynthetic materials for photovoltaics

International Nuclear Information System (INIS)

Imahori, Hiroshi; Kashiwagi, Yukiyasu; Hasobe, Taku; Kimura, Makoto; Hanada, Takeshi; Nishimura, Yoshinobu; Yamazaki, Iwao; Araki, Yasuyuki; Ito, Osamu; Fukuzumi, Shunichi

2004-01-01

We have developed artificial photosynthetic systems in which porphyrins and fullerenes are self-assembled as building blocks into nanostructured molecular light-harvesting materials and photovoltaic devices. Multistep electron transfer strategy has been combined with our finding that porphyrin and fullerene systems have small reorganization energies, which are suitable for the construction of light energy conversion systems as well as artificial photosynthetic models. Highly efficient photosynthetic electron transfer reactions have been realized at ITO electrodes modified with self-assembled monolayers of porphyrin oligomers as well as porphyrin-fullerene linked systems. Porphyrin-modified gold nanoclusters have been found to have potential as artificial photosynthetic materials. These results provide basic information for the development of nanostructured artificial photosynthetic systems

One-pot synthesis of gold nanoparticles using tetradentate porphyrins

International Nuclear Information System (INIS)

Canitez, Fatma K.; Yavuz, Mustafa S.; Ozturk, Ramazan

2011-01-01

In this study, the meso-tetra (p-hydroxyphenyl) porphyrin and meso-tetra (m-hydroxyphenyl) porphyrin were coated on to gold nanoparticles (AuNPs) via thioacetate anchors which easily dissociate to form S–Au bonds. 4-tert-butyl phenyl thioacetate-AuNPs were prepared and used as a monodentate passivant to control the size of the tetradentate porphyrin-AuNPs. The porphyrin-coated AuNPs were characterized by UV–Vis, TEM, XRD, and XPS analyses. The tetradentate porphyrin-AuNPs size is within a range of 5–15 nm in diameter with exotic shapes. The plausible network formation for AuNP-p-TPP-SAc and the capping structure of the AuNP-m-TPP-SAc have been suggested.

Characterization of functionalised porphyrin films using synchrotron radiation

Energy Technology Data Exchange (ETDEWEB)

Arima, V. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy)]. E-mail: valentina.arima@unile.it; Matino, F. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy); Thompson, J. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy); Del Sole, R. [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, via per Arnesano, 73100 Lecce (Italy); Mele, G. [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, via per Arnesano, 73100 Lecce (Italy); Vasapollo, G. [Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, via per Arnesano, 73100 Lecce (Italy); Cingolani, R. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy); Rinaldi, R. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy); Blyth, R.I.R. [National Nanotechnology Laboratory of INFM, Distretto Tecnologico ISUFI, Universita di Lecce Via Arnesano, 73100 Lecce (Italy)

2005-07-30

Porphyrins and C{sub 60} are strategic materials for the fabrication of nanoscale molecular devices by virtue of their optical, photo-electro-chemical and chemical properties. We have developed procedures to immobilise cobalt tetra-butyl-phenyl porphyrins (CoTBPPs) on gold surfaces via ligation to self-assembled monolayers of aromatic aminothiophenols (4-ATP). We have used synchrotron radiation photoemission and near-edge X-ray absorption, NEXAFS, to characterise such films, both in their native state, and with ligated fulleropyrrolidines N-methyl-2-(p-pyridyl)-3,4-fulleropyrrolidine (Py-C{sub 60}), forming charge-separation complexes which may have applications in solar cells. While photoemission spectra appear dominated by the individual CoTBPP and Py-C{sub 60} components, we observe an apparent signature of charge separation in fulleropyrrolidine NEXAFS spectra.

Corroles-Porphyrins: A Teamwork for Gas Sensor Arrays

Directory of Open Access Journals (Sweden)

Rosamaria Capuano

2015-04-01

Full Text Available Porphyrins provide an excellent material for chemical sensors, and they have been used for sensing species both in air and solution. In the gas phase, the broad selectivity of porphyrins is largely dependant on molecular features, such as the metal ion complexed at the core of the aromatic ring and the peripheral substituents. Although these features have been largely exploited to design gas sensor arrays, so far, little attention has been devoted to modify the sensing properties of these macrocycles by variation of the molecular aromatic ring. In this paper, the gas sensing properties of a porphyrin analog, the corrole, are studied in comparison with those of the parent porphyrin. Results show that changes in the aromatic ring have important consequences on the sensitivity and selectivity of the sensors and that porphyrins and corroles can positively cooperate to enhance the performance of sensor arrays.

Multifunctional porphyrinic materials encapsulated into macronets with photo chemotherapeutic applications

Energy Technology Data Exchange (ETDEWEB)

Ion, R. -M.; Fierascu, R. -C.; Dimitriu, I. [Valahia University, Materials Science Department, Targoviste (Romania)

2008-07-01

Supramolecidar chemistry is expected to keep a high developing advanced of molecular devices based on multifunctional materials. Porphyrins and their analogues should play a significant role as a consequence of their catalytic, electrocatalytic, photochemical and photoelectrochemical properties. Such molecular materials contain a high porosity with large cavities and galleries that can be functionalization yielding to a desired chirality and structure. The functionalization implies inserting into macrocydic cavity, followed by auto-assembling as columnar aggregates. The obtained cavities are used as host for different molecular guests. H and J-aggregates of some porphyrins are based on the intermolecular interactions of 3-5 Kcal/mol per porphyrin face. The columnar structure formed by porphyrins has a length of 5 to 27 porphyrin unities. In this paper we focused on our own strategy based on coordination chemistry for the design and build-up of supermolecules and supra molecular structures constituted by a porphyrin (TSPPJ and a new and revolutionary method for stabilizing porphyrins (as organic part), by their incapsulation into supports with controlled porosity as macronets (as inorganic parts), obtaining some hybrids materials. Included are also their properties and potential applications. Key words: porphyrins, macronets, photochemotherapy.

Ni62(n,γ) and Ni63(n,γ) cross sections measured at the n_TOF facility at CERN

Science.gov (United States)

Lederer, C.; Massimi, C.; Berthoumieux, E.; Colonna, N.; Dressler, R.; Guerrero, C.; Gunsing, F.; Käppeler, F.; Kivel, N.; Pignatari, M.; Reifarth, R.; Schumann, D.; Wallner, A.; Altstadt, S.; Andriamonje, S.; Andrzejewski, J.; Audouin, L.; Barbagallo, M.; Bécares, V.; Bečvář, F.; Belloni, F.; Berthier, B.; Billowes, J.; Boccone, V.; Bosnar, D.; Brugger, M.; Calviani, M.; Calviño, F.; Cano-Ott, D.; Carrapiço, C.; Cerutti, F.; Chiaveri, E.; Chin, M.; Cortés, G.; Cortés-Giraldo, M. A.; Dillmann, I.; Domingo-Pardo, C.; Duran, I.; Dzysiuk, N.; Eleftheriadis, C.; Fernández-Ordóñez, M.; Ferrari, A.; Fraval, K.; Ganesan, S.; García, A. R.; Giubrone, G.; Gómez-Hornillos, M. B.; Gonçalves, I. F.; González-Romero, E.; Gramegna, F.; Griesmayer, E.; Gurusamy, P.; Harrisopulos, S.; Heil, M.; Ioannides, K.; Jenkins, D. G.; Jericha, E.; Kadi, Y.; Karadimos, D.; Korschinek, G.; Krtička, M.; Kroll, J.; Langer, C.; Lebbos, E.; Leeb, H.; Leong, L. S.; Losito, R.; Lozano, M.; Manousos, A.; Marganiec, J.; Marrone, S.; Martinez, T.; Mastinu, P. F.; Mastromarco, M.; Meaze, M.; Mendoza, E.; Mengoni, A.; Milazzo, P. M.; Mingrone, F.; Mirea, M.; Mondalaers, W.; Paradela, C.; Pavlik, A.; Perkowski, J.; Plag, R.; Plompen, A.; Praena, J.; Quesada, J. M.; Rauscher, T.; Riego, A.; Roman, F.; Rubbia, C.; Sarmento, R.; Schillebeeckx, P.; Schmidt, S.; Tagliente, G.; Tain, J. L.; Tarrío, D.; Tassan-Got, L.; Tsinganis, A.; Tlustos, L.; Valenta, S.; Vannini, G.; Variale, V.; Vaz, P.; Ventura, A.; Vermeulen, M. J.; Versaci, R.; Vlachoudis, V.; Vlastou, R.; Ware, T.; Weigand, M.; Weiß, C.; Wright, T. J.; Žugec, P.; n TOF Collaboration

2014-02-01

The cross section of the Ni62(n,γ) reaction was measured with the time-of-flight technique at the neutron time-of-flight facility n_TOF at CERN. Capture kernels of 42 resonances were analyzed up to 200 keV neutron energy and Maxwellian averaged cross sections (MACS) from kT = 5-100 keV were calculated. With a total uncertainty of 4.5%, the stellar cross section is in excellent agreement with the the KADoNiS compilation at kT=30 keV, while being systematically lower up to a factor of 1.6 at higher stellar temperatures. The cross section of the Ni63(n ,γ) reaction was measured for the first time at n_TOF. We determined unresolved cross sections from 10 to 270 keV with a systematic uncertainty of 17%. These results provide fundamental constraints on s-process production of heavier species, especially the production of Cu in massive stars, which serve as the dominant source of Cu in the solar system.

Barrier Height Variation in Ni-Based AlGaN/GaN Schottky Diodes

NARCIS (Netherlands)

Hajlasz, Marcin; Donkers, Johan J.T.M.; Pandey, Saurabh; Hurkx, Fred; Hueting, Raymond J.E.; Gravesteijn, Dirk J.

2017-01-01

In this paper, we have investigated Ni-based AlGaN/GaN Schottky diodes comprising capping layers with silicon-Technology-compatible metals such as TiN, TiW, TiWN, and combinations thereof. The observed change in Schottky barrier height of a Ni and Ni/TiW/TiWN/TiW contact can be explained by stress

Metal porphyrin intercalated reduced graphene oxide nanocomposite utilized for electrocatalytic oxygen reduction

Directory of Open Access Journals (Sweden)

Mingyan Wang

2017-07-01

Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin –MtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and π–π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst

Synthesis, spectroscopy and photosensitizing properties of hydroxynitrophenyl porphyrins

Energy Technology Data Exchange (ETDEWEB)

Maestrin, Ana Paula J.; Tedesco, Antonio Claudio; Neri, Claudio R.; Gandini, Maria Elisa F.; Serra, Osvaldo A.; Iamamoto, Yassuko [Sao Paulo Univ., Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras. Inst. de Quimica]. E-mail: osaserra@usp.br

2004-10-01

The hydroxynitrophenyl porphyrins, 5,10,15,20-tetrakis(2-hydroxy-5-nitrophenyl)porphyrin and 5-mono(carboxyphenyl)-10,15,20-tris(2-hydroxy-5-nitrophenyl)porphyrin described in this work were prepared through Adler's method. These compounds were characterized by {sup 1}H NMR and light absorption and emission spectroscopy in the visible region. In order to demonstrate the involvement of {sup 1}O{sub 2} production, the uric (UA) acid test was carried out, which considers the decrease in the absorbance of UA at 293 nm following laser light irradiation of a solution containing UA and a photosensitizer. The results obtained demonstrate that these hydroxynitrophenyl porphyrins can be considered as promising photosensitizers in PDT. (author)

Building-up novel coordination polymer with Zn(II) porphyrin dimer ...

Indian Academy of Sciences (India)

mer with porphyrin dimer. Solution structures of the complexes along with binding studies in solution between ... porphyrin polymers by self-assembly is fascinating ..... ture determination. ..... J K M 2000 In The Porphyrin Handbook Kadish K M,.

Microstructure and Corrosion Behavior of Ni-Alloy/CrN Nanolayered Coatings

Directory of Open Access Journals (Sweden)

Hao-Hsiang Huang

2011-01-01

Full Text Available The Ni-alloy/CrN nanolayered coatings, Ni-Al/CrN and Ni-P/CrN, were deposited on (100 silicon wafer and AISI 420 stainless steel substrates by dual-gun sputtering technique. The influences of the layer microstructure on corrosion behavior of the nanolayered thin films were investigated. The bilayer thickness was controlled approximately 10 nm with a total coating thickness of 1m. The single-layer Ni-alloy and CrN coatings deposited at 350∘C were also evaluated for comparison. Through phase identification, phases of Ni-P and Ni-Al compounds were observed in the single Ni-alloy layers. On the other hand, the nanolayered Ni-P/CrN and Ni-Al/CrN coatings showed an amorphous/nanocrystalline microstructure. The precipitation of Ni-Al and Ni-P intermetallic compounds was suppressed by the nanolayered configuration of Ni-alloy/CrN coatings. Through Tafel analysis, the corr and corr values ranged from –0.64 to –0.33 V and 1.42×10−5 to 1.14×10−6 A/cm2, respectively, were deduced for various coating assemblies. The corrosion mechanisms and related behaviors of the coatings were compared. The coatings with a nanolayered Ni-alloy/CrN configuration exhibited a superior corrosion resistance to single-layer alloy or nitride coatings.

Thermal capture cross section for 58Ni (n,γ)59 Ni reaction

International Nuclear Information System (INIS)

Carbonari, A.W.; Pecequilo, B.R.S.

1989-01-01

The 58 Ni total thermal capture cross section was determined by suming the partial cross sections calculated for the primary transitions of the reaction 58 Ni (n,γ) 59 Ni. The primary transitions energies and intensities were determined from the 58 Ni thermal neutrons prompt gamma capture gamma rays spectrum in the 3.7 to 9.3 MeV region. The obtained value for the total cross section was 4.52 + 0.10b. (author) [pt

NiTiCu/AlN/NiTiCu shape memory thin film heterostructures for vibration damping in MEMS

Energy Technology Data Exchange (ETDEWEB)

Kaur, Navjot; Kaur, Davinder, E-mail: dkaurfph@iitr.ernet.in

2014-03-25

Highlights: • Fabrication of NiTiCu/AlN/NiTiCu heterostructure using dc/rf magnetron sputtering. • Exhibits highest hardness (38 GPa) and elastic modulus (187 GPa). • Enhanced dissipation of mechanical energy (E{sub d} = 5.7 N J). • High damping capacity (0.052) and figure of merit (∼0.62). • Can be applied for vibration damping in MEMS. -- Abstract: Shape memory alloy (NiTiCu) thin films coupled with piezoelectric AlN layer produce an intelligent material for vibration damping. In the present study pure NiTiCu, NiTiCu/AlN and NiTiCu/AlN/NiTiCu heterostructures have been deposited on Si substrate using magnetron sputtering technique. By the use of the interfaces and shape memory effect provided by NiTiCu layers, the damping capacity can be increased along with increase in stiffness and mechanical hardness. The heterostructures were characterized in terms of structural, electrical, morphological and mechanical properties by X-ray diffraction (XRD), four probe resistivity method, atomic force microscopy, field emission scanning electron microscopy, and nanoindentation. The NiTiCu/AlN/NiTiCu heterostructure exhibit enhanced mechanical and damping properties as compared to NiTiCu/AlN and pure NiTiCu. This enhancement in hardness and damping of the heterostructure could be attributed to the shape memory effect of NiTiCu, intrinsic piezoelectricity of AlN and increased number of interfaces in heterostructure that help in dissipation of mechanical vibrations. The findings of this work provide additional impetus for the application of these heterostructures in emerging fields of nanotechnology and microelectro mechanical (MEMS) devices.

NiTiCu/AlN/NiTiCu shape memory thin film heterostructures for vibration damping in MEMS

International Nuclear Information System (INIS)

Kaur, Navjot; Kaur, Davinder

2014-01-01

Highlights: • Fabrication of NiTiCu/AlN/NiTiCu heterostructure using dc/rf magnetron sputtering. • Exhibits highest hardness (38 GPa) and elastic modulus (187 GPa). • Enhanced dissipation of mechanical energy (E d = 5.7 N J). • High damping capacity (0.052) and figure of merit (∼0.62). • Can be applied for vibration damping in MEMS. -- Abstract: Shape memory alloy (NiTiCu) thin films coupled with piezoelectric AlN layer produce an intelligent material for vibration damping. In the present study pure NiTiCu, NiTiCu/AlN and NiTiCu/AlN/NiTiCu heterostructures have been deposited on Si substrate using magnetron sputtering technique. By the use of the interfaces and shape memory effect provided by NiTiCu layers, the damping capacity can be increased along with increase in stiffness and mechanical hardness. The heterostructures were characterized in terms of structural, electrical, morphological and mechanical properties by X-ray diffraction (XRD), four probe resistivity method, atomic force microscopy, field emission scanning electron microscopy, and nanoindentation. The NiTiCu/AlN/NiTiCu heterostructure exhibit enhanced mechanical and damping properties as compared to NiTiCu/AlN and pure NiTiCu. This enhancement in hardness and damping of the heterostructure could be attributed to the shape memory effect of NiTiCu, intrinsic piezoelectricity of AlN and increased number of interfaces in heterostructure that help in dissipation of mechanical vibrations. The findings of this work provide additional impetus for the application of these heterostructures in emerging fields of nanotechnology and microelectro mechanical (MEMS) devices

Measurement of urinary porphyrins and porphyrin precursors in Dutch hospital laboratories: a review of quality control over 5 years.

NARCIS (Netherlands)

Zuijderhoudt, F.M.; Weykamp, C.W.; Willems, J.L.

2003-01-01

BACKGROUND: We evaluated a quality control scheme for the measurement of urinary uroporphyrin, coproporphyrin, total urinary porphyrins and precursors of urinary porphyrins, delta-aminolevulinic acid and porphobilinogen that was performed in The Netherlands during a period of 5 years. METHODS: Six

Single-step electron transfer on the nanometer scale: ultra-fast charge shift in strongly coupled zinc porphyrin-gold porphyrin dyads.

Science.gov (United States)

Fortage, Jérôme; Boixel, Julien; Blart, Errol; Hammarström, Leif; Becker, Hans Christian; Odobel, Fabrice

2008-01-01

The synthesis, electrochemical properties, and photoinduced electron transfer processes of a series of three novel zinc(II)-gold(III) bisporphyrin dyads (ZnP--S--AuP(+)) are described. The systems studied consist of two trisaryl porphyrins connected directly in the meso position via an alkyne unit to tert-(phenylenethynylene) or penta(phenylenethynylene) spacers. In these dyads, the estimated center to center interporphyrin separation distance varies from 32 to 45 A. The absorption, emission, and electrochemical data indicate that there are strong electronic interactions between the linked elements, thanks to the direct attachment of the spacer on the porphyrin ring through the alkyne unit. At room temperature in toluene, light excitation of the zinc porphyrin results in almost quantitative formation of the charge shifted state (.+)ZnP--S--AuP(.), whose lifetime is in the order of hundreds of picoseconds. In this solvent, the charge-separated state decays to the ground state through the intermediate population of the zinc porphyrin triplet excited state. Excitation of the gold porphyrin leads instead to rapid energy transfer to the triplet ZnP. In dichloromethane the charge shift reactions are even faster, with time constants down to 2 ps, and may be induced also by excitation of the gold porphyrin. In this latter solvent, the longest charge-shifted lifetime (tau=2.3 ns) was obtained with the penta-(phenylenethynylene) spacer. The charge shift reactions are discussed in terms of bridge-mediated super-exchange mechanisms as electron or hole transfer. These new bis-porphyrin arrays, with strong electronic coupling, represent interesting molecular systems in which extremely fast and efficient long-range photoinduced charge shift occurs over a long distance. The rate constants are two to three orders of magnitude larger than for corresponding ZnP--AuP(+) dyads linked via meso-phenyl groups to oligo-phenyleneethynylene spacers. This study demonstrates the critical

Synthesis and properties of 5,10,15,20-tetra[4-(3,5-dioctoxybenzamidephenyl] porphyrin and its metal complexes

Directory of Open Access Journals (Sweden)

Lian Wenhui

2012-01-01

Full Text Available A novel 5,10,15,20-tetra[4-(3,5-dioctoxybenzamidephenyl]porphyrin and its transition metal complexes are reported in this paper. Their molecular structures were characterized by elemental analysis, IR spectra, 1HNMR spectra and UV-Vis spectra. Their spectroscopic properties were studied by Raman spectra, fluorescence spectra and X-ray photoelectron spectra (XPS. The fluorescence quantum yields have been measured at room temperature. The fluorescence intensity of porphyrin ligand was stronger than that of the complexes. In Raman spectra, there was much difference between porphyrin ligand and its metal complexes due to changes of the symmetry of porphyrin plane. In the XPS spectra, the replacement of the free-base protons by a metal ion to form the metalloporphyrin increases the symmetry of the molecule also introduces an electron with-drawing group into the center of the porphyrin ligand which increases the N1s binding energy.

[meso-5,10,15,20-Tetrakis(5-bromothiophen-2-ylporphyrinato-κ4N,N′,N′′,N′′′]nickel(II

Directory of Open Access Journals (Sweden)

R. Prasath

2012-04-01

Full Text Available The NiII atom in the title porphyrin complex, [Ni(C36H16Br4N4S4], is in a square-planar geometry defined by four pyrrole N atoms. There is considerable buckling in the porphyrin ring with the dihedral angles between the N4 donor set and the pyrrole rings being in the range 17.0 (3–18.8 (3°. Each of the six-membered chelate rings is twisted about an Ni—N bond and the dihedral angles between diagonally opposite chelate rings are 13.08 (15 and 13.45 (11°; each pair of rings is orientated in opposite directions. The bromothienyl rings are twisted out of the plane of the central N4 core with dihedral angles in the range 51.7 (2–74.65 (19°. Supramolecular chains along [001] are formed through C—H...Br interactions in the crystal packing. Three of the four bromothienyl units are disordered over two coplanar positions of opposite orientation with the major components being in 0.691 (3, 0.738 (3 and 0.929 (9 fractions.

Supramolecular Allosteric Cofacial Porphyrin Complexes

International Nuclear Information System (INIS)

Oliveri, Christopher G.; Gianneschi, Nathan C.; Nguyen, Son Binh T.; Mirkin, Chad A.; Stern, Charlotte L.; Wawrzak, Zdzislaw; Pink, Maren

2008-01-01

Nature routinely uses cooperative interactions to regulate cellular activity. For years, chemists have designed synthetic systems that aim toward harnessing the reactivity common to natural biological systems. By learning how to control these interactions in situ, one begins to allow for the preparation of man-made biomimetic systems that can efficiently mimic the interactions found in Nature. To this end, we have designed a synthetic protocol for the preparation of flexible metal-directed supramolecular cofacial porphyrin complexes which are readily obtained in greater than 90% yield through the use of new hemilabile porphyrin ligands with bifunctional ether-phosphine or thioether-phosphine substituents at the 5 and 15 positions on the porphyrin ring. The resulting architectures contain two hemilabile ligand-metal domains (Rh I or Cu I sites) and two cofacially aligned porphyrins (Zn II sites), offering orthogonal functionalities and allowing these multimetallic complexes to exist in two states, 'condensed' or 'open'. Combining the ether-phosphine ligand with the appropriate Rh I or Cu I transition-metal precursors results in 'open' macrocyclic products. In contrast, reacting the thioether-phosphine ligand with RhI or CuI precursors yields condensed structures that can be converted into their 'open' macrocyclic forms via introduction of additional ancillary ligands. The change in cavity size that occurs allows these structures to function as allosteric catalysts for the acyl transfer reaction between X-pyridylcarbinol (where X = 2, 3, or 4) and 1-acetylimidazole. For 3- and 4-pyridylcarbinol, the 'open' macrocycle accelerates the acyl transfer reaction more than the condensed analogue and significantly more than the porphyrin monomer. In contrast, an allosteric effect was not observed for 2-pyridylcarbinol, which is expected to be a weaker binder and is unfavorably constrained inside the macrocyclic cavity.

Iron porphyrins doped sol-gel glasses: a chemometric study

International Nuclear Information System (INIS)

Sacco, Herica C.; Vidoto, Ednalva A.; Nascimento, Otaciro R.

2000-01-01

This paper describes the optimized conditions for preparation of iron porphyrin-template doped silica Fe PDS-template) obtained by the sol-gel process. The following porphyrins (Fe P) were used: Fe TFPP Cl, Fe TDCSPP(Na) 4 Cl and Fe TCPP(Na) 4 Cl. Pyridine or 4-phenylimidazole was used as template. The variables that present significant influence on iron porphyrin loading on xerogel were identified and the values that maximize the iron porphyrin loading on xerogel were established . The variables (Solvent volume, fractional factorial design in two levels, 2 5-1 type, generating 16 total experiments for each Fe P studied. (author)

Multi-step intramolecular excitation energy transfer in dendritic pyrene-phosphorus(V)porphyrin heptads

Energy Technology Data Exchange (ETDEWEB)

Hirakawa, Kazutaka, E-mail: hirakawa.kazutaka@shizuoka.ac.jp [Applied Chemistry and Biochemical Engineering Course, Department of Engineering, Graduate School of Integrated Science and Technology, Shizuoka University, Johoku 3-5-1, Naka-ku, Hamamatsu, Shizuoka 432-8561 (Japan); Department of Optoelectronics and Nanostructure Science, Graduate School of Science and Technology, Shizuoka University, Johoku 3-5-1, Naka-ku, Hamamatsu, Shizuoka 432-8561 (Japan); Segawa, Hiroshi [Department of Multi-Disciplinary Science - General Systems Studies, Graduate School of Arts and Sciences, The University of Tokyo, Komaba 3-8-1, Meguro-ku, Tokyo 153-8904 (Japan); Research Center for Advanced Science and Technology, The University of Tokyo, Komaba 4-6-1, Meguro-ku, Tokyo 153-8904 (Japan)

2016-11-15

Dendritic heptad molecules in which four pyrenyl groups are connected at the central phosphorus atom of the edge-porphyrins of the center-to-edge type porphyrin trimers were synthesized to investigate a multi-step excitation energy transfer. As the central energy acceptor, two types porphyrins which one was phosphorus(V)tetraphenylporphyrin (H2) and another was its derivative substituted by butoxy groups at four para-position of meso-phenyl groups (H1) were used. In the photoexcited state of the pyrene units, the excitation energy transfer to the central-porphyrin unit was observed in toluene. The excitation energy transfer is considered to be through two pathways; one is a stepwise pathway through the edge-porphyrin unit and another is a direct excitation energy transfer to the central porphyrin. The direct excitation energy transfer from pyrenes to the edge-porphyrin and central-porphyrin were observed in the case for H1. From the excited state of the edge-porphyrins, the excitation energy transfer to the central-porphyrin occurs in the H1 case. In the H2 case, the excitation energy of central-porphyrin is higher than that of H1, and the electron transfer from edge-porphyrin to the central-porphyrin become predominant process. - Highlights: • Dendritic pyrene-porphyrin heptads were synthesized. • Excitation energy transfer occurs from the pyrenyl moiety to the phosphorus(V)porphyrin. • The stepwise and direct energy transfer pathways were observed. • The quantum yields of these energy transfer pathways could be determined.

Multi-step intramolecular excitation energy transfer in dendritic pyrene-phosphorus(V)porphyrin heptads

International Nuclear Information System (INIS)

Hirakawa, Kazutaka; Segawa, Hiroshi

2016-01-01

Dendritic heptad molecules in which four pyrenyl groups are connected at the central phosphorus atom of the edge-porphyrins of the center-to-edge type porphyrin trimers were synthesized to investigate a multi-step excitation energy transfer. As the central energy acceptor, two types porphyrins which one was phosphorus(V)tetraphenylporphyrin (H2) and another was its derivative substituted by butoxy groups at four para-position of meso-phenyl groups (H1) were used. In the photoexcited state of the pyrene units, the excitation energy transfer to the central-porphyrin unit was observed in toluene. The excitation energy transfer is considered to be through two pathways; one is a stepwise pathway through the edge-porphyrin unit and another is a direct excitation energy transfer to the central porphyrin. The direct excitation energy transfer from pyrenes to the edge-porphyrin and central-porphyrin were observed in the case for H1. From the excited state of the edge-porphyrins, the excitation energy transfer to the central-porphyrin occurs in the H1 case. In the H2 case, the excitation energy of central-porphyrin is higher than that of H1, and the electron transfer from edge-porphyrin to the central-porphyrin become predominant process. - Highlights: • Dendritic pyrene-porphyrin heptads were synthesized. • Excitation energy transfer occurs from the pyrenyl moiety to the phosphorus(V)porphyrin. • The stepwise and direct energy transfer pathways were observed. • The quantum yields of these energy transfer pathways could be determined.

Bionic catalysis of porphyrin for electrochemical detection of nucleic acids

International Nuclear Information System (INIS)

Li Jie; Lei Jianping; Wang Quanbo; Wang Peng; Ju Huangxian

2012-01-01

Highlights: ► This is the first application of bionic catalysis of porphyrin as detection probe in bioanalysis. ► Porphyrin–DNA–gold nanoparticle probe is synthesized. ► Binding model between FeTMPyP and DNA is verified. ► The detection probe shows excellent electrocatalytic behaviors toward the reduction of O 2 . ► The biosensor exhibited good performance with wide linear range and high specificity. - Abstract: A novel electrochemical strategy was designed for the detection of DNA based on the bionic catalysis of porphyrin. The detection probe was prepared via the assembly of thiolated double strand DNA (dsDNA) with gold nanoparticles (AuNPs), and then interacted with cationic iron (III) meso-tetrakis (N-methylphyridinum-4-yl) porphyrin (FeTMPyP) via groove binding along the dsDNA surface. The resulting nanocomplex was characterized with transmission electron microscopy, UV–vis absorption and circular dichroism spectroscopy. The FeTMPyP–DNA–AuNPs probe on gold electrode demonstrated the excellent electrocatalytic behaviors toward the reduction of O 2 due to the largely loading of FeTMPyP and good conductivity. Based on bionic catalysis of porphyrin for the reduction of O 2 , the resulting biosensor exhibited a good performance for the detection of DNA with a wide linear range from 1 × 10 −12 to 1 × 10 −8 mol L −1 and detection limit of 2.5 × 10 −13 mol L −1 at the signal/noise of 3. More importantly, the biosensor presented excellent ability to discriminate the perfectly complementary target and the mismatched stand. This strategy could be conveniently extended for detection of other biomolecules. To the best of our knowledge, this is the first application of bionic catalysis of porphyrin as detection probe and opens new opportunities for sensitive detection of biorecognition events.

Excitation energy deactivation funnel in 3-substituted BODIPY-porphyrin conjugate

International Nuclear Information System (INIS)

Nguyen, Nguyen Tran; Verbelen, Bram; Leen, Volker; Waelkens, Etienne; Dehaen, Wim; Kruk, Mikalai

2016-01-01

BODIPYs absorb in the visible region which is complementary to that of porphyrins and therefore can be suggested as promising antenna groups to improve the light-harvesting potential of porphyrins. A boron-dipyrromethene dye was combined at the 3-position with a Zn-porphyrin to afford a conjugate. The fluorescence of the conjugate was found to originate from the BODIPY moiety independently of the excitation wavelength due to an unique set of energy transfer rates between the BODIPY and Zn-porphyrin moieties. The fluorescence intensity was shown to be tunable over a wide range using the solvent properties. This feature makes the studied BODIPY-porphyrin conjugate a promising compound for the design of new photochromic devices.

Excitation energy deactivation funnel in 3-substituted BODIPY-porphyrin conjugate

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Nguyen Tran [Chemistry Department, University of Education, The University of DaNang, Ton Duc Thang 459, Da Nang (Viet Nam); Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven (Belgium); Verbelen, Bram; Leen, Volker [Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven (Belgium); Waelkens, Etienne [Department of Cellular and Molecular Medicine, KU Leuven, Herestraat 49, Box 901, 3000 Leuven (Belgium); Dehaen, Wim, E-mail: wim.dehaen@kuleuven.be [Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven (Belgium); Kruk, Mikalai, E-mail: m.kruk@belstu.by [Belarusian State Technological University, Physics Department, Sverdlov Str., 13a, Minsk 220006 (Belarus)

2016-11-15

BODIPYs absorb in the visible region which is complementary to that of porphyrins and therefore can be suggested as promising antenna groups to improve the light-harvesting potential of porphyrins. A boron-dipyrromethene dye was combined at the 3-position with a Zn-porphyrin to afford a conjugate. The fluorescence of the conjugate was found to originate from the BODIPY moiety independently of the excitation wavelength due to an unique set of energy transfer rates between the BODIPY and Zn-porphyrin moieties. The fluorescence intensity was shown to be tunable over a wide range using the solvent properties. This feature makes the studied BODIPY-porphyrin conjugate a promising compound for the design of new photochromic devices.

Porphyrin-phospholipid interaction and ring metallation depending on the phospholipid polar head type.

Science.gov (United States)

Ramos, Ana P; Pavani, Christiane; Iamamoto, Yassuko; Zaniquelli, Maria E D

2010-10-01

The interaction between a hydrophobically modified 5,10,15,20-tetrakis(4-N-tetradecyl-pyridyl) porphyrin and three phospholipids: two negatively charged, DMPA (the sodium salt of dimyristoyl-sn-glycero-phosphatidyl acid) and DMPG (the sodium salt of 1,2-dimyristoyl-sn-glycero-3-[phospho-rac-(1-glycerol)]) and a zwitterionic DMPC (dimyristoyl-sn-glycero-phosphatidylcholine), were studied by means of surface pressure isotherms and spectroscopic methods. The interaction results in partial or total metallation of the porphyrin with zinc ions in the presence of negatively charged phospholipids, as attested by UV-vis and luminescence spectroscopy of the transferred films. In the presence of the zwitterionic phospholipid no insertion of zinc ion in the porphyrin ring is detected. These results are relevant for the understanding of photosensitizer-lipid-carrier binding for use in photodynamic therapy. Copyright 2010 Elsevier Inc. All rights reserved.

Iron porphyrins doped sol-gel glasses: a chemometric study

Energy Technology Data Exchange (ETDEWEB)

Sacco, Herica C.; Vidoto, Ednalva A.; Nascimento, Otaciro R. [Soap Paulo Univ (USP), Sao Carlos (Brazil). Inst. de Fisica; Biazzotto, Juliana C.; Serra, Osvaldo A.; Iamamoto, Yassuko [Sao Paulo Univ. (USP), Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras; Ciuffi, Katia J.; Mello, Cesar A.; Oliveira, Daniela C. de [Universidade de Franca , SP (Brazil)

2000-07-01

This paper describes the optimized conditions for preparation of iron porphyrin-template doped silica Fe (PDS-template) obtained by the sol-gel process. The following porphyrins (Fe P) were used: Fe TFPP Cl, Fe TDCSPP(Na){sub 4}Cl and Fe TCPP(Na){sub 4} Cl. Pyridine or 4-phenylimidazole was used as template. The variables that present significant influence on iron porphyrin loading on xerogel were identified and the values that maximize the iron porphyrin loading on xerogel were established. The variables Solvent volume, fractional factorial design in two levels, 2{sup 5-1} type, generating 16 total experiments for each Fe P studied. (author)

Formation and thermodynamic stability of (polymer + porphyrin) supramolecular structures in aqueous solutions

International Nuclear Information System (INIS)

Costa, Viviana C.P. da; Hwang, Barrington J.; Eggen, Spencer E.; Wallace, Megan J.; Annunziata, Onofrio

2014-01-01

Highlights: • Thermodynamic stability of a (polymer + porphyrin) supramolecular structure was characterized. • Isothermal titration calorimetry provided two ways to determine reaction enthalpies. • Exothermic (polymer + porphyrin) binding competes with porphyrin self-association. • (Polymer + porphyrin) binding is entropically favored with respect to porphyrin self-association. • Spectral shifts show importance of porphyrin central hydrogens in polymer binding. - Abstract: Optical properties of porphyrins can be tuned through (polymer + porphyrin) (host + guest) binding in solution. This gives rise to the formation of supramolecular structures. In this paper, the formation, thermodynamic stability and spectroscopic properties of (polymer + porphyrin) supramolecular structures and their competition with porphyrin self-association were investigated by both isothermal titration calorimetry (ITC) and absorption spectroscopy. Specifically, reaction enthalpies and equilibrium constants were measured for meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS) self-association and TPPS binding to the polymer poly(vinylpyrrolidone) (PVP, 40 kg/mol) in aqueous solutions at pH 7 and three different temperatures (12, 25 and 37 °C). ITC, compared to spectroscopic techniques, provides two independent means to determine reaction enthalpies: direct measurements and Van’t Hoff plot. This was used as a criterion to assess that (1) self-association of TPPS is limited to the formation of dimers and (2) TPPS binds to PVP in its monomeric state only. The formation of TPPS dimers and (PVP + TPPS) supramolecular structures are both enthalpically driven. However, (polymer + porphyrin) binding was found to be entropically favored compared to dimerization. Furthermore, the reaction enthalpies of these two processes significantly depend on temperature. This behavior was attributed to hydrophobic interactions. Finally, the limiting absorption spectra of monomeric, dimeric and polymer

Porphyrins - blood test

Science.gov (United States)

... page: //medlineplus.gov/ency/article/003372.htm Porphyrins blood test To use the sharing features on this page, ... blood or the urine . This article discusses the blood test. How the Test is Performed A blood sample ...

Depresión en niños y niñas con cáncer

Directory of Open Access Journals (Sweden)

Yolanda del Refugio González-Hernández

2006-01-01

Full Text Available La depresión infantil existe y está presente en muchos niños y niñas hoy en día, principalmente porque se han incrementando los factores de riesgo para su aparición. Uno de estos grandes factores es la pérdida de la salud, la amenaza de daño a la propia estructura física, psicológica y social del niño o la niña. El cáncer infantil logra romper esta estructura. La presente revisión bibliográfica pretende exponer aquellos estudios que se han realizado sobre la depresión infantil, su relación con el cáncer, así como el análisis de los resultados de estudios longitudinales de sobrevivientes de cáncer infantil sobre la presencia o ausencia de secuelas psicosociales importantes que influyan en su funcionamiento actual.

N -annulated perylene as an efficient electron donor for porphyrin-based dyes: Enhanced light-harvesting ability and high-efficiency Co(II/III)-based dye-sensitized solar cells

KAUST Repository

Luo, Jie; Xu, Mingfei; Li, Renzhi; Huang, Kuo-Wei; Jiang, Changyun; Qi, Qingbiao; Zeng, Wangdong; Zhang, Jie; Chi, Chunyan; Wang, Peng; Wu, Jishan

2014-01-01

Porphyrin-based dyes recently have become good candidates for dye-sensitized solar cells (DSCs). However, the bottleneck is how to further improve their light-harvesting ability. In this work, N-annulated perylene (NP) was used to functionalize

An unsymmetrical porphyrin and its metal complexes: synthesis, spectroscopy, thermal analysis and liquid crystal properties

Directory of Open Access Journals (Sweden)

CHANGFU ZHUANG

2009-09-01

Full Text Available The synthesis and characterization of a new unsymmetrical porphyrin liquid crystal, 5-(4-stearoyloxyphenylphenyl-10,15,20-triphenylporphyrin (SPTPPH2 and its transition metal complexes (SPTPPM, M(II = Zn, Fe, Co, Ni, Cu or Mn are reported. Their structure and properties were studied by elemental analysis, and UV–Vis, IR, mass and 1H-HMR spectroscopy. Their luminescent properties were studied by excitation and emission spectroscopy. The quantum yields of the S1 ® S0 fluorescence were measured at room temperature. According to thermal studies, the complexes have a higher thermal stability (no decomposition until 200 °C. Differential scanning calorimetry (DSC data and an optical textural photograph, obtained using a polarizing microscope (POM, indicate that the porphyrin ligand had liquid crystalline character and that it exhibited more than one mesophase and a low-lying phase transition temperature, with transition temperatures of 19.3 and 79.4 °C; the temperature range of the liquid crystal (LC phase of the ligand was 70.1 °C.

Effects of divalent cations, EDTA and chitosan on the uptake and photoinactivation of Escherichia coli mediated by cationic and anionic porphyrins.

Science.gov (United States)

Gsponer, Natalia S; Spesia, Mariana B; Durantini, Edgardo N

2015-03-01

The effect of divalent cations, EDTA and chitosan (CS) on the uptake and photoinactivation of Escherichia coli produced by 5,10,15,20-tetrakis(4-N,N,N-trimethylammoniumphenyl)porphyrin (TMAP(4+)), 5,10-di(4-methylphenyl)-15,20-di(4-N,N,N-trimethylammoniumphenyl)porphyrin (MPAP(2+)) and 5,10,15,20-tetra(4-sulphonatophenyl)porphyrin (TPPS(4-)) were examined under different conditions. These porphyrins were rapidly bound to E. coli cells (TMAP(4+), MPAP(2+) and TPPS(4-), respectively. The addition of Ca(2+) or Mg(2+) to the cultures enhanced the uptake of MPAP(2+) and TPPS(4-) by cells. In contrast, the amount of TMAP(4+) bound to cells was decreased. The presence of EDTA produced an increase in the uptake of porphyrins by cells, while CS mainly enhanced the amount of TPPS(4-) bound to E. coli. The photoinactivation of E. coli cells mediated by TMAP(4+) was highly effective even at low concentration (1μM) and short irradiation period (5min). However, a reduction in the phototoxicity was found for TMAP(4+) in presence of Ca(2+) and Mg(2+). In contrast, the phototoxic activity mediated by MPAP(2+) and TPPS(4-) was increased. Addition of EDTA did not show effect on the photoinactivation induced by cationic porphyrins, while a small enhance was found for TPPS(4-). Moreover, inactivation of E. coli cells was achieved in the presence CS. This cationic polymer was antimicrobial by itself in the dark. Using a slightly toxic CS concentration, the phototoxic activity induced by TMAP(4+) was diminished. This effect was mainly observed at lower concentration of TMAP(4+) (0.5-1μM). In contrast, an increase in E. coli photoinactivation was obtained for MPAP(2+) and TPPS(4-) in presence of CS. Thus, this natural polymeric destabilizer agent mainly benefited the photoinactivation mediated by TPPS(4-). Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrogen bond controlled adduct formation of meso-tetra(4-sulfonatophenyl)porphyrin with protic acids: a UV-vis spectroscopic study.

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Zakavi, Saeed; Rahiminezhad, Hajar; Alizadeh, Robabeh

2010-12-01

Interaction of meso-tetra(4-sulfonatophenyl)porphyrin (H2tppS4) with weak and strong protic acid have been studied by UV-vis spectroscopy in water, dichloromethane and methanol. Different shifts of the Soret and Q(0,0) bands in the three solvents, the aggregation of diprotonated species and the stability of porphyrin-acid adducts in the solution, may be explained by the inter- and intramolecular hydrogen bonds. Whilst, the addition of excess amounts of tetra-n-butylammonium chloride to H2tppS4(Cl)2 in dichloromethane has little to no effect on the UV-vis spectrum of the dication, gradual addition of tetra-n-butylammonium hydrogen sulfate to the dichloromethane solution of H2tppS4(H2SO4)2 leads to the degradation of adducts and the release of porphryin. The results of this study clearly show the crucial role played by hydrogen bonds between the porphyrin diprotonated species and the counter ion in the stability of porphyrin diacids in solution. Copyright © 2010 Elsevier B.V. All rights reserved.

Molecular modeling of cationic porphyrin-anthraquinone hybrids as DNA topoisomerase IIβ inhibitors.

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Arba, Muhammad; Ruslin; Ihsan, Sunandar; Tri Wahyudi, Setyanto; Tjahjono, Daryono H

2017-12-01

Human DNA Topoisomerase II has been regarded as a promising target in anticancer drug discovery. In the present study, we designed six porphyrin-anthraquinone hybrids bearing pyrazole or pyridine group as meso substituents and evaluated their potentials as DNA Topoisomerase IIβ inhibitor. First, we investigated the binding orientation of porphyrin hybrids into DNA topoisomerase IIβ employing AutoDock 4.2 and then performed 20-ns molecular dynamics simulations to see the dynamic stability of each porphyrin-Topo IIβ complex using Amber 14. We found that the binding of porphyrin hybrids occured through intercalation and groove binding mode in addition interaction with the amino acid residues constituting the active cavity of Topo IIβ. Each porphyrin-Topo IIβ complex was stabilized during 20-ns dynamics simulations. The MM-PBSA free energy calculation shows that the binding affinities of porphyrin hybrids were modified with the number of meso substituent. Interestingly, the affinity of all porphyrin hybrids to Topo IIβ was stronger than that of native ligand (EVP), indicating the potential of the designed porphyrin to be considered in experimental research. Copyright © 2017 Elsevier Ltd. All rights reserved.

Efficient sensitization of dye-sensitized solar cells by novel triazine-bridged porphyrin-porphyrin dyads.

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Zervaki, Galateia E; Roy, Mahesh S; Panda, Manas K; Angaridis, Panagiotis A; Chrissos, Emmanouel; Sharma, Ganesh D; Coutsolelos, Athanassios G

2013-09-03

Two novel porphyrin-porphyrin dyads, the symmetrical Zn[Porph]-Zn[Porph] (2) and unsymmetrical Zn[Porph]-H2[Porph] (4), where Zn[Porph] and H2[Porph] are the metalated and free-base forms of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin, respectively, in which two porphyrin units are covalently bridged by 1,3,5-triazine, have been synthesized via the stepwise amination of cyanuric chloride. The dyads are also functionalized by a terminal carboxylic acid group of a glycine moiety attached to the triazine group. Photophysical measurements of 2 and 4 showed broaden and strengthened absorptions in their visible spectra, while electrochemistry experiments and density functional theory calculations revealed negligible interaction between the two porphyrin units in their ground states but appropriate frontier orbital energy levels for use in dye-sensitized solar cells (DSSCs). The 2- and 4-based solar cells have been fabricated and found to exhibit power conversion efficiencies (PCEs) of 3.61% and 4.46%, respectively (under an illumination intensity of 100 mW/cm(2) with TiO2 films of 10 μm thickness). The higher PCE value of the 4-based DSSC, as revealed by photovoltaic measurements (J-V curves) and incident photon-to-current conversion efficiency (IPCE) spectra of the two cells, is attributed to its enhanced short-circuit current (J(sc)) under illumination, high open-circuit voltage (V(oc)), and fill factor (FF) values. Electrochemical impedance spectra demonstrated shorter electron-transport time (τd), longer electron lifetime (τe), and high charge recombination resistance for the 4-based cell, as well as larger dye loading onto TiO2.

Investigation of the porphyrine role at the mechanism of radioprotection

International Nuclear Information System (INIS)

Demoukhamedova, S.D.; Alieva, I.N.; Aliev, D.I.

2002-01-01

Full text: To date, it is well known that unfavourable radioecological conditions capable effect on the oxygen transport system in an living organism, particularly, on the conformational state of hemoglobin. Underlying mechanism is more active autoxidation of Hb(O 2 )4 into met-hemoglobin. Decreasing of the oxygen binding to the heme group of protein as a result of modified effect of ionization was observed into peripheral blood of people living on the polluted territory. Porphyrin, the main component of hemoglobin has been showed a wide range radioprotector properties. So, the conformational reorganization of the porphyrin ring plays an important role at the mechanism of hemoglobin functioning. In this report the result of conformational study, quantum-chemical calculations and theoretical calculation of frequencies and intensities of normal oscillations of IR-absorption spectrum of the porphyrin molecule at the NO-binding are presented. Computational program 'LEV' was used in all carried calculations. Due to changes into IR-spectrum of different complexes, the mechanism underlying the ligand bond formation are discussed. The theoretical frequencies of normal oscillations, satisfactorily described the porphyrin experimental IR-spectrum are received. On the base of both obtained normal oscillation forms and potential energy distribution of vibrational coordinates the detailed theoretical interpretation of the porphyrin molecule vibrational spectrum as well as the analysis of the nature of each absorption band the porphyrin molecule IR-spectrum have been carried out. Porphyrin molecule force field analysis has been showed that the ring electron density is irregular. The results of this study may be used at the theoretical calculations of IR-absorption spectrum of different metallo complexes of the porphyrin

Effects of Bulky Substituents of Push-Pull Porphyrins on Photovoltaic Properties of Dye-Sensitized Solar Cells.

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Higashino, Tomohiro; Kawamoto, Kyosuke; Sugiura, Kenichi; Fujimori, Yamato; Tsuji, Yukihiro; Kurotobi, Kei; Ito, Seigo; Imahori, Hiroshi

2016-06-22

To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push-pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push-pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO2-dye-electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO2 by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO2 resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.

Porphyrin Diacid-Polyelectrolyte Assemblies: Effective Photocatalysts in Solution

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Sabine Frühbeißer

2016-05-01

Full Text Available Developing effective and versatile photocatalytic systems is of great potential in solar energy conversion. Here we investigate the formation of supramolecular catalysts by electrostatic self-assembly in aqueous solution: Combining positively charged porphyrins with negatively charged polyelectrolytes leads to nanoscale assemblies where, next to electrostatic interactions, π–π interactions also play an important role. Porphyrin diacid-polyelectrolyte assemblies exhibit a substantially enhanced catalytic activity for the light-driven oxidation of iodide. Aggregates with the hexavalent cationic porphyrin diacids show up to 22 times higher catalytic activity than the corresponding aggregates under neutral conditions. The catalytic activity can be increased by increasing the valency of the porphyrin and by choice of the loading ratio. The structural investigation of the supramolecular catalysts took place via atomic force microscopy and small angle neutron scattering. Hence, a new facile concept for the design of efficient and tunable self-assembled photocatalysts is presented.

Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

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Thompson, Mark E.; Diev, Viacheslav; Hanson, Kenneth; Forrest, Stephen R.

2015-08-18

A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: ##STR00001## By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,.beta. fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

[Renal excretion of total porphyrins and hippuric acid in rats].

Science.gov (United States)

Gartzke, J; Burck, D

1986-09-01

The amounts of total porphyrins, hippuric acid and creatinine, excreted in urine by adult male Wistar rats, exhibited normal distributions for hippuric acid and creatinine, but a bimodal distribution for total porphyrins. This typical distribution of total porphyrins was still observed when creatinine was used as reference parameter. In biochemical and toxicological experiments in rats, the tested parameters should be therefore be investigated for homogeneity.

Effects of Immersion Solvent on Photovoltaic and Photophysical Properties of Porphyrin-Sensitized Solar Cells.

Science.gov (United States)

Hayashi, Hironobu; Higashino, Tomohiro; Kinjo, Yuriko; Fujimori, Yamato; Kurotobi, Kei; Chabera, Pavel; Sundström, Villy; Isoda, Seiji; Imahori, Hiroshi

2015-08-26

Memory effects in self-assembled monolayers (SAMs) of zinc porphyrin carboxylic acid on TiO2 electrodes have been demonstrated for the first time by evaluating the photovoltaic and electron transfer properties of porphyrin-sensitized solar cells prepared by using different immersion solvents sequentially. The structure of the SAM of the porphyrin on the TiO2 was maintained even after treating the porphyrin monolayer with different neat immersion solvents (memory effect), whereas it was altered by treatment with solutions containing different porphyrins (inverse memory effect). Infrared spectroscopy shows that the porphyrins in the SAM on the TiO2 could be exchanged with the same or analogous porphyrin, leading to a change in the structure of the porphyrin SAM. The memory and inverse memory effects are well correlated with a change in porphyrin geometry, mainly the tilt angle of the porphyrin along the long molecular axis from the surface normal on the TiO2, as well as with kinetics of electron transfer between the porphyrin and TiO2. Such a new structure-function relationship for DSSCs will be very useful for the rational design and optimization of photoelectrochemical and photovoltaic properties of molecular assemblies on semiconductor surfaces.

De la afectación a nuevas posibilidades: niñas y niños en el conflicto armado colombiano

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María Isabel Valencia-Suescún, Colombia

2015-07-01

Full Text Available (Analítico: El artículo presenta resultados preliminares de la investigación, obtenidos de la validación de instrumentos realizada con niños y niñas de Benposta-nación de muchach@s en Bogotá (talleres creativos y entrevistas semiestructuradas. Relaciona resultados obtenidos en la aproximación al estado del arte sobre niñez y conflicto armado derechos como salud y alimentación, educación, juego y esparcimiento. Evidencia vulneraciones de derechos de protección (por homicidios, reclutamiento forzado, desplazamiento y de participación. Analiza la afectación en procesos de construcción de subjetividad. Aborda potencias y capacidades de acción que se develan en estos contextos y en procesos de socialización política en los cuales niños y niñas se involucran.

Prevalencia del VIH en niños, niñas y adolescentes en situación de calle y explotación sexual comercial: una revisión sistemática

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Camilo Noreña-Herrera

Full Text Available Resumen: Describir la prevalencia de infección por el VIH en los niños, niñas y adolescentes en situación de calle y de explotación sexual comercial y las características de lugar, tiempo, población y tipo de muestreo de los estudios. Revisión sistemática, no metaanálisis, con búsqueda en 10 bases de datos electrónicas: Science Direct, MEDLINE, OVID, LILACS, Wiley InterScience, MD Consult, Springer Link, Embase, Web of Science, Ebsco. También, existe búsqueda complementada en dos bibliotecas de escuelas de salud pública y páginas de Internet de Organizaciones de las Naciones Unidas y lista de referencias de los artículos incluidos. Seleccionamos estudios observacionales con niños, niñas y adolescentes en situación de calle y explotación sexual comercial en edades entre diez y veinte años, con resultados de las prevalencias del VIH. Fueron recuperadas 9.829 referencias, 15 cumplieron los criterios de inclusión y componen esta síntesis descriptiva. De este conjunto, doce fueron realizados en niños, niñas y adolescentes en situación de calle y tres en población en explotación sexual comercial. Todos fueron estudios transversales. La prevalencia del VIH en la población en situación de calle va desde 0% en Dallas, Estados Unidos y Cochabamba, Bolivia hasta 37,4% en San Petersburgo, Rusia. En la población en explotación sexual comercial, va desde 2% en Toronto, Canadá hasta 20% en Calcuta, India. Concluimos que la infección por VIH está presente en los niños, niñas y adolescentes en situación de calle y de explotación sexual. Siendo necesarias acciones de prevención, diagnóstico y tratamiento como un asunto prioritario de la salud pública y una responsabilidad ética de los gobiernos y la sociedad.

Photophysical properties of novel Porphyrin-Flavin Dyads

International Nuclear Information System (INIS)

Stark, S.

2001-10-01

Photosynthesis belongs to the fundamentals of life on earth, therefore it is an important matter in natural sciences. The basic principle of photosynthesis is the transformation of solar light into chemical energy. The starting steps of photosynthesis are light-induced energy- and electron-transfer-steps with singular efficiency. One attempt to enlighten the molecular processes involved is to synthesize simpler model systems with similar properties. Important research goals are the dependencies of light-induced processes on distance and orientation of donor and acceptor. A second aim next to the clarification of the molecular conditions of photosynthesis is to create molecular light-driven machines. The most simple so-called biomimetic model system consists of an electron-donor connected to an electron-acceptor via a spacer-group. This simplest form is also referred to as dyad. Beyond dyads far more complicated compounds have been introduced consisting of several donors and/or acceptors, so-called triads, tetrads, pentads etc. Usually porphyrin serves as electron-donor. Next to chinones several other electron-acceptors are used, e.g. anthracene, pyromellitimide and fullerene. Artificial photosynthetic centers are often more stable and/or the excited states are easier to detect compared to the natural photosynthetic center. The photophysical characteristics of four dyads are reported in this work. The dyads consist of porphyrin (either free-base or zinc-metallated) and flavin, connected by different spacers. These dyads reveal photo-induced electron transfer from porphyrin to flavin and energy-transfer in the reversed direction with different efficiencies. The object of the study is the dependency of these processes on the structural features. The spacer of the dyads 1a-1c is an aromatic bridge which leads to well defined donor-acceptor distances. Because of this structure conjugation through the spacer is increased, whereas the absorption in the visible and near UV

Revisión de la utilidad y fiabilidad de la Confusion Assessment Method en atención especializada y primaria, 2013

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Carmen Carrera Castro

2015-05-01

Full Text Available Objetivo: El objetivo de la revisión literaria fue mostrar los estudios originales publicados en los últimos 5 años, que evalúan la sensibilidad, la especificidad y la fiabilidad de la escala Confusion Assessment Method (CAM y toman como patrón referencia al Manual Diagnóstico y Estadístico de los Trastornos Mentales (DMS para obtener una visión global y actual de la validez y confiabilidad de esta herramienta diagnóstica. Metodología: Se procedió a una búsqueda genérica en pubmed con los descriptores del MESH Confusión, sensibilidad y especificidad, Técnicas y procedimientos diagnósticos y los términos libres CAM o Confusion Assessment Method, generando 995 artículos originales, tras revisión y clasificación con tablas estructuradas, de forma independiente por cada autor. Resultados: Se hallaron 4 estudios: 2 de validación, traducción y adaptación cultural al alemán y al tailandés, 1 de validación en pacientes paliativos y 1 de un estudio de cohorte comparativo de evaluación sobre el rendimiento de la CAM con el DSM-IV y el CIE-10 (Clasificación Estadística Internacional de Enfermedades, 10ª revisión. Aunque los trabajos hallados han sido escasos y se precisa de más investigaciones, en comparación proporcional con años anteriores se han llevado a cabo más estudios. El patrón de referencia más utilizado ha sido la DSM-IV. Conclusión : La CAM es una herramienta diagnóstica válida con alta sensibilidad y especificidad cuando es manejada por personal previamente adiestrado. Es precisa, fiable, segura, rápida y económica en el ámbito de la investigación. Sin embargo, se necesitan más investigaciones.

Matriz de relación primaria en casos de niños y niñas con problemas de aprendizaje

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Marta Isabel López

2010-10-01

Full Text Available La relación entre las dificultades de aprendizaje (DA y el contexto relacional primario de niño o niña que las presenta, es un aspecto importante reportado en la literatura y en la práctica clínica, y constituye un factor esencial en la comprensión del fenómeno de las DA. Nuestro objetivo en el estudio fue comprender la historia del desarrollo relacional de nueve niños y niñas con DA en la ciudad de Medellín, Colombia, para encontrar relaciones de sentido entre dicha historia y sus DA. La metodología utilizada fue cualitativa desde el enfoque hermenéutico-fenomenológico. Encontramos una dinámica de relación primaria caracterizada por ansiedad y apoyo constante al niño o niña por parte de la madre, y por un padre por fuera de la relación madre - niño o niña. Esa dinámica se reproduce en las relaciones con otras personas y situaciones, favoreciendo la emergencia de un niño o niña en un lugar de discapacidad.

Matriz de relación primaria en casos de niños y niñas con problemas de aprendizaje

Directory of Open Access Journals (Sweden)

Marta Isabel López

2010-01-01

Full Text Available La relación entre las dificultades de aprendizaje (DA y el contexto relacional primario del niño o niña que las presenta, es un aspecto importante reportado en la literatura y en la práctica clínica, y constituye un factor esencial en la comprensión del fenómeno de las DA. Nuestro objetivo en el estudio fue comprender la historia del desarrollo relacional de nueve niños y niñas con DA en la ciudad de Medellín, Colombia, para encontrar relaciones de sentido entre dicha historia y sus DA. La metodología utilizada fue cualitativa desde el enfoque hermenéutico-fenomenológico. Encontramos una dinámica de relación primaria caracterizada por ansiedad y apoyo constante al niño o niña por parte de la madre, y por un padre por fuera de la relación madre - niño o niña. Esa dinámica se reproduce en las relaciones con otras personas y situaciones, favoreciendo la emergencia de un niño o niña en un lugar de discapacidad.

N -annulated perylene as an efficient electron donor for porphyrin-based dyes: Enhanced light-harvesting ability and high-efficiency Co(II/III)-based dye-sensitized solar cells

KAUST Repository

Luo, Jie

2014-01-08

Porphyrin-based dyes recently have become good candidates for dye-sensitized solar cells (DSCs). However, the bottleneck is how to further improve their light-harvesting ability. In this work, N-annulated perylene (NP) was used to functionalize the Zn-porphyrin, and four "push-pull"-type NP-substituted and fused porphyrin dyes with intense absorption in the visible and even in the near-infrared (NIR) region were synthesized. Co(II/III)-based DSC device characterizations revealed that dyes WW-5 and WW-6, in which an ethynylene spacer is incorporated between the NP and porphyrin core, showed pantochromatic photon-to-current conversion efficiency action spectra in the visible and NIR region, with a further red-shift of about 90 and 60 nm, respectively, compared to the benchmark molecule YD2-o-C8. As a result, the short-circuit current density was largely increased, and the devices displayed power conversion efficiencies as high as 10.3% and 10.5%, respectively, which is comparable to that of the YD2-o-C8 cell (η = 10.5%) under the same conditions. On the other hand, the dye WW-3 in which the NP unit is directly attached to the porphyrin core showed a moderate power conversion efficiency (η = 5.6%) due to the inefficient π-conjugation, and the NP-fused dye WW-4 exhibited even poorer performance due to its low-lying LUMO energy level and nondisjointed HOMO/LUMO profile. Our detailed physical measurements (optical and electrochemical), density functional theory calculations, and photovoltaic characterizations disclosed that the energy level alignment, the molecular orbital profile, and dye aggregation all played very important roles on the interface electron transfer and charge recombination kinetics. © 2013 American Chemical Society.

Dehalogenation of lindane by a variety of porphyrins and corrins.

OpenAIRE

Marks, T S; Allpress, J D; Maule, A

1989-01-01

The dehalogenation of lindane by a range of hemoproteins, porphyrins, and corrins has been tested under reducing conditions in the presence of dithiothreitol. In addition, a series of porphyrin-metal ion complexes have been prepared and have also been screened for the capacity to dehalogenate lindane. Hemoglobin, hemin, hematin, and chlorophyll alpha all catalyzed the dehalogenation of lindane, as did all of the corrins tested. The porphyrins which did not contain metal centers--coproporphyri...

Boronated porphyrins in NCT: Results with a new potent tumor localizer

International Nuclear Information System (INIS)

Kahl, S.B.; Koo, M.S.; Laster, B.H.; Fairchild, R.G.

1988-01-01

Several chemical methods are available for the solubilization of boronated porphyrins. We have previously reported the tumor localization of nido carboranyl porphyrins in which the icosahedral carborane cages have been opened to give B 9 C 2 anions. One of these species has shown tumor boron levels of nearly 50 μg B/g when delivered by week-long subcutaneous infusions. We report here recent in vivo experiments with a new, highly water-soluble porphyrin based on the hematoporphyrin-type of compound in which aqueous solubility is achieved using the two propionic acid side chains of the ''natural'' porphyrin frame. 7 refs

Peripherally Metalated Porphyrins with Applications in Catalysis, Molecular Electronics and Biomedicine.

Science.gov (United States)

Longevial, Jean-François; Clément, Sébastien; Wytko, Jennifer A; Ruppert, Romain; Weiss, Jean; Richeter, Sébastien

2018-04-24

Porphyrins are conjugated, stable chromophores with a central core that binds a variety of metal ions and an easily functionalized peripheral framework. By combining the catalytic, electronic or cytotoxic properties of selected transition metal complexes with the binding and electronic properties of porphyrins, enhanced characteristics of the ensemble are generated. This review article focuses on porphyrins bearing one or more peripheral transition metal complexes and discusses their potential applications in catalysis or biomedicine. Modulation of the electronic properties and intramolecular communication through coordination bond linkages in bis-porphyrin scaffolds is also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anion vacancy-mediated ferromagnetism in atomic-thick Ni3N nanosheets

Science.gov (United States)

Xia, Baorui; Wang, Tongtong; Chi, Xiao; Yu, Xiaojiang; Liu, Peitao; Zhang, Jingyan; Xi, Shibo; Du, Yonghua; Gao, Daqiang

2017-12-01

Realizing spin and electronic behavior of two-dimensional ultrathin nanosheets is significant to construct next generation nanoelectronics. Here, atomic-thick Ni3N nanosheets with clear room temperature ferromagnetism and high saturation magnetization (1.2 emu/g) are reported. X-ray magnetic circular dichroism and first-principles calculation results give the evidence that the observed intrinsic ferromagnetism in Ni3N nanosheets originates from the surface N-deficiency, where alignments of localized large magnetic moments of Ni in the vicinity of the N defect can be aligned parallel to activate macroscopic ferromagnetism. These ultrathin Ni3N nanosheets show great potential application in next-generation electron devices.

Novel drug delivery strategies for porphyrins and porphyrin precursors

Science.gov (United States)

Morrow, D. I. J.; Donnelly, R. F.

2009-06-01

superficial lesions, such as actinic keratosis. In addition, photodynamic antimicrobial chemotherapy (PACT) is attracting increasing interest for the treatment of infection. However, delivery strategies for topical PDT and PACT are still based on application of rather simplistic cream and solution formulations, with little consideration given to thermodynamics, targeting or the physicochemical properties of the active agent. Purpose-designed dosage forms for topical delivery of aminolevulinic acid or its esters include creams containing penetration enhancers and/or iron chelators, pressure sensitive patches and bioadhesive patches. Such systems aim to enhance drug delivery across the stratum corneum and keratinised debris overlying neoplastic lesions and improve subsequent protoporphyrin IX (PpIX) production. The alternative to using porphyrin precursors is the use of pre-formed photosensitisers. However, owing to their relatively high molecular weights, conventional topical application is not appropriate. Innovative strategies, such as the use of needle-free injections and microneedle arrays, bypass the stratum corneum, enabling rapid and targeted delivery not only porphyrin precursors but also pre-formed photosensitisers. This presentation will review drug delivery work published to date in the fields of PDT and PACT. In addition, the benefits of employing the latest advances in pharmaceutical technology will be highlighted.

Perturbations in DNA structure upon interaction with porphyrins revealed by chemical probes, DNA footprinting and molecular modelling.

Science.gov (United States)

Ford, K G; Neidle, S

1995-06-01

The interactions of several porphyrins with a 74 base-pair DNA sequence have been examined by footprinting and chemical protection methods. Tetra-(4-N-methyl-(pyridyl)) porphyrin (TMPy), two of its metal complexes and tetra-(4-trimethylanilinium) porphyrin (TMAP) bind to closely similar AT-rich sequences. The three TMPy ligands produce modest changes in DNA structure and base accessibility on binding, in contrast to the large-scale conformational changes observed with TMAP. Molecular modelling studies have been performed on TMPy and TMAP bound in the AT-rich minor groove of an oligonucleotide. These have shown that significant structural change is needed to accommodate the bulky trimethyl substituent groups of TMAP, in contrast to the facile minor groove fit of TMPy.

Porphyrin involvement in redshift fluorescence in dentin decay

Science.gov (United States)

Slimani, A.; Panayotov, I.; Levallois, B.; Cloitre, T.; Gergely, C.; Bec, N.; Larroque, C.; Tassery, H.; Cuisinier, F.

2014-05-01

The aim of this study was to evaluate the porphyrin involvement in the red fluorescence observed in dental caries with Soprolife® light-induced fluorescence camera in treatments mode (SOPRO, ACTEON Group, La Ciotat, France) and Vistacam® camera (DÜRR DENTAL AG, Bietigheim-Bissingen, Germany). The International Caries Detection and Assessment System (ICDAS) was used to rand the samples. Human teeth cross-sections, ranked from ICDAS score 0 to 6, were examined by epi-fluorescence microscopy and Confocal Raman microscopy. Comparable studies were done with Protoporphyrin IX, Porphyrin I and Pentosidine solutions. An RGB analysis of Soprolife® images was performed using ImageJ Software (1.46r, National Institutes of Health, USA). Fluorescence spectroscopy and MicroRaman spectroscopy revealed the presence of Protoporphyrin IX, in carious enamel, dentin and dental plaque. However, the presence of porphyrin I and pentosidine cannot be excluded. The results indicated that not only porphyrin were implicated in the red fluorescence, Advanced Glygation Endproducts (AGEs) of the Maillard reaction also contributed to this phenomenon.

Studies of interactions of porphyrins with transfer RNA by high-resolution NMR

International Nuclear Information System (INIS)

Birdsall, W.J.; Lehigh Univ., Bethlehem, PA; Anderson, W.R. Jr; Foster, N.

1989-01-01

The interactions of tetra-4N-methulpyridyl porphyrin and its zinc (II), copper (II) and manganese (III) complexes with brewer's yeast type V phenylalanine specific tRNA have been evaluated by high-resolution NMR. Differences in chemical shifts have been noted for thre proton resonances in response to the presence of small quantities of the fre base and the zinc and copper complexes. The protons giving rise to these signals are located on bases T54 and psi55, both of which are involved in the primary intraloop and interloop hydroen bonds that hold the D and TpsiC loops together in the tertiary structure. In addition, broadening of specific resonances due to hydrogen bonding protons in the D stem at low ratios of porphyrin to tRNA indicates that the association of porphyrins increases the rate of imino proton exchange. The titration of the tRNA with the manganese (III) complex did not eveal shifts or spcific broadening comparable to the other porpyrins at low ratios. The changes induced in the NMR spectrum of tNA by porphyrins define their site of interaction with the polynucleotide. This site, at the outside of the elbow-bend in the tRNA 'L', is different from the locus of binding in tRNA for other classical DNA intercalators. Furthermore, a new mode of binding may be involved that is neither intercalative nor simply electrostatic. (author). 36 refs.; 4 figs

Magnetic interactions in iron (III) porphyrin chlorides

International Nuclear Information System (INIS)

Ernst, J.; Subramanian, Japyesan; Fuhrhop, J.H.

1977-01-01

Intermolecular exchange interactions in iron(III) porphyrin chlorides (porphyrin = OEP, proto, TPP) have been studied by X-ray structure, EPR and magnetic susceptibility studies. The crystal structure of Fe(III)OEP-Cl was found to be different from that of the other two. Different types of exchange broadened EPR-spectra are obtained which are attributable to the arrangement in the crystals. The EPR results correlate well with magnetic susceptibility data. (orig.) [de

Urinary porphyrin excretion in hepatitis C infection

OpenAIRE

Vogeser, Michael; Jacob, Karl; Zachoval, Reinhart

1999-01-01

A high prevalence of hepatitis C virus infection in porphyria cutanea tarda in some populations suggests a close link between viral hepatitis and alteration of porphyrin metabolism. Moreover, there is evidence of a role of porphyrinopathies in hepatocarcinogenesis. The aim of our study was to obtain data on the prevalence and patterns of heme metabolism alterations in patients with chronic hepatitis C virus infection. Urinary porphyrin excretion was prospectively studied in 100 consecutive ou...

Reduced graphene oxide and porphyrin. An interactive affair in 2-D.

Science.gov (United States)

Wojcik, Aleksandra; Kamat, Prashant V

2010-11-23

Photoexcited cationic 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP) undergoes charge-transfer interaction with chemically reduced graphene oxide (RGO). Formation of the ground-state TMPyP-RGO complex in solution is marked by the red-shift of the porphyrin absorption band. This complexation was analyzed by Benesi-Hildebrand plot. Porphyrin fluorescence lifetime reduced from 5 to 1 ns upon complexation with RGO, indicating excited-state interaction between singlet excited porphyrin and RGO. Femtosecond transient absorption measurements carried out with TMPyP adsorbed on RGO film revealed fast decay of the singlet excited state, followed by the formation of a longer-living product with an absorption maximum around 515 nm indicating the formation of a porphyrin radical cation. The ability of TMPyP-RGO to undergo photoinduced charge separation was further confirmed from the photoelectrochemical measurements. TMPyP-RGO coated conducting glass electrodes are capable of generating photocurrent under visible excitation. These results are indicative of the electron transfer between photoexcited porphyrin and RGO. The role of graphene in accepting and shuttling electrons in light-harvesting assemblies is discussed.

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

KAUST Repository

Anderson, Carly E.; Vagin, Sergei I.; Hammann, Markus; Zimmermann, Leander; Rieger, Bernhard

2013-01-01

Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

KAUST Repository

Anderson, Carly E.

2013-09-18

Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical and electrical characteristics of annealed Ni/Au and Ni/Ir/Au contacts on AlGaN

Energy Technology Data Exchange (ETDEWEB)

Ngoepe, P.N.M., E-mail: phuti.ngoepe@up.ac.za [Department of Physics, University of Pretoria, Private Bag X20, Hatfield 0028 (South Africa); Meyer, W.E.; Auret, F.D.; Omotoso, E.; Diale, M. [Department of Physics, University of Pretoria, Private Bag X20, Hatfield 0028 (South Africa); Swart, H.C.; Duvenhage, M.M.; Coetsee, E. [Department of Physics, University of the Free State, P.O. Box 339, Bloemfontein 9300 (South Africa)

2016-01-01

The evolution of Ni/Au and Ni/Ir/Au metal contacts deposited on AlGaN was investigated at different annealing temperatures. The samples were studied with electrical and chemical composition techniques. I–V characteristics of the Schottky diodes were optimum after 500 and 600 °C annealing for Ni/Au and Ni/Ir/Au based diodes, respectively. The depth profiles of the contacts were measured by x-ray photoelectron spectroscopy and time of flight secondary ion mass spectroscopy. These chemical composition techniques were used to examine the evolution of the metal contacts in order to verify the influence the metals have on the electrical properties of the diodes. The insertion of Ir as a diffusion barrier between Ni and Au effected the electrical properties, improving the stability of the contacts at high temperatures. Gold diffused into the AlGaN film, degrading the electrical properties of the Ni/Au diode. At 500 °C, the insertion of Ir, however, prevented the in-diffusion of Au into the AlGaN substrate.

Enhanced photocatalytic efficiency in zirconia buffered n-NiO/p-NiO single crystalline heterostructures by nanosecond laser treatment

Energy Technology Data Exchange (ETDEWEB)

Molaei, R.; Bayati, M. R.; Alipour, H. M.; Nori, S.; Narayan, J. [Department of Materials Science and Engineering, NC State University, EB-1, Raleigh, North Carolina 27695-7907 (United States)

2013-06-21

We report the formation of NiO based single crystalline p-n junctions with enhanced photocatalytic activity induced by pulsed laser irradiation. The NiO epilayers were grown on Si(001) substrates buffered with cubic yttria-stabilized zirconia (c-YSZ) by using pulsed laser deposition. The NiO/c-YSZ/Si heterostructures were subsequently laser treated by 5 pulses of KrF excimer laser (pulse duration = 25 Multiplication-Sign 10{sup -9} s) at lower energies. Microstructural studies, conducted by X-ray diffraction ({theta}-2{theta} and {phi} techniques) and high resolution transmission electron microscope, showed a cube-on-cube epitaxial relationship at the c-YSZ/Si interface; the epitaxial relationship across the NiO/c-YSZ interface was established as NiO<111 > Double-Vertical-Line Double-Vertical-Line c-YSZ<001> and in-plane NiO<110> Double-Vertical-Line Double-Vertical-Line c-YSZ<100>. Electron microscopy studies showed that the interface between the laser annealed and the pristine region as well as the NiO/c-YSZ interface was atomically sharp and crystallographically continuous. The formation of point defects, namely oxygen vacancies and NiO, due to the coupling of the laser photons with the NiO epilayers was confirmed by XPS. The p-type electrical characteristics of the pristine NiO epilayers turned to an n-type behavior and the electrical conductivity was increased by one order of magnitude after laser treatment. Photocatalytic activity of the pristine (p-NiO/c-YSZ/Si) and the laser-annealed (n-NiO/p-NiO/c-YSZ/Si) heterostructures were assessed by measuring the decomposition rate of 4-chlorophenol under UV light. The photocatalytic reaction rate constants were determined to be 0.0059 and 0.0092 min{sup -1} for the as-deposited and the laser-treated samples, respectively. The enhanced photocatalytic efficiency was attributed to the suppressed charge carrier recombination in the NiO based p-n junctions and higher electrical conductivity. Besides, the oxygen vacancies

Electrical characteristic of spin coated Fe-Porphyrin on Cu substrates

Energy Technology Data Exchange (ETDEWEB)

Utari, E-mail: utari@ugm.ac.id [Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Sebelas Maret, Jl. Ir. Sutami 36A Kentingan Surakarta 57126 (Indonesia); Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Bulaksumur BLS 21 Yogyakarta 55281 (Indonesia); Kusumandari,; Purnama, Budi, E-mail: bpurnama@mipa.uns.ac.id [Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Sebelas Maret, Jl. Ir. Sutami 36A Kentingan Surakarta 57126 (Indonesia); Mudasir [Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Bulaksumur BLS 21 Yogyakarta 55281 (Indonesia); Abraha, Kamsul [Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Bulaksumur BLS 21 Yogyakarta 55281 (Indonesia)

2016-06-17

This paper describes the electrical-characteristics of Fe-Porphyrin thin films on Cu substrates. The thin layer samples used were deposited by spin coating methods on Cu-substrates at room temperature with and without induced magnetic field in the plane direction of the surface films. Fe-porphyrin was dissolved in chloroform and mixed with a magnetic stirrer for 60 min at a rotational speed of 200 rpm. The experimental results show that the mobility carrier charge of the Fe-Porphyrin layer with induced magnetic field during deposition has lower value than that without induced magnetic field case. The decrease of the mobility can be attribute to the change of the surface morphology in Fe-porphyrin films by means of increase in the nano-granular/nano-molecular size caused by the induce magnetic field.

Challenging Density Functional Theory Calculations with Hemes and Porphyrins

Science.gov (United States)

de Visser, Sam P.; Stillman, Martin J.

2016-01-01

In this paper we review recent advances in computational chemistry and specifically focus on the chemical description of heme proteins and synthetic porphyrins that act as both mimics of natural processes and technological uses. These are challenging biochemical systems involved in electron transfer as well as biocatalysis processes. In recent years computational tools have improved considerably and now can reproduce experimental spectroscopic and reactivity studies within a reasonable error margin (several kcal·mol−1). This paper gives recent examples from our groups, where we investigated heme and synthetic metal-porphyrin systems. The four case studies highlight how computational modelling can correctly reproduce experimental product distributions, predicted reactivity trends and guide interpretation of electronic structures of complex systems. The case studies focus on the calculations of a variety of spectroscopic features of porphyrins and show how computational modelling gives important insight that explains the experimental spectra and can lead to the design of porphyrins with tuned properties. PMID:27070578

Challenging Density Functional Theory Calculations with Hemes and Porphyrins

Directory of Open Access Journals (Sweden)

Sam P. de Visser

2016-04-01

Full Text Available In this paper we review recent advances in computational chemistry and specifically focus on the chemical description of heme proteins and synthetic porphyrins that act as both mimics of natural processes and technological uses. These are challenging biochemical systems involved in electron transfer as well as biocatalysis processes. In recent years computational tools have improved considerably and now can reproduce experimental spectroscopic and reactivity studies within a reasonable error margin (several kcal·mol−1. This paper gives recent examples from our groups, where we investigated heme and synthetic metal-porphyrin systems. The four case studies highlight how computational modelling can correctly reproduce experimental product distributions, predicted reactivity trends and guide interpretation of electronic structures of complex systems. The case studies focus on the calculations of a variety of spectroscopic features of porphyrins and show how computational modelling gives important insight that explains the experimental spectra and can lead to the design of porphyrins with tuned properties.

Porphyrin-containing polyaspartamide gadolinium complexes as potential magnetic resonance imaging contrast agents.

Science.gov (United States)

Yan, Guo-Ping; Li, Zhen; Xu, Wei; Zhou, Cheng-Kai; Yang, Lian; Zhang, Qiao; Li, Liang; Liu, Fan; Han, Lin; Ge, Yuan-Xing; Guo, Jun-Fang

2011-04-04

Porphyrin-containing polyaspartamide ligands (APTSPP-PHEA-DTPA) were synthesized by the incorporation of diethylenetriaminepentaacetic acid (DTPA) and 5-(4'-aminophenyl)-10,15,20-tris(4'-sulfonatophenyl) porphyrin, trisodium salt (APTSPP) into poly-α,β-[N-(2-hydroxyethyl)-l-aspartamide] (PHEA). These ligands were further reacted with gadolinium chloride to produce macromolecule-gadolinium complexes (APTSPP-PHEA-DTPA-Gd). Experimental data of (1)H NMR, IR, UV and elemental analysis evidenced the formation of the polyaspartamide ligands and gadolinium complexes. In vitro and in vivo property tests indicated that APTSPP-PHEA-DTPA-Gd possessed noticeably higher relaxation effectiveness, less toxicity to HeLa cells, and significantly higher enhanced signal intensities (SI) of the VX2 carcinoma in rabbits with lower injection dose requirement than that of Gd-DTPA. Moreover, APTSPP-PHEA-DTPA-Gd was found to greatly enhance the contrast of MR images of the VX2 carcinoma, providing prolonged intravascular duration, and distinguished the VX2 carcinoma and normal tissues in rabbits according to MR image signal enhancements. These porphyrin-containing polyaspartamide gadolinium complexes can be used as the candidates of contrast agents for targeted MRI to tumors. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Pobreza, niñez y diferenciación social

Directory of Open Access Journals (Sweden)

María Paula Montesinos

2003-11-01

Full Text Available Del conjunto de dimensiones que atraviesa la existencia de los niños que viven en contextos de pobreza urbana y diversidad cultural, nos interesa centrarnos en algunas de las que se hacen presentes en las escuelas a las que asisten, ubicadas en el cordón sur de la ciudad de Buenos Aires. Las distintas representaciones y practicas respecto de esta niñez contribuyen a la producción de espacios institucionales de inclusión / exclusión y en la conformación de los itinerarios sociales, escolares y urbanos que efectivamente transitan estos niños. Dar cuenta de estos cruces complejos es el objeto de este trabajo, cuyo material empirico se apoya en un amplio conjunto de entrevistas realizadas a directores de escuelas primarias de la zona mencionada.

Futuros posibles, el potencial creativo de niñas y niños para la construcción de paz

Directory of Open Access Journals (Sweden)

David Arturo Ospina-Ramírez

2017-01-01

Full Text Available Este artículo visibiliza algunos resultados de una investigación que busca desnaturalizar la violencia como elemento constitutivo de la subjetividad de niñas y niños provenientes de contextos de conflicto armado y reconocer las capacidades que hay en ellas y ellos y en sus relaciones más significativas para aportar a procesos de construcción de paz, democracia y reconciliación. Se toman recursos del construccionismo social y las narrativas generativas. La investigación cuenta con una metodología cualitativa con orientación hermenéutica y crítica, mediante un análisis categorial de narrativas. Este documento se centra en los potenciales del desarrollo humano para construir paz que despliegan niñas y niños en contextos de conflicto armado, haciendo especial énfasis en el potencial creativo para la transformación de conflictos, encontrando que las niñas, los niños y sus familias logran construir paz por medio de la creatividad y el afecto para encontrar futuros posibles.

Electrochemical behavior of free-radical derivatives of tetra(4hydroxyl-3,5-di-tert-butylphenyl) porphyrin

Energy Technology Data Exchange (ETDEWEB)

Pokhodenko, V.D.; Melezhik, A.V.; Platonova, E.P.; Vovk, D.N.

1984-08-01

The electrochemical behavior of free-radical derivatives of tetra(4hydroxyl-3,5-di-tert-butylphenyl) porphyrins and their complexes with Mg(II), Zn(II), Ni(II), CU(II), and Pd(II) ions was studied by the methods of voltamperometry, ESR, and spectrophotometry. It was shown that the introduction of free-radical substituents into the porphin macrocycle leads to a substantial decrease in the oxidation and reduction potentials of the complexes. The degree of conjunction of substituents with the porphin macrocycle is estimated according to the difference of the redox potentials of free-radical and quinoid derivatives of metalloporphyrins.

Confusion

Science.gov (United States)

... suddenly or there are other symptoms, such as: Cold or clammy skin Dizziness or feeling faint Fast pulse Fever Headache Slow or rapid breathing Uncontrolled shivering Also call 911 if: Confusion has come on ...

Fe-N and (Fe, Ni)-N Fine Powders for Magnetic Recording

International Nuclear Information System (INIS)

Chen Ziyu; Li Fashen

1998-01-01

Combining Moessbauer spectroscopy with magnetic property measurement, we have studied Fe-N and (Fe, Ni)-N powders for magnetic recording. The typical particles of the core (α-Fe)/shell (γ'-Fe 4 N) structure have been successfully prepared. All the products are stabilized in a multi-organic solution. It has been found that the coercivity can be changed from 300 to 800 Oe by adjusting the shape of the particles. The special saturation magnetization of the particles can be adjusted from 120 to 180emu/g and their chemical stability is improved by substituting nickel for iron in γ'-Fe 4 N. Following experiments for corrosion resistance, it is expected that (Fe, Ni)-N and the core/shell particles will be applied as recording media in the near future

Fe-N and (Fe, Ni)-N Fine Powders for Magnetic Recording

Energy Technology Data Exchange (ETDEWEB)

Chen Ziyu; Li Fashen [Lanzhou University, Department of Physics (China)

1998-12-15

Combining Moessbauer spectroscopy with magnetic property measurement, we have studied Fe-N and (Fe, Ni)-N powders for magnetic recording. The typical particles of the core ({alpha}-Fe)/shell ({gamma}'-Fe{sub 4}N) structure have been successfully prepared. All the products are stabilized in a multi-organic solution. It has been found that the coercivity can be changed from 300 to 800 Oe by adjusting the shape of the particles. The special saturation magnetization of the particles can be adjusted from 120 to 180emu/g and their chemical stability is improved by substituting nickel for iron in {gamma}'-Fe{sub 4}N. Following experiments for corrosion resistance, it is expected that (Fe, Ni)-N and the core/shell particles will be applied as recording media in the near future.

Innovación Pedagógica para la integración de los niños y niñas con discapacidad auditiva a la educación regular

Directory of Open Access Journals (Sweden)

Sonia Freyle Pérez

2002-05-01

Full Text Available Se analizó la integración de niños (as con discapacidad auditiva a escuelas regulares y la utilización de innovaciones pedagógicas que faciliten el aprendizaje de dichos niños. Se utilizó la obserrvación y entrevista validadas con la triangulación de fuentes. Metodología cualitativa. Se constató que la integración del discapacitado auditivo presentó debilidades en el proceso de enseñanza-aprendizaje, por falta de acompañamiento, carencia de estrategias que coadyuven en la participación de los representates del niños discapacitado, tampoco existe actualización del docente. Se requiere un instructor-traductor en el lenguaje de señas. Se necesitan adecuaciones curriculares según las necesidades del discapacitado auditivo.

Local Electric Field Effects on Rhodium-Porphyrin and NHC-Gold Catalysts

Science.gov (United States)

2015-01-05

AFRL-OSR-VA-TR-2015-0023 (NII) - Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold Catalysts MATTHEW KANAN LELAND STANFORD JUNIOR UNIV...Effects on Rhodium -Porphyrin and NHC-Gold Catalysts Principal Investigator: Matthew W. Kanan Project Publications: 1. “An Electric Field–Induced Change...Stanford University Grant/Contract Title The full title of the funded effort. (NII)-Local Electric Field Effects on Rhodium -Porphyrin and NHC-Gold

Interactions of tetracationic porphyrins with DNA and their effects on DNA cleavage

Science.gov (United States)

Lebedeva, Natalya Sh.; Yurina, Elena S.; Gubarev, Yury A.; Syrbu, Sergey A.

2018-06-01

The interaction of tetracationic porphyrins with DNA was studied using UV-Vis absorption, fluorescence spectroscopy and viscometry, and the particle sizes were determined. Аs cationic porphyrins, two isomer porphyrins, 3,3‧,3″,3‴-(5,10,15,20-Porphyrintetrayl)tetrakis(1-methylpyridinium) (TMPyP3) and 4,4‧,4″,4‴-(5,10,15,20-Porphyrintetrayl)tetrakis(1-methylpyridinium) (TMPyP4), were studied. They differ in the position of NCH3+ group in phenyl ring of the porphyrins and hence, in degree of freedom of rotation of the phenyl rings about the central macrocycle. It was found that intercalated complexes are formed at DNA/porphyrin molar ratios (R) of 2.2 and 3.9 for TMPyP3 и TMPyP4, respectively. Decreasing R up to 0.4 and 0.8 for TMPyP3 и TMPyP4, respectively, leads mainly to formation of outside complexes due to π-π stacking between the porphyrin chromophores interacting electrostatically with phosphate framework of DNA. Each type of the obtained complexes was characterized using Scatchard approach. It was ascertained that the affinity of TMPyP4 to DNA is stronger than TMPyP3, meanwhile the wedge effect of the latter is higher. The differences between the porphyrin isomers become more evident at irradiation of their complexes with DNA. It was established that irradiation of the intercalated complexes results in DNA fragmentation. In the case of TMPyP4, DNA fragments of different size are formed. The irradiation of the outside DNA/porphyrin complexes leads to cleavage of DNA (TMPyP3 and TMPyP4) and partial destruction of the complex due to photolysis of the porphyrin (TMPyP3).

Electron transfer between a zinc porphyrin photo-sensitized in the visible, and various acceptors, in aqueous and micellar solutions

International Nuclear Information System (INIS)

Le Roux, Dominique

1983-01-01

This research thesis addresses the study of reactions occurring during the transformation of solar energy in chemical energy, and more precisely the search for photochemical systems allowing the dissociation of water into hydrogen and oxygen. In this study on water photolysis, the author chose to use a porphyrin soluble in water, the zinc tetra-meta-N-methylpyridinium porphyrin, as one of its isomer provided a good efficiency in hydrogen formation. Before reporting the study of electron photo-transfer, the author reports the study of photo-physical and photochemical properties of this porphyrin. Then, in the case of a well known electron acceptor (methyl viologen), he studied the influence of Coulomb effects on the kinetics of direct electron transfer, and on the kinetics of recombination of formed species. He also studied the influence of organised systems (cationic micelles) on these reactions when using a viologen with long chains. He finally reports the study of reactions of the triplet state of this porphyrin with metallic complexes

Role of complement in porphyrin-induced photosensitivity

International Nuclear Information System (INIS)

Lim, H.W.; Gigli, I.

1981-01-01

Addition of porphyrins to sera of guinea pigs in vitro, followed by irradiation with 405 nm light, resulted in dose-dependent inhibitions of hemolytic activity of complement. With guinea pig as an animal model, we also found that systemically administered porphyrins, followed by irradiation with 405 nm light, resulted in dose-dependent inhibition of CH50 in vivo. The erythrocytes from porphyrin-treated guinea pigs showed an increased susceptibility to hemolysis induced by 405 nm irradiation in vitro. Clinical changes in these animals were limited to light-exposed areas and consisted of erythema, crusting, and delayed growth of hair. Histologically, dermal edema, dilation of blood vessels, and infiltration of mononuclear and polymorphonuclear cells were observed. Guinea pigs irradiated with ultraviolet-B developed erythema, but had no alteration of their complement profiles. It is suggested that complement products may play a specific role in the pathogenesis of the cutaneous lesions of some porphyrias

The synthesis of chlorophyll-a biosynthetic precursors and methyl substituted iron porphyrins

International Nuclear Information System (INIS)

Matera, K.M.

1988-01-01

The biosynthetic intermediates were incubated in a plant system. The activity levels calculated show that magnesium 6-acrylate porphyrins and one of the magnesium 6-β-hydroxypropionate porphyrins are not intermediates. In addition, plant systems incubated with 18 O 2 were found to synthesize magnesium 2,4-divinyl pheoporphyrin-a 5 incorporated with 18 O at the 9-carbonyl oxygen. Mass spectroscopy confirmed the presence of the oxygen label, thus eliminating one of two hypothesized pathways to chlorophyll-a. An overall description is given of iron porphyrins and iron porphyrin containing proteins. The function of the propionic side chains of the heme prosthetic group during electron transport reactions will be investigated. The synthesis of a series of iron(III) hexamethyl porphyrins with increasingly longer substituents in the remaining two peripheral positions of the porphyrin is described. Models for NMR studies of iron chlorin containing enzymes are discussed. Iron(III) pyropheophorbide-a and methyl pyropheophorbide-a were synthesized in addition to 5-CD 3 , 10-CD 2 iron(III) pyropheophorbide-a and methyl pyropheophorbide-a. Together, these pyropheophorbides were used to assign NMR resonances and ultimately provide a model for other iron chlorins. The synthesis of nickel(II) anhydro-mesorhodoporphyrin from zinc(III) anhydromesorhodochlorin is described; this nickel porphyrin was used as a standard for ring current calculations of reduced nickel analogs of anhydromesorhodoporphyrin

Three novel metal-organic frameworks based on flexible porphyrin tetracarboxylic acids as highly effective catalysts

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zengqi [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi’an, Shaanxi 710069 (China); Su, Xiaoqin [School of Materials and Chemical Engineering, Xi’an Technological University, Xi’an, Shaanxi 710021 (China); Yu, Fan; Li, Jun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi’an, Shaanxi 710069 (China)

2016-06-15

Targeted synthesis of metalloporphyrinic frameworks (MPFs) with Cu(II) (1), Ni(II) (2, 3) 5, 10, 15, 20-tetrakis[4-(carboxymethyleneoxy)phenyl]porphyrin (Cu(TCMOPP) and Ni(TCMOPP)) as building blocks afforded three new extended coordination polymers inter-linked by Zn(II) (1) and K(I) (2, 3). 1 shows 2D frameworks while 2, 3 are 3D frameworks. The open channel are 7–17 Å wide and accessible to guest/solvent molecules. Besides, the thermogravimetric analyses (TGA) indicate that the framework structures of the three compounds are stable until 300 °C. In addition, the catalytic activities of 1–3 to the alkylbenzenes oxidation are examined, and the results indicate that 1 exhibit high catalytic activity to oxidation of ethylbenzene and 1,2,3,4-tetrahydronaphthalene with conversion of 64.1% and 80.3% respectively. - Graphical abstract: Three novel metalloporphyrinic frameworks (1, 2, 3) were synthesized based on tetracarboxylic Cu(II) (1), Ni(II) (2, 3) metalloporphyrin inter-linked by Zn(II) (1) , K(I) (2, 3), and 1 shows high catalytic activity to oxidation reaction of alkylbenzenes with conversion 80.3%. Display Omitted.

Structural and Molecular Characterization of meso-Substituted Zinc Porphyrins: A DFT Supported Study

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Giuseppe Mele

2011-12-01

Full Text Available Structural parameters of a range of over 100 meso-substituted zinc porphyrins were reviewed and compared to show how far the nature of the functional group may affect the interatomic distances and bond angles within the porphyrin core. It was proved that even despite evident deformations of the molecular structure, involving twisting of the porphyrin's central plane, the coupled π-bonding system remains flexible and stable. DFT calculations were applied to a number of selected porphyrins representative for the reviewed compounds to emphasize the relevance of theoretical methods in structural investigations of complex macrocyclic molecular systems. Experimental and DFT-simulated IR spectral data were reported and analyzed in context of the individual molecular features introduced by the meso substituents into the porphyrin moiety base. Raw experimental spectral data, including 1H- and 13C-NMR, UV-Vis, FTIR, XRD, and other relevant physicochemical details have been provided for a specially chosen reference zinc porphyrin functionalized by tert-butylphenyl groups.

Tunable photophysical processes of porphyrin macrocycles on the surface of ZnO nanoparticles

KAUST Repository

Parida, Manas R.

2015-01-23

We investigated the impact of the molecular structure of cationic porphyrins on the degree of electrostatic interactions with zinc oxide nanoparticles (ZnO NPs) using steady-state and time-resolved fluorescence and transient absorption spectroscopy. Our results demonstrate that the number of cationic pyridinium units has a crucial impact on the photophysics of the porphyrin macrocycle. Fluorescence enhancement, relative to initial free porphyrin fluorescence, was found to be tuned from 3.4 to 1.3 times higher by reducing the number of cationic substituents on the porphyrin from 4 to 2. The resulting enhancement of the intensity of the fluorescence is attributed to the decrease in the intramolecular charge transfer (ICT) character between the porphyrin cavity and its meso substituent. The novel findings reported in this work provide an understanding of the key variables involved in nanoassembly, paving the way toward optimizing the interfacial chemistry of porphyrin-ZnO NP assembly for photodynamic therapy and energy conversion.

Electrocatalytic miRNA Detection Using Cobalt Porphyrin-Modified Reduced Graphene Oxide

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Camille De Souza

2014-06-01

Full Text Available Metalated porphyrins have been described to bind nucleic acids. Additionally, cobalt porphyrins present catalytic properties towards oxygen reduction. In this work, a carboxylic acid-functionalized cobalt porphyrin was physisorbed on reduced graphene oxide, then immobilized on glassy carbon electrodes. The carboxylic groups were used to covalently graft amino-terminated oligonucleotide probes which are complementary to a short microRNA target. It was shown that the catalytic oxygen electroreduction on cobalt porphyrin increases upon hybridization of miRNA strand (“signal-on” response. Current changes are amplified compared to non-catalytic amperometric system. Apart from oxygen, no added reagent is necessary. A limit of detection in the sub-nanomolar range was reached. This approach has never been described in the literature.

Functionalized Nanostructures: Redox-Active Porphyrin Anchors for Supramolecular DNA Assemblies

KAUST Repository

Börjesson, Karl

2010-09-28

We have synthesized and studied a supramolecular system comprising a 39-mer DNA with porphyrin-modified thymidine nucleosides anchored to the surface of large unilamellar vesicles (liposomes). Liposome porphyrin binding characteristics, such as orientation, strength, homogeneity, and binding site size, was determined, suggesting that the porphyrin is well suited as a photophysical and redox-active lipid anchor, in comparison to the inert cholesterol anchor commonly used today. Furthermore, the binding characteristics and hybridization capabilities were studied as a function of anchor size and number of anchoring points, properties that are of importance for our future plans to use the addressability of these redox-active nodes in larger DNA-based nanoconstructs. Electron transfer from photoexcited porphyrin to a lipophilic benzoquinone residing in the lipid membrane was characterized by steady-state and time-resolved fluorescence and verified by femtosecond transient absorption. © 2010 American Chemical Society.

Emission properties of porphyrin compounds in new polymeric PS:CBP host

Science.gov (United States)

Jafari, Mohammad Reza; Bahrami, Bahram

2015-06-01

In this study, a device with fundamental structure of ITO/PEDOT:PSS (60 nm)/PS:CBP (70 nm)/Al (150 nm) was fabricated. The electroluminescence spectrum of device designated a red shift rather than PS:CBP photoluminescence spectra. It can be suggested that the electroplex emission occurs at PS:CBP interface. By following this step, red light-emitting devices using porphyrin compounds as a red dopant in a new host material PS:CBP with a configuration of ITO/PEDOT:PSS (60 nm)/PS:CBP:porphyrin compounds(70 nm)/Al (150 nm) have been fabricated and investigated. The electroluminescent spectra of the porphyrin compounds were red-shifted as compared with the PS:CBP blend. OLED devices based on doping 3,4PtTPP and TPPNO2 in PS:CBP showed purer red emission compared with ZnTPP and CoTPP doped devices. We believe that the electroluminescence performance of OLED devices based on porphyrin compounds depends on overlaps between the absorption of the porphyrin compounds and the emission of PS:CBP.

Fluorescence quenching behaviour of uric acid interacting with water-soluble cationic porphyrin

International Nuclear Information System (INIS)

Makarska-Bialokoz, Magdalena; Borowski, Piotr

2015-01-01

The process of association between 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate (H 2 TTMePP) and uric acid as well as its sodium salt has been studied in aqueous NaOH solution analysing its absorption and steady-state fluorescence spectra. The fluorescence quenching effect observed during interactions porphyrin-uric acid compounds points at the fractional accessibility of the fluorophore for the quencher. The association and fluorescence quenching constants are of the order of magnitude of 10 5 mol −1 . The fluorescence lifetimes and the quantum yields of the porphyrin anionic form were established. The results demonstrate that uric acid and its sodium salt can interact with H 2 TTMePP at basic pH and through formation of stacking complexes are able to quench its ability to emission. - Highlights: • Association study of water soluble cationic porphyrin with uric acid. • Porphyrin absorption spectra undergo the bathochromic and hypochromic effects. • Uric acid interacts with porphyrin in inhibiting manner, quenching its emission. • Fluorescence quenching effect testifies for the partial inactivation of a porphyrin. • The association and fluorescence quenching constants were calculated

Fluorescence quenching behaviour of uric acid interacting with water-soluble cationic porphyrin

Energy Technology Data Exchange (ETDEWEB)

Makarska-Bialokoz, Magdalena, E-mail: makarska@hektor.umcs.lublin.pl [Department of Inorganic Chemistry, Maria Curie-Sklodowska University M. C. Sklodowska Sq. 2, 20-031 Lublin (Poland); Borowski, Piotr [Faculty of Chemistry, Maria Curie-Sklodowska University M. C. Sklodowska Sq. 3, 20-031 Lublin (Poland)

2015-04-15

The process of association between 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]-21H,23H-porphine tetra-p-tosylate (H{sub 2}TTMePP) and uric acid as well as its sodium salt has been studied in aqueous NaOH solution analysing its absorption and steady-state fluorescence spectra. The fluorescence quenching effect observed during interactions porphyrin-uric acid compounds points at the fractional accessibility of the fluorophore for the quencher. The association and fluorescence quenching constants are of the order of magnitude of 10{sup 5} mol{sup −1}. The fluorescence lifetimes and the quantum yields of the porphyrin anionic form were established. The results demonstrate that uric acid and its sodium salt can interact with H{sub 2}TTMePP at basic pH and through formation of stacking complexes are able to quench its ability to emission. - Highlights: • Association study of water soluble cationic porphyrin with uric acid. • Porphyrin absorption spectra undergo the bathochromic and hypochromic effects. • Uric acid interacts with porphyrin in inhibiting manner, quenching its emission. • Fluorescence quenching effect testifies for the partial inactivation of a porphyrin. • The association and fluorescence quenching constants were calculated.

Gestación por sustitución: ni maternidad subrogada ni alquiler de vientres

OpenAIRE

Lamm, Eleonora

2013-01-01

La gestación por sustitución es una forma alternativa de acceder a la paternidad o maternidad, en el marco de las técnicas de reproducción humana asistida. Se trata de una práctica cada vez más frecuente, pues se estima que en la actualidad nacen unos veinte mil niños cada año como consecuencia de un acuerdo de este tipo. Esta obra expone la realidad de esta práctica, la gran cantidad de jurisprudencia nacional e internacional existente, las distintas opciones legales que recoge el derecho...

Radioboletín informativo para niños

Directory of Open Access Journals (Sweden)

Jorge Valdés

2015-01-01

Full Text Available En "Auge y caída de los vÍdeo juegos" el autor señala que las tecnologías digitales cambian aceleradamente. Cada cambio impacta en el entorno de la sociedad y la cultura ¿Cómo adaptarse a estos retos? ¿Cómo controlarlos? se responde en el artículo. Otro artículo hace alusión a la conmemoración de los 10 años de la Declaración del Nuevo Orden Internacional de la Información y Comunicación - NOIIC-. Radio boletín informativo para niños cita las recomendaciones dadas en el Seminario realizado por el CIESPAL, la O E A , Radio Nederland y la Fundación Friedrich E. y confirma la necesidad de que si se va a comunicar a los niños, es necesario capacitarse. Se analiza el decálogo del comunicador infantil, enfatizando en que los niños valen y exigen. "Avances psicológicos de la publicidad" es un resumen del libro de William Meyers "Los creadores de imagen" trata básicamente del poder de persuasión de Madison Avenue en sus campañas publicitarias y explica la cultura consumista en Estados Unidos, luego de la segunda guerra Mundial.

Escenarios de explotación sexual comercial de niños, niñas y adolescentes, modalidad abierta, Medellín, 2012

Directory of Open Access Journals (Sweden)

Iván F. Muñoz-Echeverri

2016-02-01

Full Text Available Resumen La explotación sexual de niños, niñas y adolescentes (escnna es una grave violación los derechos de niños, niñas y adolescentes. En Medellín, existe poca información sobre cuantificación y sectores de ocurrencia del problema, que permita la ejecución de estrategias para su prevención y atención. Objetivo: describir magnitud y ubicación, días y horarios de ocurrencia de la escnna, modalidad abierta, en Medellín y las características de los escenarios donde ocurre. Metodología: Estudio descriptivo, con uso de sistemas de información geográfica y realización de mapas temáticos. Se realizó en tres fases: pre-mapeo, mapeo y validación. Se acudió también a técnicas cualitativas. Resultados: de los 634 tramos visitados, hubo reporte de escnna en 18,9%. Se observó agrupación del fenómeno en 11 lugares de concentración. En éstos lugares confluyen factores contextuales que favorecen la escnna: fallas del alumbrado público; poca presencia estatal y de la policía; microtráfico de drogas; cercanía a bares, hoteles y casas de masajes; permisividad social; acceso a drogas y hospedaje. Conclusión: La georreferenciación de estos sectores y el reconocimiento de los factores contextuales que promueven la problemática resultan de gran importancia para contribuir al control y erradicación de esta situación que vulnera la dignidad de niños, niñas y adolescentes de la ciudad. Abstract Commercial sexual exploitation of children and adolescents (cseca is a severe violation of the rights of children and adolescents. In Medellin, data on the quantity and locations where this issue takes place is scarce, and it could be useful for implementing strategies for preventing and addressing this issue. Objective: To describe the magnitude of street-based cseca along with the places, days, hours and characteristics of the scenarios in which it takes place in Medellín. Methodology: A descriptive study in which geographical

Platinum porphyrins as ionophores in polymeric membrane electrodes

DEFF Research Database (Denmark)

Lvova, Larisa; Verrelli, Giorgio; Nardis, Sara

2011-01-01

A comparative study of Pt(II)- and Pt(IV)-porphyrins as novel ionophores for anion-selective polymeric membrane electrodes is performed. Polymeric membranes of different compositions, prepared by varying plasticizers, cationic and anionic additives and Pt porphyrins, have been examined...... within the electrode membranes, while those based on Pt(IV)TPPCl2 operate via a mixed mode carrier mechanism, evidencing also a partial reduction of the starting ionophore to Pt(II)TPP. Spectrophotometric measurements of thin polymeric films indicate that no spontaneous formation of hydroxide ion bridged...... porphyrin dimers occurs in the membrane plasticized both with high or low dielectric constant plasticizer, due to a low oxophilicity of central Pt. The computational study of various anion–Pt(IV)TPPCl2 complex formation by means of semi-empirical and density functional theory (DFT) methods revealed a good...

Synthetic Porphyrins and Metalloporphyrins

Science.gov (United States)

1976-12-10

disease syndromes , drug metabolism and cancer. Porphyrins and metalloporphyrins such as tetraphenylporphine sulfonate and hema- toporphyrin have been found...267(1941). 34. A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, J. Assour and L. Korsakoff , J. Org. Chem., 32, 476(1967). 35. H. W

Synthesis and Performance Evaluation of Pulse Electrodeposited Ni-AlN Nanocomposite Coatings

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Kamran Ali

2018-01-01

Full Text Available This research work presents the microscopic analysis of pulse electrodeposited Ni-AlN nanocomposite coatings using SEM and AFM techniques and their performance evaluation (mechanical and electrochemical by employing nanoindentation and electrochemical methods. The Ni-AlN nanocomposite coatings were developed by pulse electrodeposition. The nickel matrix was reinforced with various amounts of AlN nanoparticles (3, 6, and 9 g/L to develop Ni-AlN nanocomposite coatings. The effect of reinforcement concentration on structure, surface morphology, and mechanical and anticorrosion properties was studied. SEM and AFM analyses indicate that Ni-AlN nanocomposite coatings have dense, homogenous, and well-defined pyramid structure containing uniformly distributed AlN particles. A decent improvement in the corrosion protection performance is also observed by the addition of AlN particles to the nickel matrix. Corrosion current was reduced from 2.15 to 1.29 μA cm−2 by increasing the AlN particles concentration from 3 to 9 g/L. It has been observed that the properties of Ni-AlN nanocomposite coating are sensitive to the concentration of AlN nanoparticles used as reinforcement.

Liquid phase interaction in TiC0,5N0,5-TiNi-Mo and TiC0,5N0,5-TiNi-Ti-Mo

International Nuclear Information System (INIS)

Askarova, L.Kh; Grigorov, I.G.; Zajnulin, Yu.G.

1998-01-01

Using the methods of X ray diffraction analysis, electron microscopy and X ray spectrum microanalysis a study was made into specific features of phase and structure formation in alloys TiC 0,5 N 0,5 -TiNi-Mo and TiC 0,5 N 0,5 -TiNi-Mo in the presence of a liquid phase at temperatures of 1380-1600 deg C. It is revealed that the physical and chemical processes taking place during the liquid-phase sintering result in the formation of a three-phase alloy consisting of nonstoichiometric titanium carbonitride TiC 0.5-x N 0.5-x , a molybdenum base solid solution of titanium, nickel and carbon Mo(Ti, Ni, C) and one of two intermetallic compounds, either TiNi or Ni 3 Ti. Metallic element concentration in individual phase constituents of the alloy is determined by means of X ray spectrum microanalysis

Glycol porphyrin derivatives and temoporfin elicit resistance to photodynamic therapy by different mechanisms

Czech Academy of Sciences Publication Activity Database

Králová, Jarmila; Kolář, Michal; Kahle, Michal; Truksa, Jaroslav; Lettlová, Sandra; Balusiková, K.; Bartůněk, Petr

2017-01-01

Roč. 7, Mar 15 (2017), č. článku 44497. ISSN 2045-2322 R&D Projects: GA MŠk LO1220 Institutional support: RVO:68378050 ; RVO:86652036 Keywords : Glycol porphyrin derivates * chemotherapy * cancer * multidrug resistance Subject RIV: EB - Genetics ; Molecular Biology; EB - Genetics ; Molecular Biology (BTO-N) OBOR OECD: Biochemistry and molecular biology; Biochemistry and molecular biology (BTO-N) Impact factor: 4.259, year: 2016

Empatía y agresión en el uso de videojuegos en niños y niñas

OpenAIRE

Brenes-Peralta, Carlos; Pérez-Sánchez, Rolando

2015-01-01

En esta investigación estudiamos el papel de la agresión y la empatía como predictores de la tendencia en niños y niñas a jugar videojuegos solos o acompañados. En el estudio utilizamos el enfoque revisado del manejo emocional aplicado al uso de videojuegos (Vorderer, Hartmann & Klimmt, 2006). Realizamos una encuesta con 395 estudiantes costarricenses de escuelas públicas y privadas de San José (M= 10.69 años). Los resultados señalan que los niños y niñas con puntuaciones altas en agresión co...

The effects of urea, guanidinium chloride and sorbitol on porphyrin ...

Indian Academy of Sciences (India)

This paper compares the inhibition effect of porphyrin aggregation in the presence of urea, guanidinium chloride (Gdn) and sorbitol by molecular dynamics simulation. It demonstrates that porphyrin aggregation increases in sorbitol, but decreases towards addition of urea and Gdn. It shows that urea, Gdn and sorbitol can ...

Los niños y la televisión

Directory of Open Access Journals (Sweden)

Valerio Fuenzalida

2014-12-01

Full Text Available Trata sobre los cambios que están ocurriendo en la televisión y las audiencias infantiles. Primero el desplazamiento hacia canales del cable de la audiencia infantil. Segundo la manera de producir programas de televisión. Los nuevos programas muestran a niños en un rol activo y protagónico emprendiendo actividades y tareas donde se exhiben como capaces de iniciativas creativas y de resolución inteligente de problemas. Y tercero, los niños ven toda clase de programas no solo los infantiles por lo que es toda la televisión la que debe mejorar.

Cooperative effects in CdSe/ZnS-PEGOH quantum dot luminescence quenching by a water soluble porphyrin

International Nuclear Information System (INIS)

Borissevitch, I.E.; Parra, G.G.; Zagidullin, V.E.; Lukashev, E.P.; Knox, P.P.; Paschenko, V.Z.; Rubin, A.B.

2013-01-01

In this work we report on the study of the interaction of CdSe/ZnS-PEGOH 570 Quantum Dot (QD) with negatively charged meso-tetrakis(p-sulfonato-phenyl)porphyrin (TPPS 4 ) using optical absorption and fluorescence spectroscopies accompanied with time resolved “single photon counting” and dynamic and resonance light scattering techniques. In the steady-state experiments the QD luminescence quenching by TPPS 4 was well approximated by a square law. In the time-resolved experiments we observed a typical multi-exponential luminescence decay curve, successfully fitted by a bi-exponential approximation. At QD interaction with porphyrin the time quenching of both components was described by a linear Stern–Volmer dependence. The discrepancy between Stern–Volmer dependences in the steady-state and time resolved experiments may be due to formation of mixed m(TPPS 4 )+n(QD) complexes, in which one TPPS 4 molecule can quench several excited QDs. This idea is in accordance with the dynamic and resonance light scattering data, which demonstrate an increase of the scattering particle size at the TPPS 4 addition to QD solutions. - Highlights: ► Quantum Dot luminescence quenching by TPPS porphyrin was studied in water solutions. ► The size of particles in QD solutions possessed increase at the TPPS4 addition. ► Quenching of the QD luminescence by TPPS4 is realized in contact QD–porphyrin complexes. ► The formation of mixed quantum dot–porphyrin aggregates takes place.

Photoluminescence and dynamics of excitation relaxation in graphene oxide-porphyrin nanorods composite

International Nuclear Information System (INIS)

Khenfouch, M.; Wéry, J.; Baïtoul, M.; Maaza, M.

2014-01-01

Generally, porphyrin nanostructured materials are known by playing many roles such as photoconductors, photovoltaics and capable of light induced charging. Also their combination with acceptors like graphene, the rising two dimension material, added exciting physical and chemical properties. In this work, Morphology, optical absorption and photoluminescence properties were investigated in order to elucidate the interaction between the few layered graphene oxide (FGO) and pophyrin nanorods. Reporting on the photoluminescence (PL) of both porphyrin nanorods and FGO/porphyrin nanorods composite, synthesized via a self-assembly method, we have experimentally demonstrated the generation of a new photoluminescence band giving rise to a white light. This luminescence was studied by the analysis of its origins and dynamics which show a huge change of exciton life time found to be longer after the interaction with graphene oxide (GO) sheets. -- Highlights: • We prepared FGO-porphyrin nanorods composite via a simple chemical method. • Luminescence properties were studied presenting the absorption, photoluminescence and dynamics measurements. • These results show the emission of a white light which we studied its emissions origins. • TEM images show FGO sheets decorated with porphyrin nanorods. • FGO had like effect an increase of the exciton lifetime in porphyrin nanorods

Photoluminescence and dynamics of excitation relaxation in graphene oxide-porphyrin nanorods composite

Energy Technology Data Exchange (ETDEWEB)

Khenfouch, M., E-mail: khenfouch@yahoo.fr [University Sidi Mohamed Ben Abdellah, Faculty of Sciences Dhar el Mahraz, Laboratory of Solid State Physics, Group of Polymers and Nanomaterials, BP 1796 Atlas, Fez 30 000 (Morocco); iThemba LABS-National Research Foundation of South Africa, Old Faure Road, PO Box 722, Somerset West 7129, Western Cape Province (South Africa); UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Wéry, J. [Institut des Matériaux Jean Rouxel, Nantes, 2 rue de la Houssinière, BP 32229, 44322 Nantes, Cedex 3 (France); Baïtoul, M., E-mail: baitoul@yahoo.fr [University Sidi Mohamed Ben Abdellah, Faculty of Sciences Dhar el Mahraz, Laboratory of Solid State Physics, Group of Polymers and Nanomaterials, BP 1796 Atlas, Fez 30 000 (Morocco); Maaza, M. [iThemba LABS-National Research Foundation of South Africa, Old Faure Road, PO Box 722, Somerset West 7129, Western Cape Province (South Africa); UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa)

2014-01-15

Generally, porphyrin nanostructured materials are known by playing many roles such as photoconductors, photovoltaics and capable of light induced charging. Also their combination with acceptors like graphene, the rising two dimension material, added exciting physical and chemical properties. In this work, Morphology, optical absorption and photoluminescence properties were investigated in order to elucidate the interaction between the few layered graphene oxide (FGO) and pophyrin nanorods. Reporting on the photoluminescence (PL) of both porphyrin nanorods and FGO/porphyrin nanorods composite, synthesized via a self-assembly method, we have experimentally demonstrated the generation of a new photoluminescence band giving rise to a white light. This luminescence was studied by the analysis of its origins and dynamics which show a huge change of exciton life time found to be longer after the interaction with graphene oxide (GO) sheets. -- Highlights: • We prepared FGO-porphyrin nanorods composite via a simple chemical method. • Luminescence properties were studied presenting the absorption, photoluminescence and dynamics measurements. • These results show the emission of a white light which we studied its emissions origins. • TEM images show FGO sheets decorated with porphyrin nanorods. • FGO had like effect an increase of the exciton lifetime in porphyrin nanorods.

Real-time porphyrin detection in plaque and caries: a case study

Science.gov (United States)

Timoshchuk, Mari-Alina I.; Ridge, Jeremy S.; Rugg, Amanda L.; Nelson, Leonard Y.; Kim, Amy S.; Seibel, Eric J.

2015-02-01

An ultrathin scanning fiber endoscope, originally developed for cancer diagnosis, was used in a case study to locate plaque and caries. The imaging system incorporated software mitigation of background auto-fluorescence (AF). In conventional fluorescence imaging, varying AF across a tooth surface can mask low-level porphyrin signals. Laser-induced auto-fluorescence signals of dental tissue excited using a 405-nm laser typically produce fluorescence over a wavelength range extending from 440-nm to 750-nm. Anaerobic bacterial metabolism produces various porphyrin species (eg. protoporphyrin IX) that are located in carious enamel, dentin, gingivitis sites, and plaque. In our case study, these porphyrin deposits remained as long as one day after prophylaxis. Imaging the tooth surface using 405-nm excitation and subtracting the natural AF enhances the image contrast of low-level porphyrin deposits, which would otherwise be masked by the high background AF. In a case study, healthy tissues as well as sites of early and advanced caries formations were scanned for visual and quantitative signs of red fluorescence associated with porphyrin species using a background mitigation algorithm. Initial findings show increasing amplitudes of red fluorescence as caries severity increases from early to late stages. Sites of plaque accumulation also displayed red fluorescence similar to that found in carious dental tissue. The use of real-time background mitigation of natural dental AF can enhance the detection of low porphyrin concentrations that are indicators of early stage caries formation.

Interaction of porphyrins with CdTe quantum dots

International Nuclear Information System (INIS)

Zhang Xing; Liu Zhongxin; Ma Lun; Hossu, Marius; Chen Wei

2011-01-01

Porphyrins may be used as photosensitizers for photodynamic therapy, photocatalysts for organic pollutant dissociation, agents for medical imaging and diagnostics, applications in luminescence and electronics. The detection of porphyrins is significantly important and here the interaction of protoporphyrin-IX (PPIX) with CdTe quantum dots was studied. It was observed that the luminescence of CdTe quantum dots was quenched dramatically in the presence of PPIX. When CdTe quantum dots were embedded into silica layers, almost no quenching by PPIX was observed. This indicates that PPIX may interact and alter CdTe quantum dots and thus quench their luminescence. The oxidation of the stabilizers such as thioglycolic acid (TGA) as well as the nanoparticles by the singlet oxygen generated from PPIX is most likely responsible for the luminescence quenching. The quenching of quantum dot luminescence by porphyrins may provide a new method for photosensitizer detection.

A panchromatic anthracene-fused porphyrin sensitizer for dye-sensitized solar cells

KAUST Repository

Ball, James M.

2012-01-01

The development of ruthenium-free sensitizers which absorb light over a broad range of the solar spectrum is important for improving the power conversion efficiency of dye-sensitized solar cells. Here we study three chemically tailored porphyrin-based dyes. We show that by fusing the porphyrin core to an anthracene unit, we can extend the conjugation length and lower the optical gap, shifting the absorption spectrum into the near-infrared (NIR). All three dyes were tested in dye-sensitized solar cells, using both titanium dioxide and tin dioxide as the electron-transport material. Solar cells incorporating the anthracene-fused porphyrin dye exhibit photocurrent collection at wavelengths up to about 1100 nm, which is the longest reported for a porphyrin-based system. Despite extending the photon absorption bandwidth, device efficiency is found to be low, which is a common property of cells based on porphyrin dyes with NIR absorption. We show that in the present case the efficiency is reduced by inefficient electron injection into the oxide, as opposed to dye regeneration, and highlight some important design considerations for panchromatic sensitizers. © 2012 The Royal Society of Chemistry.

Neutron-capture rates for explosive nucleosynthesis: the case of 68Ni(n, γ)69Ni

Science.gov (United States)

Spyrou, A.; Larsen, A. C.; Liddick, S. N.; Naqvi, F.; Crider, B. P.; Dombos, A. C.; Guttormsen, M.; Bleuel, D. L.; Couture, A.; Crespo Campo, L.; Lewis, R.; Mosby, S.; Mumpower, M. R.; Perdikakis, G.; Prokop, C. J.; Quinn, S. J.; Renstrøm, T.; Siem, S.; Surman, R.

2017-04-01

Neutron-capture reactions play an important role in heavy element nucleosynthesis, since they are the driving force for the two processes that create the vast majority of the heavy elements. When a neutron capture occurs on a short-lived nucleus, it is extremely challenging to study the reaction directly and therefore the use of indirect techniques is essential. The present work reports on such an indirect measurement that provides strong constraints on the 68Ni(n, γ)69Ni reaction rate. This is done by populating the compound nucleus 69Ni via the β decay of 69Co and measuring the γ-ray deexcitation of excited states in 69Ni. The β-Oslo method was used to extract the γ-ray strength function and the nuclear level density. In addition the half-life of 69Co was extracted and found to be in agreement with previous literature values. Before the present results, the 68Ni(n, γ)69Ni reaction was unconstrained and the purely theoretical reaction rate was highly uncertain. The new uncertainty on the reaction rate based on the present experiment (variation between upper and lower limit) is approximately a factor of 3. The commonly used reaction libraries JINA-REACLIB and BRUSLIB are in relatively good agreement with the experimental rate. The impact of the new rate on weak r-process calculations is discussed.

Distribution of exogenous porphyrins in vivo; implications for neutron capture therapy

International Nuclear Information System (INIS)

Fairchild, R.G.; Gabel, D.; Hillman, M.; Watts, K.

1982-01-01

Endogenous porphyrins (HpD) are already in clinical use for phototherapy, in which red light is used to stimulate a cytotoxic response in tumors. The evident success, at least with superficial cancers, gives biological evidence of selective concentrations of porphyrins in tumors adequate for therapy. The authors have investigated, in addition, the biodistribution of a synthetic porphyrin (tetraphenylporphinesulfonate, or TPPS) in seven different animal tumor models. Their data, as well as those of others, indicate abundant accumulations of TPPS in tumor. If boronated analogs behave in the same way, boron concentrations would be up to 10 times that needed for therapy. Utilization of such porphyrin analogs in the neutron capture therapy (NCT) procedure is similar in concept to phototherapy currently being used clinically, with the distinct advantage of deeper tissue penetration produced by the activating neutrons

Room-Temperature Synthesis of Thiostannates from {[Ni(tren)]2[Sn2S6]}n.

Science.gov (United States)

Hilbert, Jessica; Näther, Christian; Weihrich, Richard; Bensch, Wolfgang

2016-08-15

The compound {[Ni(tren)]2[Sn2S6]}n (1) (tren = tris(2-aminoethyl)amine, C6H18N4) was successfully applied as source for the room-temperature synthesis of the new thiostannates [Ni(tren)(ma)(H2O)]2[Sn2S6]·4H2O (2) (ma = methylamine, CH5N) and [Ni(tren)(1,2-dap)]2[Sn2S6]·2H2O (3) (1,2-dap = 1,2-diaminopropane, C3H10N2). The Ni-S bonds in the Ni2S2N8 bioctahedron in the structure of 1 are analyzed with density functional theory calculations demonstrating significantly differing Ni-S bond strengths. Because of this asymmetry they are easily broken in the presence of an excess of ma or 1,2-dap immediately followed by Ni-N bond formation to N donor atoms of the amine ligands thus generating [Ni(tren)(amine)](2+) complexes. The chemical reactions are fast, and compounds 2 and 3 are formed within 1 h. The synthesis concept presented here opens hitherto unknown possibilities for preparation of new thiostannates.

Electrochemical Behavior and Hydrophobic Properties of CrN and CrNiN Coatings in Simulated Proton Exchange Membrane Fuel Cell Environment

Directory of Open Access Journals (Sweden)

JIN Jie

2016-10-01

Full Text Available The CrN and CrNiN coatings were prepared on the surface of 304 stainless steel by closed field unbalanced magnetron sputtering.X ray diffraction and field emission scanning electron microscopy were used to characterize the structure and morphology of the coatings.The electrochemical corrosion properties under the simulated proton exchange membrane fuel cell(PEMFC environment, interfacial contact resistance and hydrophobic properties of the two kinds of different coatings were investigated by electrochemical methods,contact resistance test and hydrophobic test,respectively.The results indicate that CrN coating mainly consists of CrN and Cr2N phase,CrN and Cr2N phases in the CrNiN coating are less compared to CrN film, and Ni exist as element in CrNiN coating; dynamic polarization tests show the coating is of better corrosion resistance,whereas the corrosion resistance of CrNiN coating is worse than that of CrN coating,constant potential polarization test shows the corrosion current density of CrN and CrNiN coatings are equivalent; CrN and CrNiN coatings significantly reduce the interfacial contact resistance of the 304 stainless steel,among which CrN coating has the smallest contact resistance; and CrNiN coating which has better hydrophobicity than that of CrN coating is more beneficial for the water management in proton exchange membrane fuel cell.

Tratamientos integrales en el POS para la rehabilitación de niños, niñas y adolescentes con anorexia y bulimia

OpenAIRE

Monroy Fontalvo, Tania Paola

2012-01-01

Este trabajo busca establecer si en Colombia el ordenamiento jurídico contempla un tratamiento integral para la rehabilitación de los niños, niñas y adolescentes que padecen de anorexia y bulimia. Para ello, se hará una descripción de la anorexia y la bulimia en niños, niñas y adolescentes, se examinarán las normas que desarrollan el POS estableciendo la reglamentación que se consagra para la rehabilitación de estas enfermedades y se llegará a la conclusión de acuerdo al pronunciamiento de la...

Growth of single-crystal W whiskers during humid H2/N2 reduction of Ni, Fe-Ni, and Co-Ni doped tungsten oxide

International Nuclear Information System (INIS)

Wang Shiliang; He Yuehui; Zou Jou; Wang Yong; Huang Han

2009-01-01

Numbers of W whiskers were obtained by reducing Ni, Ni-Fe, and Ni-Co doped tungsten oxide in a mixed atmosphere of humid H 2 and N 2 . The phases and morphologies of the reduction products were characterized by XRD and SEM. Intensive TEM and EDS analyses showed that the obtained whiskers were W single crystals which typical have alloyed particles (Ni-W, Fe-Ni, or Co-Ni-W) at the growth tips. The formed W whiskers were presumed to be induced by the alloyed particles. Our experimental results revealed that, during the reduction process of tungsten oxide, the pre-reduced Ni, Fe-Ni, or Co-Ni particles not only served as nucleation aids for the initial growth of W phase from W oxide but also played the roles of catalysts during the reductive decomposition of gaseous WO 2 (OH) 2 .

3D hierarchical dandelion-like NiCo{sub 2}O{sub 4}/N-doped carbon/Ni foam for an effective binder-free supercapacitor electrode

Energy Technology Data Exchange (ETDEWEB)

Xu, Xiaoyang; Hong, Wei; Zhao, Huilin; Song, Yahui; Qiu, Haixia, E-mail: haixiaqiuls@163.com; Gao, Jianping

2017-01-15

In this work, the 3D hierarchical dandelion-like NiCo{sub 2}O{sub 4}/N-doped carbon/Ni foam has been developed by introducing PANI as the precursor of N-doped carbon. Meanwhile, the NiCo{sub 2}O{sub 4}/N-doped carbon/Ni foam with a novel 3D hierarchical dandelion-like structure was verified by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy, etc. In addition, the NiCo{sub 2}O{sub 4}/N-doped carbon/Ni foam was directly used as a binder-free supercapacitor electrode and its performances were investigated by cycle voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. The results show that the obtained NiCo{sub 2}O{sub 4}/N-doped carbon/Ni foam electrode owns good electrochemical performances, such as high specific capacitance (864 F/g at 1 A/g) and good cycling stability, owing to the porous feature from its novel 3D hierarchical dandelion-like structure. - Highlights: • The 3D hierarchical dandelion-like NiCo{sub 2}O{sub 4}/N-doped carbon/Ni foam was prepared. • It can be directly used as a binder-free supercapacitor electrode. • It owns good electrochemical performances.

Nonvolatile memory characteristics influenced by the different crystallization of Ni-Si and Ni-N nanocrystals

International Nuclear Information System (INIS)

Chen, W.-R.; Yeh, J.-L.; Chang, C.-Y.; Chang, T.-C.; Chen, S.-C.

2008-01-01

The formation of Ni-Si and Ni-N nanocrystals by sputtering a Ni 0.3 Si 0.7 target in argon and nitrogen environment were proposed in this paper. A transmission electron microscope analysis shows the nanocrystals embedded in the nitride layer. X-ray photoelectron spectroscopy and x-ray diffraction also offer the chemical material analysis of nanocrystals with surrounding dielectric and the crystallization of nanocrystals for different thermal annealing treatments. Nonvolatile Ni-Si nanocrystal memories reveal superior electrical characteristics for charge storage capacity and reliability due to the improvement of thermal annealing treatment. In addition, we used energy band diagrams to explain the significance of surrounding dielectric for reliability

Molecular Nickel Phosphide Carbonyl Nanoclusters: Synthesis, Structure, and Electrochemistry of [Ni11P(CO)18]3- and [H6-nNi31P4(CO)39]n- (n = 4 and 5).

Science.gov (United States)

Capacci, Chiara; Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Funaioli, Tiziana; Zacchini, Stefano; Zanotti, Valerio

2018-02-05

The reaction of [NEt 4 ] 2 [Ni 6 (CO) 12 ] in thf with 0.5 equiv of PCl 3 affords the monophosphide [Ni 11 P(CO) 18 ] 3- that in turn further reacts with PCl 3 resulting in the tetra-phosphide carbonyl cluster [HNi 31 P 4 (CO) 39 ] 5- . Alternatively, the latter can be obtained from the reaction of [NEt 4 ] 2 [Ni 6 (CO) 12 ] in thf with 0.8-0.9 equiv of PCl 3 . The [HNi 31 P 4 (CO) 39 ] 5- penta-anion is reversibly protonated by strong acids leading to the [H 2 Ni 31 P 4 (CO) 39 ] 4- tetra-anion, whereas deprotonation affords the [Ni 31 P 4 (CO) 39 ] 6- hexa-anion. The latter is reduced with Na/naphthalene yielding the [Ni 31 P 4 (CO) 39 ] 7- hepta-anion. In order to shed light on the polyhydride nature and redox behavior of these clusters, electrochemical and spectroelectrochemical studies were carried out on [Ni 11 P(CO) 18 ] 3- , [HNi 31 P 4 (CO) 39 ] 5- , and [H 2 Ni 31 P 4 (CO) 39 ] 4- . The reversible formation of the stable [Ni 11 P(CO) 18 ] 4- tetra-anion is demonstrated through the spectroelectrochemical investigation of [Ni 11 P(CO) 18 ] 3- . The redox changes of [HNi 31 P 4 (CO) 39 ] 5- show features of chemical reversibility and the vibrational spectra in the ν CO region of the nine redox states of the cluster [HNi 31 P 4 (CO) 39 ] n- (n = 3-11) are reported. The spectroelectrochemical investigation of [H 2 Ni 31 P 4 (CO) 39 ] 4- revealed the presence of three chemically reversible reduction processes, and the IR spectra of [H 2 Ni 31 P 4 (CO) 39 ] n- (n = 4-7) have been recorded. The different spectroelectrochemical behavior of [HNi 31 P 4 (CO) 39 ] 5- and [H 2 Ni 31 P 4 (CO) 39 ] 4- support their formulations as polyhydrides. Unfortunately, all the attempts to directly confirm their poly hydrido nature by 1 H NMR spectroscopy failed, as previously found for related large metal carbonyl clusters. Thus, the presence and number of hydride ligands have been based on the observed protonation/deprotonation reactions and the spectroelectrochemical

Tetrakis(4-tert-butylphenyl) substituted and fused quinoidal porphyrins

KAUST Repository

Zeng, Wangdong

2012-01-01

4-tert-Butylphenyl-substituted and fused quinoidal porphyrins 1 and 2 are prepared for the first time. They show (1) intense one-photon absorption in the far-red/near-infrared region, (2) enhanced two-photon absorption compared with aromatic porphyrin monomers, and (3) amphoteric redox behavior. Their geometry and electronic structure are studied by DFT calculations. This journal is © 2012 The Royal Society of Chemistry.

Fe/Ni-N-CNFs electrochemical catalyst for oxygen reduction reaction/oxygen evolution reaction in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhuang [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Li, Mian [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Fan, Liquan; Han, Jianan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Xiong, Yueping, E-mail: ypxiong@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China)

2017-04-15

Highlights: • Novel Fe/Ni-N-CNFs electrocatalysts are prepared by electrospinning technique. • The Fe1Ni1-N-CNFs catalyst exhibits the excellent ORR and OER catalytic activity. • Synergy of Fe/Ni alloy is responsible for the excellent catalytic performance. - Abstract: The novel of iron, nickel and nitrogen doped carbon nanofibers (Fe/Ni-N-CNFs) as bifunctional electrocatalysts are prepared by electrospinning technique. In alkaline media, the Fe/Ni-N-CNFs catalysts (especially for Fe1Ni1-N-CNFs) exhibit remarkable electrocatalytic performances of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER). For ORR catalytic activity, Fe1Ni1-N-CNFs catalyst offers a higher onset potential of 0.903 V, a similar four-electron reaction pathway, and excellent stability. For OER catalytic activity, Fe1Ni1-N-CNFs catalyst possesses a lower onset potential of 1.528 V and a smaller charge transfer resistance of 48.14 Ω. The unparalleled catalytic activity of ORR and OER for the Fe1Ni1-N-CNFs is attributed to the 3D porous cross-linked microstructures of carbon nanofibers with Fe/Ni alloy, N dopant, and abundant M-N{sub x} and NiOOH as catalytic active sites. Thus, Fe1Ni1-N-CNFs catalyst can be acted as one of the efficient and inexpensive catalysts of metal-air batteries.

La diversidad en la construcción de mundo de niños y niñas de dos culturas

Directory of Open Access Journals (Sweden)

Nolfa Ibáñez-Salgado

2015-02-01

Full Text Available Asumiendo la concepción de diversidad como distintas construcciones de mundo, pretendo en este trabajo develar las lógicas que guían las interacciones en las que participan niños y niñas de dos culturas: cultura mayor y cultura mapuche. Comparo las interacciones habituales en el hogar de niños y niñas de clase media de Santiago, y de niños y niñas mapuche de comunidades rurales, y posteriormente en sus respectivas aulas. La metodología es cualitativa, de enfoque etnográfico. Los resultados muestran que las lógicas que guían la interacción en las familias de los niños y niñas mapuche son distintas y en algunos casos opuestas a las que imperan en la escuela, que la diversidad no es acogida pedagógicamente por el profesorado, y que aprendizajes previos de los niños y niñas mapuche se invisibilizan en el aula.

Dye linked conjugated homopolymers: using conjugated polymer electroluminescence to optically pump porphyrin-dye emission

DEFF Research Database (Denmark)

Nielsen, K.T.; Spanggaard, H.; Krebs, Frederik C

2004-01-01

. Electroluminescent devices of the homopolymer itself and of the zinc-porphyrin containing polymer were prepared and the nature of the electroluminescence was characterized. The homopolymer segments were found to optically pump the emission of the zinc-porphyrin dye moities. The homopolymer exhibits blue......Zinc-porphyrin dye molecules were incorporated into the backbone of a conjugated polymer material by a method, which allowed for the incorporation of only one zinc-porphyrin dye molecule into the backbone of each conjugated polymer molecule. The electronic properties of the homopolymer were...

Salud, bienestar y desarrollo de niños y niñas con medida de separación familiar en protección infantil

OpenAIRE

Llanos López, Alexia

2013-01-01

INTRODUCCIÓN: El Sistema de Protección a la Infancia actual tiene como reto fundamental conseguir la promoción de un desarrollo personal de la infancia óptimo, siendo así ineludible paliar las consecuencias de la desprotección. En este contexto, en el de atender las necesidades individuales de cada caso, cobra protagonismo la supremacía del interés del menor y, por tanto, se hace indispensable evaluar minuciosamente el estado en el que llega al Sistema cada niño o niña y su situación para pod...

Preparation and characterization of NiW-nHA composite catalyst for hydrocracking

Science.gov (United States)

Zhou, Gang; Hou, Yongzhao; Liu, Lei; Liu, Hongru; Liu, Can; Liu, Jing; Qiao, Huiting; Liu, Wenyong; Fan, Yubo; Shen, Shituan; Rong, Long

2012-11-01

The synthesis, characterization and catalytic capability of the NiW-nano-hydroxyapatite (NiW-nHA) composite were investigated in this paper. The NiW-nHA catalyst was prepared by a co-precipitation method. Then Fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDX) were used to analyze this material. In addition, the catalytic capacity of the NiW-nHA composite was also examined by FT-IR and gas chromatography (GC). The results of FT-IR analysis indicated that Ni, W and nHA combined closely. TEM observation revealed that this catalyst was needle shaped and the crystal retained a nanometer size. XRD data also suggested that a new phase of CaWO4 appeared and the lattice parameters of nHA changed in this system. nHA was the carrier of metals. The rates of Ni/W-loading were 73.24% and 65.99% according to the EDX data, respectively. Furthermore, the conversion of 91.88% Jatropha oil was achieved at 360 °C and 3 MPa h-1 over NiW-nHA catalyst. The straight chain alkanes ranging from C15 to C18 were the main components in the production. The yield of C15-C18 alkanes was up to 83.56 wt%. The reaction pathway involved hydrocracking of the C&z.dbd;C bonds of these triglycerides from Jatropha oil. This paper developed a novel non-sulfided catalyst to obtain a ``green biofuel'' from vegetable oil.

Uncharged water-soluble porphyrin tweezers as a supramolecular sensor for α-amino acids

International Nuclear Information System (INIS)

Villari, Valentina; Mineo, Placido; Micali, Norberto; Angelini, Nicola; Vitalini, Daniele; Scamporrino, Emilio

2007-01-01

The binding between uncharged cobalt porphyrin tweezers and L-amino acids in aqueous solutions is studied by means of UV-vis and circular dichroism spectroscopy. By varying the length of the aliphatic bridge between the two porphyrin units, the number of cobalt ions in the porphyrin cores and the pH of the solution, the chirality induction phenomenon has been investigated. The binding of the amino acid to the porphyrin seems to occur via a coordination mechanism between the metal and the nitrogen of the amino group; the steric, hydrophobic and π-π interactions operate to stabilize the complexes. The chirogenesis displays an opposite behaviour in the presence of aromatic guests with respect to the non-aromatic ones. Moreover, the UV-vis and the induced circular dichroism spectral changes suggest that the amino acid arrangement in the tweezers is determined by many factors, so that, unlike in organic solvent, the porphyrin tweezers in aqueous solution allow for two different arrangements of the same aromatic amino acid. The experimental findings indicate that the porphyrins tweezers reported in the paper are promising in opening perspectives toward their application as a selective molecular sensor in aqueous solutions directly

Electronic structures of N- and C-doped NiO from first-principles calculations

International Nuclear Information System (INIS)

Long, Run; English, Niall J.; Mooney, Damian A.

2010-01-01

The large intrinsic band gap of NiO has hindered severely its potential application under visible-light irradiation. In this Letter, we have performed first-principles calculations on the electronic properties of N- and C-doped NiO to ascertain if its band gap may be narrowed theoretically. It was found that impurity bands driven by N 2p or C 2p states appear in the band gap of NiO and that some of these locate at the conduction band minimum, which leads to a significant band gap narrowing. Our results show that N-doped NiO may serve as a potential photocatalyst relative to C-doped NiO, due to the presence of some recombination centres in C-doped NiO.

MINERALOGY OF HALLOYSITES AND THEIR INTERACTION WITH PORPHYRINE

Directory of Open Access Journals (Sweden)

Vašutová V.

2013-09-01

Full Text Available Samples representing two modifications of halloysites, dehydrated (7 Å and hydrated (10 Å forms, respectively, were examined with the aim to select suitable candidates for to be used as carriers of porphyrine photoactive molecules. The samples were analysed by powder X-ray diffraction (pXRD, infrared spectroscopy (FT-IR, and high resolution transmission electron microscopy (HRTEM. Chemical composition was also determined. For the determination of cationic exchange capacity (CEC the silver thiourea method (AgTU was used. Silver cations concentrations in the solution before and after the interaction were determined by atomic absorption spectrometry (AAS. By the interaction of two pure hydrated halloysites with porphyrine it was found that porphyrine does not intercalate the interlayer space, but it is adsorbed on the outer surface of halloysite. This interaction changed the colour of clay sample from white to green. The changes were also clearly visible on diffuse reflectance spectra (DRS.

High thermally stable Ni /Ag(Al) alloy contacts on p-GaN

Science.gov (United States)

Chou, C. H.; Lin, C. L.; Chuang, Y. C.; Bor, H. Y.; Liu, C. Y.

2007-01-01

Ag agglomeration was found to occur at Ni /Ag to p-GaN contacts after annealing at 500°C. This Ag agglomeration led to the poor thermal stability showed by the Ni /Ag contacts in relation to the reflectivity and electrical properties. However, after alloying with 10at.% Al by e-gun deposition, the Ni /Ag(Al) p-GaN contacts were found to effectively retard Ag agglomeration thereby greatly enhancing the thermal stability. Based on the x-ray photoelectron spectroscopy analysis, the authors believe that the key for the retardation of Ag agglomeration was the formation of ternary Al-Ni-O layer at p-GaN interface.

Dissection of the mechanism of manganese porphyrin-catalyzed chlorine dioxide generation.

Science.gov (United States)

Umile, Thomas P; Wang, Dong; Groves, John T

2011-10-17

Chlorine dioxide, an industrially important biocide and bleach, is produced rapidly and efficiently from chlorite ion in the presence of water-soluble, manganese porphyrins and porphyrazines at neutral pH under mild conditions. The electron-deficient manganese(III) tetra-(N,N-dimethyl)imidazolium porphyrin (MnTDMImP), tetra-(N,N-dimethyl)benzimidazolium (MnTDMBImP) porphyrin, and manganese(III) tetra-N-methyl-2,3-pyridinoporphyrazine (MnTM23PyPz) were found to be the most efficient catalysts for this process. The more typical manganese tetra-4-N-methylpyridiumporphyrin (Mn-4-TMPyP) was much less effective. Rates for the best catalysts were in the range of 0.24-32 TO/s with MnTM23PyPz being the fastest. The kinetics of reactions of the various ClO(x) species (e.g., chlorite ion, hypochlorous acid, and chlorine dioxide) with authentic oxomanganese(IV) and dioxomanganese(V)MnTDMImP intermediates were studied by stopped-flow spectroscopy. Rate-limiting oxidation of the manganese(III) catalyst by chlorite ion via oxygen atom transfer is proposed to afford a trans-dioxomanganese(V) intermediate. Both trans-dioxomanganese(V)TDMImP and oxoaqua-manganese(IV)TDMImP oxidize chlorite ion by 1-electron, generating the product chlorine dioxide with bimolecular rate constants of 6.30 × 10(3) M(-1) s(-1) and 3.13 × 10(3) M(-1) s(-1), respectively, at pH 6.8. Chlorine dioxide was able to oxidize manganese(III)TDMImP to oxomanganese(IV) at a similar rate, establishing a redox steady-state equilibrium under turnover conditions. Hypochlorous acid (HOCl) produced during turnover was found to rapidly and reversibly react with manganese(III)TDMImP to give dioxoMn(V)TDMImP and chloride ion. The measured equilibrium constant for this reaction (K(eq) = 2.2 at pH 5.1) afforded a value for the oxoMn(V)/Mn(III) redox couple under catalytic conditions (E' = 1.35 V vs NHE). In subsequent processes, chlorine dioxide reacts with both oxomanganese(V) and oxomanganese(IV)TDMImP to afford chlorate

Fluorescence spectroscopic studies on substituted porphyrins in homogeneous solvents and cationic micellar medium

International Nuclear Information System (INIS)

Phukan, Smritakshi; Mishra, Bhupendra; Chandra Shekar, K.P.; Kumar, Anil; Kumar, Dalip; Mitra, Sivaprasad

2013-01-01

Steady state and time-resolved fluorescence properties of porphyrin appended 1,3,4-oxadiazoles and thiazoles were described in homogeneous medium as well as in presence of cationic surfactant cetyltrimethylammonium bromide (CTAB). The electron withdrawing substituent on the porphyrin moiety in both the cases make a donor–spacer–acceptor type of intramolecular photoinduced electron transfer (PET) system resulting substantial quenching in porphyrin fluorescence due to partial energy migration towards the acceptor in the excited state. The increase in fluorescence yield as well as appreciable difference in fluorescence decay behavior in aqueous buffer solution of pH 4.2 from that in chloroform solution is believed due to partial protonation of the porphyrin ring. All the investigated systems show preferential binding into the interfacial region of the micellar sub-domain with varying degree of penetration depending on the nature of the substituent. Almost 2–4 fold increase in fluorescence yield for the probes is explained on the basis of restricted flexibility and corresponding decrease in total nonradiative rate inside the micellar interface layer. - Highlights: ► Synthesis and detail fluorescence studies of a series of porphyrin appended 1,3,4-oxadiazoles and thiazoles. ► Comparison of homogeneous solvent study with that in CTAB. ► Substantial porphyrin fluorescence quenching in donor–spacer–acceptor type system. ► Preferential binding of the substituted porphyrins in micellar sub-domain. ► Appreciable increase in fluorescence yield in micellar interface layer is due to decrease in total nonradiative rate.

La formacción participativa de niñas y niños: Una mirada a la Diversidad Funcional desde el deporte del Patinaje.

OpenAIRE

Caicedo Arellano, Yaneth Del Carmen

2017-01-01

“La formación participativa de niñas y niños: una mirada a la diversidad funcional desde el deporte del patinaje” El presente artículo sintetiza la investigación: “La formación participativa de niñas y niños: una mirada a la diversidad funcional desde el deporte del patinaje” su propósito fundamental es comprender el sentido del vínculo deportivo que debe existir entre entrenadores y niños o deportistas diversos, en la formación en este deporte, en el marco del reconocimiento de la divers...

El niño como persona y su relación con los derechos del niño

Directory of Open Access Journals (Sweden)

Agustín Lozano Vicente

2016-11-01

Full Text Available La fundamentación normativa de los derechos del niño dista mucho de ser una cuestión clara y distinta, constituyendo todo un inventario de dificultades. Una de estas dificultades tiene como principal motivo la atribución de la categoría de persona a los menores de edad como requisito para ser titulares de derechos. Se exponen las distintas perspectivas que se tienen en cuenta para considerar al niño como persona moral así como las dificultades y controversias a las que ha dado lugar. En función de los diferentes resultados de las disciplinas científicas sobre la persona y según la perspectiva adoptada, se tienen ideas diferentes sobre el estatus de los derechos del niño.  El problema principal que suscita la idea de persona humana podría ser planteado como el problema de la naturaleza de la conexión entre la individualidad y su relación con la idea de persona. Siendo esto así, se señala que la consideración del niño como persona supone el reconocimiento universal, como norma de carácter ético, de su individualidad. Sin embargo, el estado de sujeto personal sólo se alcanzará plenamente en el seno de una determinada configuración social capaz de dotar de valor a dicha individualidad.  Siendo esto así, los derechos del niño se enuncian desde los fundamentos ideológicos y doctrinales de los legisladores que los declaran, con la artificiosidad y limitaciones que tales coordenadas llevan consigo y en pugna con otras posibles alternativas ideológicas también presentes.

A Fluorinated Cobalt(III) Porphyrin Complex for Hydroalkoxylation of Alkynes.

Science.gov (United States)

Ushimaru, Richiro; Nishimura, Takuho; Iwatsuki, Toshiki; Naka, Hiroshi

2017-01-01

A fluorinated cobalt(III) porphyrin complex [Co(TPFPP)NTf 2 ·2C 2 H 5 OH, where TPFPP=5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, Tf=CF 3 SO 2 ] promotes hydroalkoxylation of alkynes to give acetals in good to excellent yields. The acetals can be directly functionalized with nucleophiles in a one-pot procedure.

Applying the concept of consumer confusion to healthcare: development and validation of a patient confusion model.

Science.gov (United States)

Gebele, Christoph; Tscheulin, Dieter K; Lindenmeier, Jörg; Drevs, Florian; Seemann, Ann-Kathrin

2014-01-01

As patient autonomy and consumer sovereignty increase, information provision is considered essential to decrease information asymmetries between healthcare service providers and patients. However, greater availability of third party information sources can have negative side effects. Patients can be confused by the nature, as well as the amount, of quality information when making choices among competing health care providers. Therefore, the present study explores how information may cause patient confusion and affect the behavioral intention to choose a health care provider. Based on a quota sample of German citizens (n = 198), the present study validates a model of patient confusion in the context of hospital choice. The study results reveal that perceived information overload, perceived similarity, and perceived ambiguity of health information impact the affective and cognitive components of patient confusion. Confused patients have a stronger inclination to hastily narrow down their set of possible decision alternatives. Finally, an empirical analysis reveals that the affective and cognitive components of patient confusion mediate perceived information overload, perceived similarity, and perceived ambiguity of information. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

La calidad del Jardín maternal y su influencia en el desarrollo cognitivo de los niños y niñas

Directory of Open Access Journals (Sweden)

Mariela Caputo

2010-10-01

Full Text Available Frente a la necesidad de las familias de incorporar a los niños y niñas durante el primer año de vida en jardines maternales durante un significativo número de horas al día, se han planteado controversias respecto al impacto de esta realidad en el desarrollo cognitivo de los niños y niñas escolarizados tempranamente.En este artículo intentamos demostrar que la calidad de atención que reciben los niños y niñas, determinará en gran manera el desarrollo de sus habilidades de pensamiento que los beneficiarán en su desempeño escolar futuro.

Thermodynamics of complex formation of natural iron(III)porphyrins with neutral ligands

International Nuclear Information System (INIS)

Lebedeva, Nataliya Sh.; Yakubov, Sergey P.; Vyugin, Anatoly I.; Parfenyuk, Elena V.

2003-01-01

Calorimetric titrations in benzene and chloroform at 298.15 K have been performed to give the complexes stability constants and the thermodynamic parameters for the complex formation of nature iron(III)porphyrins with pyridine. Stoichimetry of the complexes formed has been determined. It has been found that the thermodynamic parameters obtained depend on nature of peripheral substituents of the porphyrins. The estimation of the influence of Cl - and Ac - ions on the processes studied has been carried out. Using thermodynamic analysis method, the crystallsolvates of nature iron(III)porphyrins with benzene have been studied. Stoichiometry, thermal and energetic stability of the π-π-complexes formed have been determined. The data obtained have been used to the estimate solvent effect on the thermodynamic parameters of axial coordination of pyridine on the iron(III)porphyrins in benzene

Cooperative effects in CdSe/ZnS-PEGOH quantum dot luminescence quenching by a water soluble porphyrin

Energy Technology Data Exchange (ETDEWEB)

Borissevitch, I.E., E-mail: iourib@ffclrp.usp.br [Departamento de Fisica, Faculdade de Filosofia Ciencia e Letras de Ribeirao Preto, Universidade de Sao Paulo, Av. Bandeirantes 3900, Ribeirao Preto, SP (Brazil); Parra, G.G. [Departamento de Fisica, Faculdade de Filosofia Ciencia e Letras de Ribeirao Preto, Universidade de Sao Paulo, Av. Bandeirantes 3900, Ribeirao Preto, SP (Brazil); Zagidullin, V.E.; Lukashev, E.P.; Knox, P.P.; Paschenko, V.Z.; Rubin, A.B. [Department of Biophysics, Faculty of Biology, M.V. Lomonosov Moscow State University, Vorobyovy Gory, 119991 Moscow (Russian Federation)

2013-02-15

In this work we report on the study of the interaction of CdSe/ZnS-PEGOH 570 Quantum Dot (QD) with negatively charged meso-tetrakis(p-sulfonato-phenyl)porphyrin (TPPS{sub 4}) using optical absorption and fluorescence spectroscopies accompanied with time resolved 'single photon counting' and dynamic and resonance light scattering techniques. In the steady-state experiments the QD luminescence quenching by TPPS{sub 4} was well approximated by a square law. In the time-resolved experiments we observed a typical multi-exponential luminescence decay curve, successfully fitted by a bi-exponential approximation. At QD interaction with porphyrin the time quenching of both components was described by a linear Stern-Volmer dependence. The discrepancy between Stern-Volmer dependences in the steady-state and time resolved experiments may be due to formation of mixed m(TPPS{sub 4})+n(QD) complexes, in which one TPPS{sub 4} molecule can quench several excited QDs. This idea is in accordance with the dynamic and resonance light scattering data, which demonstrate an increase of the scattering particle size at the TPPS{sub 4} addition to QD solutions. - Highlights: Black-Right-Pointing-Pointer Quantum Dot luminescence quenching by TPPS porphyrin was studied in water solutions. Black-Right-Pointing-Pointer The size of particles in QD solutions possessed increase at the TPPS4 addition. Black-Right-Pointing-Pointer Quenching of the QD luminescence by TPPS4 is realized in contact QD-porphyrin complexes. Black-Right-Pointing-Pointer The formation of mixed quantum dot-porphyrin aggregates takes place.

Influence of substituents in meso-aryl groups of iron l-oxo porphyrins\

Czech Academy of Sciences Publication Activity Database

Tabor, Edyta; Poltowicz, J.; Pamin, K.; Basag, S.; Kubiak, W.

2016-01-01

Roč. 119, NOV 2016 (2016), s. 342-349 ISSN 0277-5387 Institutional support: RVO:61388955 Keywords : iron porphyrins * μ-Oxo porphyrins * oxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.926, year: 2016

Enhancing the Photovoltage of Ni/ n-Si Photoanode for Water Oxidation through a Rapid Thermal Process.

Science.gov (United States)

Li, Shengyang; She, Guangwei; Chen, Cheng; Zhang, Shaoyang; Mu, Lixuan; Guo, Xiangxin; Shi, Wensheng

2018-03-14

The Ni in the Ni/ n-Si photoanode can not only protect Si from corrosion, but also catalyze the water oxidation reaction. However, the high density of interface states at the Ni/ n-Si interface could pin the Fermi level of silicon, which will lower the Schottky barrier height of the Ni/ n-Si. As a result, a low photovoltage and consequent high onset potential of Ni/ n-Si photoanode for water oxidation were generated. In this study, the interfacial states of the Ni/ n-Si photoanodes were efficiently diminished through a rapid thermal process (RTP). Calculated from the Mott-Schottky plots, the Schottky barrier height of Ni/ n-Si was increased from 0.58 to 0.78 eV after RTP. Under the illumination of 100 mW cm -2 of the Xe lamp, the onset potential of the Ni/ n-Si photoanode for water oxidation was negatively shifted for 150 mV after RTP. Besides, the RTP-treated Ni/ n-Si photoanode exhibited a high stability during the PEC water oxidation of 8 h in 1 M KOH solution.

Porphyrin-based Nanostructure-Dependent Photodynamic and Photothermal Therapies

Science.gov (United States)

Jin, Cheng S.

This thesis presents the investigation of nanostructure-dependent phototherapy. We reviewed the liposomal structures for delivery of photosensitizers, and introduced a novel class of phototransducing liposomes called "porphysomes". Porphysomes are self-assembled from high packing density of pyropheophorbide alpha-conjugated phospholipids, resulting in extreme self-quenching of porphyrin fluorescence and comparable optical absorption to gold nanoparticles for high photothermal efficiency. We demonstrated this self-assembly of porphyrin-lipid conjugates converts a singlet oxygen generating mechanism (photodynamic therapy PDT activity) of porphyrin to photothermal mechanism (photothermal therapy PTT activity). The efficacy of porphysome-enhanced PTT was then evaluated on two pre-clinical animal models. We validated porphysome-enabled focal PTT to treat orthotopic prostate cancer using MRI-guided focal laser placement to closely mimic the current clinic procedure. Furthermore, porphysome-enabled fluorescence-guided transbronchial PTT of lung cancer was demonstrated in rabbit orthotopic lung cancer models, which led to the development of an ultra-minimally invasive therapy for early-stage peripheral lung cancer. On the other hand, the nanostructure-mediated conversion of PDT to PTT can be switched back by nanoparticle dissociation. By incorporating folate-conjugated phospholipids into the formulation, porphysomes were internalized into cells rapidly via folate receptor-mediated endocytosis and resulted in efficient disruption of nanostructures, which turned back on the photodynamic activity of densely packed porphyrins, making a closed loop of conversion between PDT and PTT. The multimodal imaging and therapeutic features of porphysome make it ideal for future personalized cancer treatments.

Tapping the biotechnological potential of insect microbial symbionts: new insecticidal porphyrins.

Science.gov (United States)

Martinez, Ana Flávia Canovas; de Almeida, Luís Gustavo; Moraes, Luiz Alberto Beraldo; Cônsoli, Fernando Luís

2017-06-27

The demand for sustainable agricultural practices and the limited progress toward newer and safer chemicals for use in pest control maintain the impetus for research and identification of new natural molecules. Natural molecules are preferable to synthetic organic molecules because they are biodegradable, have low toxicity, are often selective and can be applied at low concentrations. Microbes are one source of natural insecticides, and microbial insect symbionts have attracted attention as a source of new bioactive molecules because these microbes are exposed to various selection pressures in their association with insects. Analytical techniques must be used to isolate and characterize new compounds, and sensitive analytical tools such as mass spectrometry and high-resolution chromatography are required to identify the least-abundant molecules. We used classical fermentation techniques combined with tandem mass spectrometry to prospect for insecticidal substances produced by the ant symbiont Streptomyces caniferus. Crude extracts from this bacterium showed low biological activity (less than 10% mortality) against the larval stage of the fall armyworm Spodoptera frugiperda. Because of the complexity of the crude extract, we used fractionation-guided bioassays to investigate if the low toxicity was related to the relative abundance of the active molecule, leading to the isolation of porphyrins as active molecules. Porphyrins are a class of photoactive molecules with a broad range of bioactivity, including insecticidal. The active fraction, containing a mixture of porphyrins, induced up to 100% larval mortality (LD 50  = 37.7 μg.cm -2 ). Tandem mass-spectrometry analyses provided structural information for two new porphyrin structures. Data on the availability of porphyrins in 67 other crude extracts of ant ectosymbionts were also obtained with ion-monitoring experiments. Insect-associated bacterial symbionts are a rich source of bioactive compounds. Exploring

Confused or not Confused?: Disentangling Brain Activity from EEG Data Using Bidirectional LSTM Recurrent Neural Networks.

Science.gov (United States)

Ni, Zhaoheng; Yuksel, Ahmet Cem; Ni, Xiuyan; Mandel, Michael I; Xie, Lei

2017-08-01

Brain fog, also known as confusion, is one of the main reasons for low performance in the learning process or any kind of daily task that involves and requires thinking. Detecting confusion in a human's mind in real time is a challenging and important task that can be applied to online education, driver fatigue detection and so on. In this paper, we apply Bidirectional LSTM Recurrent Neural Networks to classify students' confusion in watching online course videos from EEG data. The results show that Bidirectional LSTM model achieves the state-of-the-art performance compared with other machine learning approaches, and shows strong robustness as evaluated by cross-validation. We can predict whether or not a student is confused in the accuracy of 73.3%. Furthermore, we find the most important feature to detecting the brain confusion is the gamma 1 wave of EEG signal. Our results suggest that machine learning is a potentially powerful tool to model and understand brain activity.

New carbon-carbon linked amphiphilic carboranyl-porphyrins as boron neutron capture agents

International Nuclear Information System (INIS)

Vicente, M.G.H.; Wickramasinghe, A.; Shetty, S.J.; Smith, K.M.

2000-01-01

Novel amphiphilic carboranyl-porphyrins have been synthesized for Boron Neutron Capture Therapy (BNCT). These compounds have carbon-carbon bonds between the carborane residues and the porphyrin meso-phenyl groups, and contain 28-31% boron by weight . (author)

Photoexcited iron porphyrin as biomimetic catalysts

International Nuclear Information System (INIS)

Bartocci, C.; Maldotti, A.; Varani, G.; Consiglio Nazionale delle Ricerche, Ferrara

1996-01-01

Photoexcited iron porphyrins can be of some interest in both fine and industrial chemistry in view of the preparation of new efficient biomimetic catalysts, working with high selectivity under mild temperature and pressure

Huellas tempranas del género en la adquisición y transmisión cultural: concepciones de niños y niñas sobre el aprendizaje de la escritura

Directory of Open Access Journals (Sweden)

Montserrat de la Cruz

2004-01-01

Full Text Available Este estudio pretende integrar el enfoque de género en la investigación de las concepciones en la niñez sobre el aprendizaje. En particular, está orientado a establecer si se observan diferencias de género en las concepciones de niños y niñas acerca del aprendizaje de la escritura y, en el caso en que se registren diferencias, caracterizarlas e interpretarlas. Los sujetos son 30 niños y 30 niñas de sectores sociales medios y marginados en Bariloche, Argentina, que cursan preescolar, primer grado y cuarto grado. Para indagar sus concepciones acerca del aprendizaje de la escritura, se diseñó y empleó una entrevista individual estructurada que incluye preguntas abiertas acerca de: la práctica familiar y personal de la escritura, el proceso de aprendizaje de la escritura, la historia personal del aprendizaje, las dificultades al escribir, la enseñanza de la escritura, las ayudas para aprender y la permanencia del aprendizaje. Las respuestas textuales de los niños y niñas fueron analizadas mediante el método lexicométrico. Se utilizó principalmente el procedimiento de selección automática de las respuestas modales. El análisis cualitativo posterior de las respuestas típicas de niños y niñas muestra importantes diferencias de género en las siguientes dimensiones, en notable coincidencia con los resultados de los estudios de género en la juventud y la adultez: asunción de la agencia y la asertividad en el aprendizaje; uso de comparaciones y de un marco de referencia autobiográfico; consideración y preocupación por las otras personas; referencias mentalistas; referencia a obligaciones; contextos de aprendizaje, enseñanza y práctica; bases de las ayudas para aprender (colaboración o punición; expresión de la emoción

Huellas tempranas del género en la adquisición y transmisión cultural: concepciones de niños y niñas sobre el aprendizaje de la escritura

Directory of Open Access Journals (Sweden)

Montserrat de la Cruz

2004-05-01

Full Text Available Este estudio pretende integrar el enfoque de género en la investigación de las concepciones en la niñez sobre el aprendizaje. En particular, está orientado a establecer si se observan diferencias de género en las concepciones de niños y niñas acerca del aprendizaje de la escritura y, en el caso en que se registren diferencias, caracterizarlas e interpretarlas. Los sujetos son 30 niños y 30 niñas de sectores sociales medios y marginados en Bariloche, Argentina, que cursan preescolar, primer grado y cuarto grado. Para indagar sus concepciones acerca del aprendizaje de la escritura, se diseñó y empleó una entrevista individual estructurada que incluye preguntas abiertas acerca de: la práctica familiar y personal de la escritura, el proceso de aprendizaje de la escritura, la historia personal del aprendizaje, las dificultades al escribir, la enseñanza de la escritura, las ayudas para aprender y la permanencia del aprendizaje. Las respuestas textuales de los niños y niñas fueron analizadas mediante el método lexicométrico. Se utilizó principalmente el procedimiento de selección automática de las respuestas modales. El análisis cualitativo posterior de las respuestas típicas de niños y niñas muestra importantes diferencias de género en las siguientes dimensiones, en notable coincidencia con los resultados de los estudios de género en la juventud y la adultez: asunción de la agencia y la asertividad en el aprendizaje; uso de comparaciones y de un marco de referencia autobiográfico; consideración y preocupación por las otras personas; referencias mentalistas; referencia a obligaciones; contextos de aprendizaje, enseñanza y práctica; bases de las ayudas para aprender (colaboración o punición; expresión de la emoción.

Functionalized porphyrin conjugate thin films deposited by matrix assisted pulsed laser evaporation

Energy Technology Data Exchange (ETDEWEB)

Iordache, S. [University of Bucharest, 3Nano-SAE Research Center, PO Box MG-38, Bucharest-Magurele (Romania); Cristescu, R., E-mail: rodica.cristescu@inflpr.ro [National Institute for Lasers, Plasma and Radiation Physics, Lasers Department, P.O. Box MG-36, Bucharest-Magurele (Romania); Popescu, A.C.; Popescu, C.E.; Dorcioman, G.; Mihailescu, I.N. [National Institute for Lasers, Plasma and Radiation Physics, Lasers Department, P.O. Box MG-36, Bucharest-Magurele (Romania); Ciucu, A.A. [University of Bucharest, Faculty of Chemistry, Bucharest (Romania); Balan, A.; Stamatin, I. [University of Bucharest, 3Nano-SAE Research Center, PO Box MG-38, Bucharest-Magurele (Romania); Fagadar-Cosma, E. [Institute of Chemistry Timisoara of Romanian Academy, M. Viteazul Ave. 24, 300223-Timisoara (Romania); Chrisey, D.B. [Tulane University, Departments of Physics and Biomedical Engineering, New Orleans, LA 70118 (United States)

2013-08-01

We report on the deposition of nanostructured porphyrin-base, 5(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin thin films by matrix assisted pulsed laser evaporation onto silicon substrates with screen-printed electrodes. AFM investigations have shown that at 400 mJ/cm{sup 2} fluence a topographical transition takes place from the platelet-like stacking porphyrin-based nanostructures in a perpendicular arrangement to a quasi-parallel one both relative to the substrate surface. Raman spectroscopy has shown that the chemical structure of the deposited thin films is preserved for fluences within the range of 200–300 mJ/cm{sup 2}. Cyclic voltammograms have demonstrated that the free porphyrin is appropriate as a single mediator for glucose in a specific case of screen-printed electrodes, suggesting potential for designing a new class of biosensors.

Depresión y autoconcepto en niños institucionalizados y no institucionalizados

Directory of Open Access Journals (Sweden)

Luis. F. Raffo Benavides

1994-12-01

Full Text Available El estudio investiga la depresión y el autoconcepto en grupos de niños Peruanos expuestos a situaciones socioafectivas negativas, destacando la importancia y características especificas de este desorden en el campo psicológico y clínico. Fueron seleccionados 35 niños institucionalizados, 30 niños de una zona marginal de Lima y 20 niños con diagnóstico de depresión; todos varones entre 8 y 14 años. Se estudió la correlación entre ambas variables, se comparó los puntajes a nivel intergrupal y se adaptó el CDI (Children Depressive Inventory, Kovacs, 1983. Se obtuvo una correlación negativa y significativa entre las variables de depresión y autoconcepto. Asimismo, se encuentra que la institucionalización y el bajo nivel socioeconómico tienen influencia en el grado de depresión hallado en los niños examinados, en cambio tienen poca trascendencia en el nivel de autoconcepto. La evaluación de la validez y confiabillidad de los instrumentos utilizados brinda resultados óptimos, presentándose datos adicionales importantes.

High-conductance surface-anchoring of a mechanically flexible platform-based porphyrin complex

International Nuclear Information System (INIS)

Hauptmann, Nadine; Buchmann, Kristof; Scheil, Katharina; Berndt, Richard; Groß, Lynn; Herrmann, Carmen; Schütt, Christian; Otte, Franziska L; Herges, Rainer

2015-01-01

The conductances of molecular model junctions comprising a triazatriangulenium platform with or without an ethynyl spacer and an upright Zn-porphyrin are probed with a low-temperature scanning probe microscope. The platform alone is found to be highly conductive. The ethynyl-linked Zn-porphyrin moiety reduces the conductance by three orders of magnitude and leads to an unexpected, non-monotonous variation of the force that was measured simultaneously at the tip of the microscope. Density functional theory calculations show that this variation results from an induced tilting of the porphyrin. (paper)

Pt(II) porphyrin modified TiO{sub 2} composites as photocatalysts for efficient 4-NP degradation

Energy Technology Data Exchange (ETDEWEB)

Mingyue, Duan [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xian, Shaanxi 710069 (China); Li Jun, E-mail: junli@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xian, Shaanxi 710069 (China); Min, Li [Datang Wujiang Gas Turbine Power Limited Liability Company, Jiangsu 215214 (China); Zengqi, Zhang; Chen, Wang [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xian, Shaanxi 710069 (China)

2012-05-01

Three Pt(II) porphyrins 5,10,15,20-tetra-[2 or 3 or 4-(3-phenoxy)propoxy]phenyl porphyrin]platinum(II) (1-3) were synthesized and characterized spectroscopically. The corresponding Pt(II) porphyrins-TiO{sub 2} composites were then prepared and characterized by means of FT-IR and diffused reflectance spectra, X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of Pt(II) porphyrins-TiO{sub 2} catalyst was investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under irradiation with Xenon lamp. The results indicated that Pt(II) porphyrins greatly enhanced the photocatalytic efficiency of bare TiO{sub 2} in photodegrading the 4-NP, and the distinct space tropisms of peripheral substituents in meso-sites of porphyrin ring led to different results.

Niños, televisión y violencia: una propuesta de educación para la recepción

OpenAIRE

García Núñez de Cáceres, Elsa Patricia

2005-01-01

A través de esta investigación documental se buscó una propuesta de solución al problema de recepción de violencia televisiva de los niños. Se revisaron tres temas: (a) la televisión y el niño, (b) la violencia en la televisión y (c) la educación para la recepción.Con el objetivo de enmarcar bajo la luz del conocimiento surgido del estudios de estas líneas de investigación y así se ofrece como resultado una propuesta de educación para la recepción enfocada a mejorar los hábitos de co...

Depresión y autoconcepto en niños institucionalizados y no institucionalizados

OpenAIRE

Luis. F. Raffo Benavides

1994-01-01

El estudio investiga la depresión y el autoconcepto en grupos de niños Peruanos expuestos a situaciones socioafectivas negativas, destacando la importancia y características especificas de este desorden en el campo psicológico y clínico. Fueron seleccionados 35 niños institucionalizados, 30 niños de una zona marginal de Lima y 20 niños con diagnóstico de depresión; todos varones entre 8 y 14 años. Se estudió la correlación entre ambas variables, se comparó los puntajes a nivel intergrupal y s...

Structural, electronic, and mechanical properties of CoN and NiN. An ab initio study

Energy Technology Data Exchange (ETDEWEB)

Amudhavalli, A.; Manikandan, M.; Cinthia, A. Jemmy; Rajeswarapalanichamy, R. [NMSSVN College, Tamil Nadu (India). Dept. of Physics; Iyakutti, K. [SRM Univ., Tamil Nadu (India). Dept. of Physics and Nanotechnology

2017-07-01

The structural stabilities of cobalt mononitride (CoN) and nickel mono-nitride (NiN) were investigated among the crystal structures, namely, NaCl (B1), CsCl (B2), and zinc blende (B3). It was found that the zinc blende (B3) phase was the most stable phase for both nitrides. A pressure-induced structural phase transition from B3 to B1 phase was predicted in these nitrides. The computed lattice parameter values were in agreement with the experimental values and other theoretical values. The electronic structures reveal that these nitrides are metallic at zero pressure. The computed elastic constants indicate that CoN and NiN are mechanically stable in the B1 and B3 phases. The variations of the elastic constants, bulk modulus, shear modulus, Poisson's ratio, and elastic anisotropy factor with pressure were investigated. The Debye temperature θ{sub D} values are reported for both the nitrides in their B1 and B3 phases. The high-pressure NaCl phase of both CoN and NiN were found to be ferromagnetic.

A one-dimensional polymeric cobalt(III–potassium complex with 18-crown-6, cyanide and porphyrinate ligands

Directory of Open Access Journals (Sweden)

Yassine Belghith

2014-03-01

Full Text Available The reaction of CoII(TpivPP {TpivPP is the dianion of 5,10,15,20-tetrakis[2-(2,2-dimethylpropanamidophenyl]porphyrin} with an excess of KCN salts and an excess of the 18-crown-6 in chlorobenzene leads to the polymeric title compound catena-poly[[dicyanido-2κ2C-(1,4,7,10,13,16-hexaoxacyclooctadecane-1κ6O{μ3-(2α,2β-5,10,15,20-tetrakis[2-(2,2-dimethylpropanamidophenyl]porphyrinato-1κO5:2κ4N,N′,N′′,N′′′:1′κO15}cobalt(IIIpotassium] dihydrate], {[CoK(CN2(C12H24O6(C64H64N8O4]·2H2O}n. The CoIII ion lies on an inversion center, and the asymmetric unit contains one half of a [CoIII(2α,2β-TpivPP(CN2]− ion complex and one half of a [K(18-C-6]+ counter-ion (18-C-6 is 1,4,7,10,13,16-hexaoxacyclooctadecane, where the KI ion lies on an inversion center. The CoIII ion is hexacoordinated by two C-bonded axial cyanide ligands and the four pyrrole N atoms of the porphyrin ligand. The KI ion is chelated by the six O atoms of the 18-crown-6 molecule and is further coordinated by two O atoms of pivalamido groups of the porphyrin ligands, leading to the formation of polymeric chains running along [011]. In the crystal, the polymeric chains and the lattice water molecules are linked by N—H...O and O—H...N hydrogen bonds, as well as weak C—H...O, O—H...π and C—H...π interactions into a three-dimensional supramolecular architecture.

Porphyrin doped vanadium pentoxide xerogel as electrode material

Energy Technology Data Exchange (ETDEWEB)

Anaissi, F.J.; Engelmann, F.M.; Araki, K.; Toma, H.E. [Sao Paulo Univ., SP (Brazil). Inst. de Quimica

2003-04-01

The lamellar composite material, VXG-TMPyP, obtained from the combination of cationic, water-soluble meso-(tetra-4-methyl-pyridinium)porphyrin (TMPyP) and vanadium pentoxide gel was investigated and employed as electrode modifying material. This material was isolated as a xerogel and characterized by X-ray diffraction, UV-Vis spectroscopy, cyclic voltammetry, spectro-electrochemistry and TG analysis. According to the X-ray diffraction data, the original VXG lamellar matrix framework is kept in the composite, evidencing a topotatic reaction. UV-Vis spectra indicated a strong interaction between VXG and TMPyP leading to the protonation of the porphyrin ring. In contrast with the vanadium oxide xerogel the new material is stable in water. The presence of the cationic porphyrin species in its structure turns it able to incorporate negatively charged ions, such as ferrocyanide and I{sup -}. The presence of the I{sub 2}/I{sup -} couple gives rise to a dramatic increase in the reversibility of the V{sup V/IV} process and in the charge capacity of the material. (authors)

Confusing the heterotic string

Science.gov (United States)

Benett, D.; Brene, N.; Mizrachi, Leah; Nielsen, H. B.

1986-10-01

A confusion mechanism is proposed as a global modification of the heterotic string model. It envolves a confusion hypersurface across which the two E 8's of the heterotic string are permuted. A remarkable numerical coincidence is found which prevents an inconsistency in the model. The low energy limit of this theory (after compactification) is typically invariant under one E 8 only, thereby removing the shadow world from the original model.

Percepción de la creatividad en niños, padres y pares: efectos en la producción creativa

Directory of Open Access Journals (Sweden)

Gabriela Krumm

2015-01-01

Full Text Available Objetivo . El presente estudio tuvo como objetivo evaluar la percepción de la creatividad en niños, padres y pares, y el efecto de estas percepciones sobre la producción creativa de los niños en actividades de papel y lápiz. Método. Participaron 359 alumnos de 9 a 13 años de diferentes escuelas y colegios de la provincia de Entre Ríos de la República Argentina. Para conocer la producción creativa, los niños completaron la prueba de figuras del Test de Pensamiento Creativo de Torrance Forma B. Para estudiar la valoración de los pares, padres y niños sobre la creatividad se aplicó el Sociograma “Compañero creativo”, la Escala de Personalidad Creadora (versión heteroevaluación a los padres o tutores y la versión autoevaluación a los niños de 11 a 13 años. Resultados. Los resultados mostraron que tanto la percepción parental ( F (2, 356 = 6.55, p = 0.002, así como la evaluación que realizan los pares ( F (2, 356 = 4.90, p = 0.008 sobre la creatividad mejoran la producción creativa del niño en las tareas de papel y lápiz. No se encontraron diferencias significativas en la producción creativa según la evaluación del niño sobre su propia creatividad. Conclusión. Los datos muestran la importancia cardinal de los factores contextuales, particularmente, la percepción de los padres y de los pares en los procesos de formación del yo en cuanto a las competencias y habilidades que son necesarias para realizar una actividad creadora.

Perfil cognitivo de niños con rendimientos bajos en comprensión lectora

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Lorena Canet-Juric

2013-10-01

Full Text Available La mayoría de los niños con dificultades en la comprensión lectora poseen rendimientos inferiores en un conjunto de procesos cognitivos. El objetivo del presente estudio es establecer un perfil cognitivo asociado al bajo rendimiento en comprensión lectora en relación a la habilidad de monitoreo, a la producción de inferencias, al vocabulario, a la amplitud de memoria de trabajo y a la capacidad inhibitoria, en niños hispanoparlantes. Para ello se administraron tareas correspondientes a dichos procesos en niños con altos y bajos rendimientos en comprensión lectora. Los resultados mostraron que si bien los niños con mala comprensión presentan bajos rendimientos en estas habilidades, no puede establecerse un perfil consistente ya que hay niños con problemas en comprensión que presentan normal o superior rendimiento en algunas de estas habilidades cognitivas.

HREEL study of c(53x9)rect-N structure on Ni(111) surface

International Nuclear Information System (INIS)

Papagno, M.; Pacile, D.; Giallombardo, C.; Cupolillo, A.; Papagno, L.

2005-01-01

In this work we have prepared and characterized by low energy electron diffraction (LEED) and high-resolution electron energy loss spectroscopy (HREELS) the Ni(111)-c(53x9)rect-N surface structure formed by saturating the Ni(111) surface with nitrogen atoms. This structure was obtained by the ion-gauge assisted N 2 exposure method. The loss spectra show features at 50 and 25meV assigned to the N-Ni vibration and to a phonon of the reconstructed surface, respectively. We also investigated the case in which the Ni(111) surface was covered with a low coverage of N atoms

Syntheses and biological evaluation of F-18 and I-123 labeled porphyrins as potential tumor imaging agents

Energy Technology Data Exchange (ETDEWEB)

Lee, J. H.; Ji, D. Y. [Inha University, Incheon (Korea, Republic of); Moon, B. S.; Lee, T. S.; Lee, D. H.; Lee, K. C.; Ahn, G. I.; Yang, S. D.; Choi, C. W.; Jun, K. S. [KIRAMS, Seoul (Korea, Republic of)

2005-07-01

Photofrin has currently been approved for general use by licensing authorities to treatment for solid tumor and cancer using photodynamic therapy (PDT) that treat to photochemical effect induced by light. Recently, meso-tetra(3-hydroxyphenyl)porphyrin has been developed as one of best tumor localizer and also shown a favorable tissue distribution. We have studied to develop I-123 labeled meso-tetra(3-methoxyphenyl)porphyrins for tumor imaging. We have studied to develop iodine-123 labeled meso-tetra(3-carboxymethoxy phenyl)porphyrin for tumor imaging agent. The radioiodinated porphyrin compound was obtained by the iodination reaction of tin precursor (50 ig) of porphyrin with Na-123I (200 {mu}L, 100-200 mCi), in the presence of peracetic acid (40 {mu}L) in ethanol. Iodine-123 labeled porphyrin derivative was obtained in 20-30% radiochemical yield and purified by HPLC at 2 mL/min using EtOH/water gradient condition and the fraction at 24-26 min was collected and characterized to desired compound by co injection with cold porphyrin analogue. Total time was around 120 min. The in vitro and in vivo of I-123 labeled porphyrin derivative is under studying.

Syntheses and biological evaluation of F-18 and I-123 labeled porphyrins as potential tumor imaging agents

International Nuclear Information System (INIS)

Lee, J. H.; Ji, D. Y.; Moon, B. S.; Lee, T. S.; Lee, D. H.; Lee, K. C.; Ahn, G. I.; Yang, S. D.; Choi, C. W.; Jun, K. S.

2005-01-01

Photofrin has currently been approved for general use by licensing authorities to treatment for solid tumor and cancer using photodynamic therapy (PDT) that treat to photochemical effect induced by light. Recently, meso-tetra(3-hydroxyphenyl)porphyrin has been developed as one of best tumor localizer and also shown a favorable tissue distribution. We have studied to develop I-123 labeled meso-tetra(3-methoxyphenyl)porphyrins for tumor imaging. We have studied to develop iodine-123 labeled meso-tetra(3-carboxymethoxy phenyl)porphyrin for tumor imaging agent. The radioiodinated porphyrin compound was obtained by the iodination reaction of tin precursor (50 ig) of porphyrin with Na-123I (200 μL, 100-200 mCi), in the presence of peracetic acid (40 μL) in ethanol. Iodine-123 labeled porphyrin derivative was obtained in 20-30% radiochemical yield and purified by HPLC at 2 mL/min using EtOH/water gradient condition and the fraction at 24-26 min was collected and characterized to desired compound by co injection with cold porphyrin analogue. Total time was around 120 min. The in vitro and in vivo of I-123 labeled porphyrin derivative is under studying

Educación de la expresión de la sexualidad y la inteligencia emocional en niñas, niños y adolescentes con derechos

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Sonia Carballo Vargas

2006-01-01

Full Text Available En el presente artículo se integra la educación de la inteligencia emocional y la educación de la expresión de la sexualidad humana tomando como principal base los planteamientos de H. Gardner, D. Goleman y los aportes de la experiencia de la investigadora como educadora sexual, en la Universidad de Costa Rica y en el sistema educativo costarricense. A manera de conclusión se concretan lineamientos para educar en niños, niñas y adolescentes la expresión de la sexualidad en forma inteligente cognitiva y emocionalmente.

Planificación cognitiva en niños con déficit auditivo

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Ángela González Vinasco

2008-01-01

Full Text Available Este estudio busca abordar y explorar la habilidad para planificar de los niños con déficit auditivo ante una Situación de Resolución de Problemas (SRP, por medio del uso de las Tecnologías de la Información y la Comunicación (TIC, como una herramienta para acceder, de manera objetiva, a los procesos cognitivos del niño con déficit auditivo, sin demandarle ningún tipo de lenguaje verbal, escrito o por medio de señas. Se analizó el desempeño de 11 niños con déficit auditivo que asisten al Instituto para Niños Ciegos y Sordos del Valle del Cauca, con edades entre 4 y 5 años, quienes utilizan ayudas tecnológicas tales como el implante coclear y audífonos. Se realizó un estudio de carácter descriptivo y transversal a partir de una escala de medición continua, con un análisis de los resultados de tipo cuantitativo y cualitativo. Entre los principales resultados del estudio se encuentran: la presencia de mejoras en el desempeño de los niños a través de los tres intentos que debían realizar para resolver la SRP. Aunque las diferencias inter-intentos no fueron estadísticamente significativas, se observó que los niños con déficit auditivo son capaces de trazarse planes parciales y de utilizar estrategias sofisticadas en la resolución de la tarea. Se concluye sobre la importancia de utilizar instrumentos de recolección de la información, adaptados a las necesidades y características de cada población, al momento de evaluar, describir y potencializar los procesos cognitivos de los niños, en este caso de los niños con déficit auditivo.

Photokinetic and ultrastructural studies on porphyrin photosensitization of HeLa cells

International Nuclear Information System (INIS)

Milanesi, Carla; Sorgato, Fiorella; Jori, Giulio

1989-01-01

Liposome-bound haematoporphyrin or haematoporphyrin dimethylester, as well as haematoporphyrin dissolved in phosphate-buffered saline, were added to HeLa cell monolayers at a dose of 1 μg of porphyrin per 10 5 cells. After 2 min or 20 min incubation liposome-bound porphyrins were accumulated by cells in an about two-fold larger amount than the water-dissolved haematoporphyrin. This caused a more efficient photosensitization of HeLa cells by liposome-delivered porphyrins upon illumination with 366 nm light. Ultrastructural studies of HeLa cells, which had been incubated in a physiological medium for 24 h after the end of irradiation, showed that liposomal porphyrins induce an early and extensive endocytoplasmic damage, leading to mitochondrial swelling and vesiculation; changes of permeability of the cytoplasmic membrane are also evident, especially in the case of haematoporphyrin dimethylester. On the other hand, water-dissolved haematoporphyrin predominantly photosensitizes damage of the plasma membrane. The different pattern of cell photodamage probably reflects a different subcellular distribution of the photosensitizing drugs. (author)

Optical acetylcholine sensor based on free base porphyrin as a chromoionophore.

Science.gov (United States)

Mroczkiewicz, Monika; Pietrzak, Mariusz; Górski, Łukasz; Malinowska, Elżbieta

2011-09-21

In this work, the possibility of application of free base porphyrin as a lipophilic pH chromoionophore for the preparation of optical cation-selective sensors was investigated. The properties of polymeric membranes, containing porphyrins of different structures, namely tetraphenylporphyrin (TPP) and octaethylporphyrin (OEP), were compared. Changes in equilibrium between protonated and deprotonated form of porphyrin, resulting from variations in ACh concentration, were evaluated. The influence of various factors (kind and quantity of anionic additive and porphyrin in the membrane phase, pH of sample solution) on initial equilibrium was studied. The best membrane composition was chosen as: TPP 3 wt.%, KTFPB 175 mol.% relative to ionophore, PVC:o-NPOE (1 : 4) and measuring buffer solution: 0.05 M MES, pH 4.5. Selectivity, response stability, reversibility and repeatability tests were carried out for chosen sensor. Developed sensor allowed for the determination of a model analyte, acetylcholine, at the concentration range of 10(-5) to 10(-2) M, both in stationary and flow-injection system. Sensor response was reversible and repeatable in the mentioned concentration range.

Confusing the heterotic string

International Nuclear Information System (INIS)

Benett, D.L.; Mizrachi, L.

1986-01-01

A confusion mechanism is proposed as a global modification of the heterotic string model. It envolves a confusion hypersurface across which the two E 8 's of the heterotic string are permuted. A remarkable numerical coincidence is found which prevents an inconsistency in the model. The low energy limit of this theory (after compactification) is typically invariant under one E 8 only, thereby removing the shadow world from the original model. (orig.)

Confusing the heterotic string

Energy Technology Data Exchange (ETDEWEB)

Benett, D.L.; Brene, N.; Nielsen, H.B.; Mizrachi, L.

1986-10-02

A confusion mechanism is proposed as a global modification of the heterotic string model. It envolves a confusion hypersurface across which the two E/sub 8/'s of the heterotic string are permuted. A remarkable numerical coincidence is found which prevents an inconsistency in the model. The low energy limit of this theory (after compactification) is typically invariant under one E/sub 8/ only, thereby removing the shadow world from the original model.

DFT/TD-semiempirical study on the structural and electronic properties and absorption spectra of supramolecular fullerene-porphyrine-metalloporphyrine triads based dye-sensitized solar cells

Science.gov (United States)

Rezvani, M.; Darvish Ganji, M.; Jameh-Bozorghi, S.; Niazi, A.

2018-04-01

In the present work density functional theory (DFT) and time-dependent semiempirical ZNIDO/S (TD-ZNIDO/S) methods have been used to investigate the ground state geometries, electronic structures and excited state properties of triad systems. The influences of the type of metal in the porphyrin ring, change in bridge position and porphyrine-ZnP duplicate on the energies of frontier molecular orbital and UV-Vis spectra has been studied. Geometry optimization, the energy levels and electron density of the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO), chemical hardness (η), electrophilicity index (ω), electron accepting power (ω+) were calculated using ZINDO/S method to predict which molecule is the most efficient with a great capability to be used as a triad molecule in solar industry. Moreover the light harvesting efficiency (LHE) was calculated by means of the oscillator strengths which are obtained by TD-ZINDO/S calculation. Theoretical studies of the electronic spectra by ZINDO/S method were helpful in interpreting the observed electronic transitions. This aspect was systematically explored in a series of C60-Porphyrine-Metalloporphyrine (C60-P-Mp) triad system with M being Fe, Co, Ni, Ti, and Zn. Generally, transition metal coordination compounds are used as effective sensitizers, due to their intense charge-transfer absorption over the whole visible range and highly efficient metal-to-ligand charge transfer. We aim to optimize the performance of the title solar cells by altering the frontier orbital energy gaps. The results reveal that cell efficiency can be enhanced by metal functionalization of the free base porphyrin. Ti-porphyrin was found to be the most efficient dye sensitizer for dye sensitized solar cells (DSSCs) based on C60-P-Mptriad system due to C60-Por-TiP complex has lower chemical hardness, gap energy and chemical potential as well as higher electron accepting power among other complexes. In

Relación entre la televisión y la manifestación de problemas conductuales en niños preescolares

OpenAIRE

Oliva Zárate, Laura; Sevillano García, María Luisa

2007-01-01

En este estudio se realiza el análisis del uso de la televisión en niños de 4 a 5 años de edad y su relación con los problemas de conducta. Los instrumentos utilizados fueron el Cuestionario sobre el comportamiento de niños de 11/2-5 años de T. Achenbach y L. Rescorla (2002), aplicado a 535 padres de niños de 20 escuelas de nivel preescolar que resultaron de un muestreo representativo de la ciudad de Xalapa-México a fin de identificar problemas conductuales en los niños, el Cuestion...

Relación entre la televisión y la manifestación de problemas conductuales en niños preescolares

OpenAIRE

Oliva Zárate, Laura; Sevillano García, María Luisa

2007-01-01

RESUMEN: En este estudio se realiza el análisis del uso de la televisión en niños de 4 a 5 años de edad y su relación con los problemas de conducta. Los instrumentos utilizados fueron el Cuestionario sobre el comportamiento de niños de 11/2-5 años de T. Achenbach y L. Rescorla (2002), aplicado a 535 padres de niños de 20 escuelas de nivel preescolar que resultaron de un muestreo representativo de la ciudad de Xalapa-México a fin de identificar problemas conductuales en los niños, el Cuestiona...

Relación entre la televisión y la manifestación de problemas conductuales en niños preescolares

OpenAIRE

Oliva Zárate, Laura; Sevillano García, María Luisa

2007-01-01

[ES] En este estudio se realiza el análisis del uso de la televisión en niños de 4 a 5 años de edad y su relación con los problemas de conducta. Los instrumentos utilizados fueron el Cuestionario sobre el comportamiento de niños de 11/2-5 años de T. Achenbach y L. Rescorla (2002), aplicado a 535 padres de niños de 20 escuelas de nivel preescolar que resultaron de un muestreo representativo de la ciudad de Xalapa-México a fin de identificar problemas conductuales en los niños, el Cuestionario ...

Light-activated nanotube–porphyrin conjugates as effective antiviral agents

International Nuclear Information System (INIS)

Banerjee, Indrani; Douaisi, Marc P; Mondal, Dhananjoy; Kane, Ravi S

2012-01-01

Porphyrins have been used for photodynamic therapy (PDT) against a wide range of targets like bacteria, viruses and tumor cells. In this work, we report porphyrin-conjugated multi-walled carbon nanotubes (NT-P) as potent antiviral agents. Specifically, we used Protoporphyrin IX (PPIX), which we attached to acid-functionalized multi-walled carbon nanotubes (MWNTs). We decided to use carbon nanotubes as scaffolds because of their ease of recovery from a solution through filtration. In the presence of visible light, NT-P was found to significantly reduce the ability of Influenza A virus to infect mammalian cells. NT-P may be used effectively against influenza viruses with little or no chance of them developing resistance to the treatment. Furthermore, NT-P can be easily recovered through filtration which offers a facile strategy to reuse the active porphyrin moiety to its fullest extent. Thus NT-P conjugates represent a new approach for preparing ex vivo reusable antiviral agents. (paper)

O{sub 2} adsorption and dissociation on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Li, Sha; Yang, Yongpeng; Huang, Shiping, E-mail: huangsp@mail.buct.edu.cn

2017-07-15

Highlights: • O{sub 2} adsorption and dissociation on Pd{sub 13-n}Ni{sub n}@Pt{sub 42} NPs are performed by DFT. • Adsorption energies of O{sub 2} and O are strongly affected by the coordination number. • Adsorption energy and d-band center displays the opposite change tendency. • Ni{sub 13}@Pt{sub 42} is the most active catalyst among Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) NPs. - Abstract: Density functional theory calculations are performed to investigate O{sub 2} adsorption and dissociation on the icosahedral Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles. The parallel adsorption of O{sub 2} on Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) is stronger than the vertical adsorption. The adsorption of O{sub 2} on the bridge site (B1) is favorable in the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) nanoparticles, while the adsorption of O atom on the hollow site (H1) is preferred. The adsorption energies of O{sub 2} and O are strongly affected by the coordination number. Low coordination site shows strong adsorption of O{sub 2} and O on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) nanoparticles. The adsorption energies of O{sub 2} and O atoms are found to be correlated well with the d-band center of surface Pt. For the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and13) nanoparticles catalysts, the ORR activity follows the order of Ni{sub 13}@Pt{sub 42} > Pd{sub 13}@Pt{sub 42} > Pd{sub 12}Ni{sub 1}@Pt{sub 42} > Pd{sub 1}Ni{sub 12}@Pt{sub 42}, illustrating that the Ni{sub 13}@Pt{sub 42} is the strongest ORR activity among the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and13) nanoparticles catalysts. Our results have important significance to understand the mechanism of O{sub 2} dissociation on the Pd{sub 13-n}Ni{sub n}@Pt{sub 42} (n = 0, 1, 12, and 13) tri-metallic nanoparticles.

La importancia de las políticas públicas de formación en investigación de niños, niñas y jóvenes en Colombia, para el desarrollo social

Directory of Open Access Journals (Sweden)

Héctor Mauricio Rojas Betancur

2008-10-01

Full Text Available Dos presupuestos contienen el nudo de justificación de la inclusión y del desarrollo de políticas públicas para la formación en investigación de niños, niñas y jóvenes: el primero es asumir que la investigación científica es la producción, apropiación y aplicación de conocimientos a través de ciertas reglas de uso y validación. El segundo presupuesto indica que las políticas públicas en temas de ciencia, tecnología y sociedad, deben privilegiar el ámbito de formación de niños, niñas y jóvenes. Para ello debe promoverse una revisión social de la formación y de las prácticas pedagógicas pues el país muestra un atraso significativo en ciencia, especialmente en la formación de comunidades académicas que garanticen el relevo generacional ampliado, presente y futuro, y la realización de una investigación con sentido social.En este artículo se pretende mostrar que, si bien el objeto de formar niños, niñas y jóvenes en ciencia está articulado con los grandes temas del desarrollo social, su aplicación deriva en una estrategia didáctica de muy poco impacto educativo e investigativo, pues aun cuando los niños, niñas y jóvenes tienen una alta capacidad problematizadora para ser científicos o científicas, la mayor responsabilidad recae en unas instituciones educativas escolares que no están diseñadas para potenciar su aprovechamiento y que no están muy dispuestas a transformar sus prácticas académicas y administrativas.

Investigation of cobalt porphyrin doped polymer membrane films for the optical sensing of imidazole and its derivatives

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Yueyang Tan

2015-03-01

Full Text Available A cobalt(II porphyrin was successfully incorporated into polymer membranes for the optical sensing of imidazole and its derivatives. This research has led to a better understanding of the behavior of Co(II porphyrin in solution and in polymeric membranes. In aprotic dichloromethane (DCM, the Co(II tetraphenylporphyrin (CoTPP and Co(II octaethylporphyrin (CoOEP show a sensitive response to imidazole due to the strong ligation of the N-3 on the imidazole ring to the Co(II center, which induces an absorbance change to the Soret band. However, when doped in polymeric films, only the CoTPP exhibits moderate sensitivity towards aqueous imidazole, histamine and histidine. This weakened coordination ability of CoTPP towards imidazole in the polymer films may be due to the coordination of the plasticizer, the impurities from the THF and polymer matrix at the Co(II center. The selectivity of the polymer films towards imidazole over common anions is high. Lifetime of the cobalt(II porphyrin incorporated polymer film was relatively short.

Water Soluble Cationic Porphyrin Sensor for Detection of Hg2+, Pb2+, Cd2+, and Cu2+

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Matibur Zamadar

2016-01-01

Full Text Available Here we report the sensing properties of the aqueous solution of meso-tetra(N-methyl-4-pyridylporphine tetrachloride (1 for simultaneous detection of toxic metal ions by using UV-vis spectroscopy. Cationic porphyrin 1 displayed different electronic absorptions in UV-vis region upon interacting with Hg2+, Pb2+, Cd2+, and Cu2+ ions in neutral water solution at room temperature. Quite interestingly, the porphyrin 1 showed that it can function as a single optical chemical sensor and/or metal ion receptor capable of detecting two or more toxic metal ions, particularly Hg2+, Pb2+, and Cd2+ ions coexisting in a water sample. Porphyrin 1 in an aqueous solution provides a unique UV-vis sensing system for the determination of Cd2+ in the presence of larger metal ions such as Hg2+, or Pb2+. Finally, the examination of the sensing properties of 1 demonstrated that it can operate as a Cu2+ ion selective sensor via metal displacement from the 1-Hg2+, 1-Pb2+, and 1-Cd2+.

Physical origin of third order non-linear optical response of porphyrin nanorods

International Nuclear Information System (INIS)

Mongwaketsi, N.; Khamlich, S.; Pranaitis, M.; Sahraoui, B.; Khammar, F.; Garab, G.; Sparrow, R.; Maaza, M.

2012-01-01

The non-linear optical properties of porphyrin nanorods were studied using Z-scan, Second and Third harmonic generation techniques. We investigated in details the heteroaggregate behaviour formation of [H 4 TPPS 4 ] 2- and [SnTPyP] 2+ mixture by means of the UV-VIS spectroscopy and aggregates structure and morphology by transmission electron microscopy. The porphyrin nanorods under investigation were synthesized by self assembly and molecular recognition method. They have been optimized in view of future application in the construction of the light harvesting system. The focus of this study was geared towards understanding the influence of the type of solvent used on these porphyrins nanorods using spectroscopic and microscopic techniques. Highlights: ► We synthesized porphyrin nanorods by self assembly and molecular recognition method. ► TEM images confirmed solid cylindrical shapes. ► UV-VIS spectroscopy showed the decrease in the absorbance peaks of the precursors. ► The enhanced third-order nonlinearities were observed.

Synthesis and photophysical properties of phosphorus(V) porphyrins functionalized with axial carbazolylvinylnaphthalimides.

Science.gov (United States)

Zhan, Yong; Cao, Kaiyu; Wang, Chenguang; Jia, Junhui; Xue, Pengchong; Liu, Xingliang; Duan, Xuemei; Lu, Ran

2012-11-21

We have synthesized new D-A-D type phosphorus(V) porphyrin derivatives and functionalized with axial carbazolylvinylnaphthalimide units. The absorption bands of the obtained phosphorus(V) porphyrins were in the range 250-640 nm with high molar absorption coefficients, meaning strong light-harvesting abilities. Notably, it is found that the devices based on phosphorus(V) porphyrins with a configuration structure of [ITO/PEDOT : PSS/organic active film/LiF/Al] give an incident-photon-to-current conversion efficiency (IPCE) response. The maximal IPCE value reaches 2.76% for the device based on compound , which is much higher than that of 0.20% for compound . The reason might be due to the low oxidation potential and the strong light-harvesting ability of the enlarged conjugation of the axial units in compound . Therefore, we deduced that photo-induced electron transfer happened in phosphorus(V) porphyrins bearing axial conjugated donor units, which would make them good candidates for photovoltaic materials that could be applied in solar cells.

Ni0 encapsulated in N-doped carbon nanotubes for catalytic reduction of highly toxic hexavalent chromium

Science.gov (United States)

Yao, Yunjin; Zhang, Jie; Chen, Hao; Yu, Maojing; Gao, Mengxue; Hu, Yi; Wang, Shaobin

2018-05-01

N-doped carbon nanotubes encapsulating Ni0 nanoparticles (Ni@N-C) were fabricated via thermal reduction of dicyandiamide and NiCl2·6H2O, and used to remove CrVI in polluted water. The resultant products present an excellent catalytic activity for CrVI reduction using formic acid under relatively mild conditions. The CrVI reduction efficiency of Ni@N-C was significantly affected by the preparation conditions including the mass of nickel salt and synthesis temperatures. The impacts of several reaction parameters, such as initial concentrations of CrVI and formic acid, solution pH and temperatures, as well as inorganic anions in solution on CrVI reduction efficiency were also evaluated in view of scalable industrial applications. Owing to the synergistic effects amongst tubes-coated Ni0, doped nitrogen, oxygen containing groups, and the configuration of carbon nanotubes, Ni@N-C catalysts exhibit excellent catalytic activity and recyclable capability for CrVI reduction. Carbon shell can efficiently protect inner Ni0 core and N species from corrosion and subsequent leaching, while Ni0 endows the Ni@N-C catalysts with ferromagnetism, so that the composites can be easily separated via a permanent magnet. This study opens up an avenue for design of N-doped carbon nanotubes encapsulating Ni0 nanoparticles with high CrVI removal efficiency and magnetic recyclability as low-cost catalysts for industrial applications.

Utilidad de la Escala de Conners en la identificación de síntomas de déficit de atención e hiperactividad en niños y niñas con retraso mental

OpenAIRE

Luis Felipe Gomez Quiñonez

2013-01-01

Antecedentes: Los síntomas de déficit de atención e hiperactividad son muy frecuentes en niños y niña con retraso mental, sin embargo, no se ha informado la utilidad de la escala de Conners en la identificación de estos síntomas en esta población. Objetivo: Validar la escala de Conners para trastorno por déficit de atención e hiperactividad en niños y niñas con retraso mental de la consulta externa de un hospital psiquiátrico. Método: Fueron evaluados 34 niños y niñas con retraso mental en ed...

El niño con discapacidad: elementos orientadores para su inclusión social

Directory of Open Access Journals (Sweden)

Eliana Isabel Parra Esquivel

2015-01-01

Full Text Available Objetivos: proporcionar orientaciones conceptuales y prácticas a cuidadores, maestros, profesionales que trabajen con población infantil y comunidad en general respecto a es - trategias inclusivas acertadas para el niño con discapacidad (cero a doce años. Para ello se mencionan algunas herramientas prácticas (procedimientos, instrumentos, estrategias, adecuaciones, cuya utilización ayuda a comprender la situación y a mejorar la participación del niño en contextos de desempeño ocupacional cotidiano: hogar, escuela, actividades de juego y de tiempo libre. En últimas, se espera favorecer una participación más efectiva del niño en sus ambientes y roles ocupacionales, al reconocer las demandas de estos, así como el manejo más acertado, desde la perspectiva profesional de Terapia Ocupacional. Materiales: metodológicamente, este estudio rastreó fuentes especializadas nacionales e internacionales de Terapia Ocupacional desde el año 2000 sobre tres conceptos clave: niños con discapacidad, desempeño ocupacional y estrategias inclusivas. En cada fuente se identificaron las estrategias de inclusión propuestas para favorecer la participación del niño en ocupaciones cotidianas. Conclusiones: se avanzó en plantear reflexiones sobre las implicaciones ocupacionales de la discapacidad en niños, en pro de favorecer dinámicas incluyentes. Los referentes conceptuales que explican la participación del niño en los ambientes y roles que le son cotidianos (hogar, escuela y disfrute de actividades lúdicas y de tiempo libre insisten en que las acciones con esta población deben partir de reconocer las particularidades en cada caso. Al sensibilizar sobre la complejidad de la discapacidad se asume una mirada multidi - mensional y transdisciplinaria en la comprensión, atención y valoración de las necesidades de los niños con discapacidad.

Highly Efficient Cooperative Catalysis by Co ^III (Porphyrin) Pairs in Interpenetrating Metal-Organic Frameworks

Energy Technology Data Exchange (ETDEWEB)

Lin, Zekai; Zhang, Zhi-Ming; Chen, Yu-Sheng; Lin, Wenbin (UC); (Xiamen)

2016-12-02

A series of porous twofold interpenetrated In-Co^III(porphyrin) metal–organic frameworks (MOFs) were constructed by in situ metalation of porphyrin bridging ligands and used as efficient cooperative catalysts for the hydration of terminal alkynes. The twofold interpenetrating structure brings adjacent Co^III(porphyrins) in the two networks parallel to each other with a distance of about 8.8 Å, an ideal distance for the simultaneous activation of both substrates in alkyne hydration reactions. As a result, the In-Co^III(porphyrin) MOFs exhibit much higher (up to 38 times) catalytic activity than either homogeneous catalysts or MOF controls with isolated Co^III(porphyrin) centers, thus highlighting the potential application of MOFs in cooperative catalysis.

Biodistribution, toxicity and efficacy of a boronated porphyrin for boron neutron capture therapy

International Nuclear Information System (INIS)

Miura, Michiko; Micca, P.; Fairchild, R.; Slatkin, D.; Gabel, D.

1992-01-01

Boron-containing porphyrins may be useful for boron neutron capture therapy (BNCT) in the treatment of brain tumors. Porphyrins have been shown to accumulate in tumor tissue and to be essentially excluded from normal brain. However, problems of toxicity may prevent some boron-containing porphyrins from being considered for BNCT. The authors have synthesized the boronated porphyrin 2,4-bis-vinyl-o-nidocarboranyl-deuteroporphyrin IX (VCDP). Preliminary studies in tumor-bearing mice showed considerable uptake of boron at a total dose of 150 μg/gbw with low mortality. They now report that a total dose to mice of ∼ 275 μg VCDP/gbw administered in multiple intraperitoneal (ip) injections can provide 40-50μg B per gram of tumor with acceptable toxicity. Toxicity experiments and a preliminary trial of BNCT in mice given such doses are also reported

El impacto de la detención migratoria en los niños

OpenAIRE

Farmer, Alice

2013-01-01

Los Estados con frecuencia detienen a los niños sin la debida atención al derecho internacional y en condiciones que pueden ser inhumanas y perjudiciales. Los niños solicitantes de asilo y refugiados deben ser tratados antes que nada como niños, dando prioridad a sus derechos y necesidades de protección en todas las políticas migratorias.

Electrocatalytic behaviour and application of manganese porphyrin/gold nanoparticle- surface modified glassy carbon electrodes

Energy Technology Data Exchange (ETDEWEB)

Sebarchievici, I., E-mail: incemc@incemc.ro [National Institute of Research for Electrochemistry and Condensed Matter, Aurel Paunescu Podeanu Street 144, 300569 Timisoara (Romania); Tăranu, B.O. [National Institute of Research for Electrochemistry and Condensed Matter, Aurel Paunescu Podeanu Street 144, 300569 Timisoara (Romania); Birdeanu, M. [National Institute of Research for Electrochemistry and Condensed Matter, Aurel Paunescu Podeanu Street 144, 300569 Timisoara (Romania); Institute of Chemistry Timisoara of Romanian Academy, M. Viteazul Ave. 24, 300223 Timisoara (Romania); Rus, S.F. [National Institute of Research for Electrochemistry and Condensed Matter, Aurel Paunescu Podeanu Street 144, 300569 Timisoara (Romania); Fagadar-Cosma, E., E-mail: efagadar@yahoo.com [Institute of Chemistry Timisoara of Romanian Academy, M. Viteazul Ave. 24, 300223 Timisoara (Romania)

2016-12-30

Highlights: • Mn-porphyrin/gold nanoparticle-modified glassy carbon electrodes were obtained. • AFM investigations of thin films display multilayer of triangular type architecture. • Oxidation and reduction processes of H{sub 2}O{sub 2} are diffusion controled. • There is a linear dependence between H{sub 2}O{sub 2} concentration and the currents intensity. • The modified electrodes show better electrochemical detection ability to H{sub 2}O{sub 2}. - Abstract: The main purpose of this research was to obtain manganese porphyrin/gold nanoparticle-modified glassy carbon electrodes and to use them for the detection of H{sub 2}O{sub 2}. Two sets of modified electrodes were prepared by drop-cast deposition of 5,10,15,20-tetra(4-methyl-phenyl)porphyrinato manganese(III) chloride alone and of the same Mn-porphyrin and gold-colloid solution and comparatively characterized by Raman, UV–vis, ellipsometry, AFM and TEM microscopy, XPS and cyclic voltammetry. XPS spectrum recorded for GC-MnP-nAu modified electrode displayed the characteristic signals of gold nanoparticles. The optical parameters have greater values for GC-MnP-nAu in comparison with GC-MnP, due to increasing charge transfer efficiency. The MnP-nAu film mediates the electron transfer between H{sub 2}O{sub 2} and GC, evidenced by an increase in the current intensity of the anodic peak, and facilitates the electrochemical regeneration of oxidized H{sub 2}O{sub 2} at cathodic potentials. From the cyclic voltammetry experiments a linear relationship between H{sub 2}O{sub 2} concentration vs oxidation and reduction currents was observed. The linear dependence between density of current and the square root of the scan rate indicates that the oxidation and reduction processes of H{sub 2}O{sub 2} are diffusion controlled. The GC-MnP-nAu modified electrode shows great potential as electrochemical sensor for determination of hydrogen peroxide.

Hierarchical hybrid of Ni{sub 3}N/N-doped reduced graphene oxide nanocomposite as a noble metal free catalyst for oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Zhao, Qi; Li, Yingjun; Li, Yetong [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Huang, Keke [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Zhang, Jun, E-mail: cejzhang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

2017-04-01

Highlights: • Hybrid of Ni{sub 3}N/N-RGO catalysts are synthesized by using a two-step method. • The catalysts manifest superior catalytic activity towards the ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: Novel nickel nitride (Ni{sub 3}N) nanoparticles supported on nitrogen-doped reduced graphene oxide nanosheets (N-RGOs) are synthesized via a facile strategy including hydrothermal and subsequent calcination methods, in which the reduced graphene oxide nanosheets (RGOs) are simultaneously doped with nitrogen species. By varying the content of the RGOs, a series of Ni{sub 3}N/N-RGO nanocomposites are obtained. The Ni{sub 3}N/N-RGO-30% hybrid nanocomposite exhibits superior catalytic activity towards oxygen reduction reaction (ORR) under alkaline condition (0.1 M KOH). Furthermore, this hybrid catalyst also demonstrates high tolerance to methanol poisoning. The RGO containing rich N confers the nanocomposite with large specific surface area and high electronic conduction ability, which can enhance the catalytic efficiency of Ni{sub 3}N nanoparticles. The enhanced catalytic activity can be attributed to the synergistic effect between Ni{sub 3}N and nitrogen doped reduced graphene oxide. In addition, the sufficient contact between Ni{sub 3}N nanoparticles and the N-RGO nanosheets simultaneously promotes good nanoparticle dispersion and provides a consecutive activity sites to accelerate electron transport continuously, which further enhance the ORR performance. The Ni{sub 3}N/N-RGO may be further an ideal candidate as efficient and inexpensive noble metal-free ORR electrocatalyst in fuel cells.

Relación entre la condición física cardiovascular y la distribución de grasa en niños y adolescentes

OpenAIRE

Casajús Mallén, José; Leiva, María; Ferrando, José; Moreno, Luis; Aragonés, María; Ara Royo, Ignacio

2006-01-01

Fundamentos: El objetivo de este estudio es determinar la relación entre el grado de condición física cardiovascular y la acumulación y distribución de masa grasa en niños y niñas de 7 a 17 años. Material y métodos: La muestra se compone de 1.625 niños y 1.244 niñas, a los que se determinó la potencia aeróbica máxima mediante el test de carrera de la Course Navette. Previamente, se realizó una evaluación antropométrica con el fin de poder establecer la cantidad total de masa grasa subcutánea ...

Malaria en niños: relaciones entre nutrición e inmunidad

Directory of Open Access Journals (Sweden)

Silvia Blair

2002-01-01

Full Text Available Objetivo. Explorar algunas relaciones entre inmunidad, nutrición y malaria en un grupo de niños de una población con alta incidencia endémica de malaria. Métodos. Estudio piloto prospectivo y transversal. En 1998, en El Bagre, Antioquia, Colombia, se tomaron consecutivamente 51 niños de uno u otro sexo con síntomas o signos de malaria y gota gruesa positiva, que conformaron el grupo de niños enfermos con malaria. De los hogares infantiles gubernamentales se tomaron aleatoriamente 49 niños sin malaria (ausencia de síntomas y signos, y gota gruesa negativa que conformaron el grupo de comparación sin malaria. Se calcularon los índices peso/edad, talla/edad y peso/talla; se midieron las concentraciones séricas de albúmina, prealbúmina, apolipoproteína A1 (apoA1, transferrina, cinc, vitamina A, inmunoglobulinas G y M, interleucina 10 (IL-10, factor de necrosis tumoral alfa, interferón gamma, linfocitos y sus poblaciones. Resultados. De los niños estudiados, 69% presentaban algún riesgo de desnutrición y 63% tenían algún riesgo de desnutrición crónica. De las variables inmunitarias y bioquímicas, los enfermos tenían menos apoA1 y albúmina y más IL-10 que los niños sin malaria. Todas las variables bioquímicas mostraron promedios inferiores en el grupo con malaria, riesgo de desnutrición y alteración inmunitaria o bioquímica, mientras que todas las variables inmunitarias presentaron promedios mayores en ese grupo. Conclusiones. a La alta frecuencia de desnutrición crónica urge a aplicar medidas de suplementación alimentaria; b los bajos valores de prealbúmina encontrados pueden deberse a las frecuentes infecciones bacterianas o virales notificadas; c se observó una grave deficiencia de vitamina A, que exige un programa de suplementación; d se encontró asociación entre los valores bajos de apoA1 y la presencia de malaria, pero no se conoce su secuencia; e no se observó relación entre los indicadores antropom

Antibatic photovoltaic response in zinc-porphyrin-liked oligothiophenes

DEFF Research Database (Denmark)

Krebs, Frederik C; Spanggaard, H.

2005-01-01

-stannylchloride and subsequent palladium catalysed Stille coupling. We further synthesised 5,15-bis(3, 4', 4", 4"', 4", 4""', 4""", 4"""'-octahexyl-[2, 2'; 5', 2" 5", 2'"; 5"', 2""; 5"", 2""'; 5""', 2"""; 5""", 2"""']octithiophene-5-yl)-10, 20-bis(3, 5-ditertbutylphenyl)zinc(II)porphyrin (5) from trimethyl(3, 4', 4", 4'", 4......"", 4""', 4""", 4"""'-Octahexyl-[2, 2'; 5', 2"; 5"; 2'"; 5"', 2""; 5"", 2"'"; 5""', 2"""; 5""", 2"""']octithiophene-5-yl)stannane (3-SnMe3) and 5, 15-dibromo-10, 20-bis(3, 5-ditertbutylphenyl)zinc(II)porphyrin (6) by Stille coupling. All the products were characterised by size exclusion chromatography...

Antecedente nacional e internacional sobre la percepción y los derechos de las niñas, los niños, los y las adolescentes

Directory of Open Access Journals (Sweden)

Rodolfo Vicente-Salazar

2008-04-01

Full Text Available Recibido 16 de octubre 2006 • Aprobado 14 de febrero 2007     Hasta mediados del siglo XVIII, el niño fue considerado como un adulto en miniatura; pero Juan Jacobo Rousseau abrió las puertas al estudio del ser en formación, y sentó las bases necesarias para la ciencia Paidología o estudio del niño, que enfoca los conflictos intelectuales y físicos de la vida infantil, y sus secuelas Paidofilaxis, Puericultura y Pediatría. De la Sociedad de las Nacionales, surgió el Consultorio de la Trata de Mujeres y la Protección del Niño, en 1919, y en Ginebra se fundó la Unión Internacional de Socorros, en 1920. En 1916, se realizó en Argentina el I Congreso Americano del Niño, al cual sucedieron otros regularmente en América. En 1924, se redactó la primera “Declaración de los Derechos del Niño” y luego se proclamó el primer decálogo referente a los Derechos del Niño. En mayo de 1929, se presentó al Congreso Constitucional un proyecto de Ley para crear una institución que tuviera por objeto la protección del Niño, que se convirtió en Ley en 1930, con el nombre del Patronato Nacional de la Infancia (PANI, con el encargo de velar por el bienestar de las personas menores de edad en su desarrollo físico, intelectual, moral y emocional. En 1930, en Costa Rica, se hizo la Primera Declaración de los Derechos del Niño Costarricense. La creación del PANI, la Declaración de los Derechos del Niño, y la instauración del Código de la Infancia, son tres hechos que sitúan a Costa Rica como uno de los países pioneros en Latinoamérica y en el mundo, respecto a la protección que se les brinda al niño y a la madre.

Delusional Confusion of Dreaming and Reality in Narcolepsy

Science.gov (United States)

Wamsley, Erin; Donjacour, Claire E.H.M.; Scammell, Thomas E.; Lammers, Gert Jan; Stickgold, Robert

2014-01-01

Study Objectives: We investigated a generally unappreciated feature of the sleep disorder narcolepsy, in which patients mistake the memory of a dream for a real experience and form sustained delusions about significant events. Design: We interviewed patients with narcolepsy and healthy controls to establish the prevalence of this complaint and identify its predictors. Setting: Academic medical centers in Boston, Massachusetts and Leiden, The Netherlands. Participants: Patients (n = 46) with a diagnosis of narcolepsy with cataplexy, and age-matched healthy healthy controls (n = 41). Interventions: N/A. Measurements and Results: “Dream delusions” were surprisingly common in narcolepsy and were often striking in their severity. As opposed to fleeting hypnagogic and hypnopompic hallucinations of the sleep/wake transition, dream delusions were false memories induced by the experience of a vivid dream, which led to false beliefs that could persist for days or weeks. Conclusions: The delusional confusion of dreamed events with reality is a prominent feature of narcolepsy, and suggests the possibility of source memory deficits in this disorder that have not yet been fully characterized. Citation: Wamsley E; Donjacour CE; Scammell TE; Lammers GJ; Stickgold R. Delusional confusion of dreaming and reality in narcolepsy. SLEEP 2014;37(2):419-422. PMID:24501437

Long-lived, charge-shift states in heterometallic, porphyrin-based dendrimers formed via click chemistry.

Science.gov (United States)

Le Pleux, Loïc; Pellegrin, Yann; Blart, Errol; Odobel, Fabrice; Harriman, Anthony

2011-05-26

A series of multiporphyrin clusters has been synthesized and characterized in which there exists a logical gradient for either energy or electron transfer between the porphyrins. A central free-base porphyrin (FbP), for example, is equipped with peripheral zinc(II) porphyrins (ZnP) which act as ancillary light harvesters and transfer excitation energy to the FbP under visible light illumination. Additional energy-transfer steps occur at the triplet level, and the series is expanded by including magnesium(II) porphyrins and/or tin(IV) porphyrins as chromophores. Light-induced electron transfer is made possible by incorporating a gold(III) porphyrin (AuP(+)) into the array. Although interesting by themselves, these clusters serve as control compounds by which to understand the photophysical processes occurring within a three-stage dendrimer comprising an AuP(+) core, a second layer formed from four FbP units, and an outer layer containing 12 ZnP residues. Here, illumination into a peripheral ZnP leads to highly efficient electronic energy transfer to FbP, followed by charge transfer to the central AuP(+). Charge recombination within the resultant charge-shift state is intercepted by secondary hole transfer to the ZnP, which occurs with a quantum yield of around 20%. The final charge-shift state survives for some microseconds in fluid solution at room temperature.

Relación de la succión no nutritiva con la maloclusión en niños ecuatorianos

Directory of Open Access Journals (Sweden)

Myriam Isabel Carrillo Valencia

2016-09-01

Full Text Available Objetivo: Determinar la relación que existe entre los Hábitos de Succión No Nutritiva (HSNN y la presencia de Maloclusiones, en los niños(as de 5 a 9 años de edad de tres Centros Educativos del cantón Ambato, Ecuador. Materiales y métodos: En el presente estudio transversal se evaluaron 435 niños de ambos sexos. El examen clínico fue realizado por un Dentista entrenado siguiendo los criterios diagnósticos de maloclusión según Hurtado et al., 2012. La recolección de datos fue a través de una ficha estructurada. Fueron estudiadas las variables relacionadas con las características propias del niño y la duración del hábito, con la presencia de HSNN y maloclusión. Los datos fueron analizados a través del test estadístico del Chi cuadrado y la correlación de Spearman con un nivel de significancia del 5%. Resultados: La prevalencia del HSNN fue del 52.6%, la prevalencia de maloclusión 38.6%, el tipo de HSNN más frecuente fue la succión digital con 21.6%, la maloclusión más frecuente fue la mordida cruzada anterior con 8.7%; en cuanto al sexo, la edad y la duración del hábito no hubo diferencias estadísticamente significativas. Conclusiones: No hubo relación estadísticamente significativa entre los HSNN y la presencia de maloclusiones, en niños(as entre 5 a 9 años de edad de los 3 centros de educación básica de la ciudad de Ambato.

Psychoanalytic peregrinations. III: Confusion of tongues, psychoanalyst as translator.

Science.gov (United States)

Chessick, Richard D

2002-01-01

A variety of problems cause a confusion of tongues between the psychoanalyst and the patient. In this sense the psychoanalyst faces the same problems as the translator of a text from one language to another. Examples are given of confusion due cultural differences, confusion due translation differences among translators, confusion due translator prejudice or ignorance, confusion due ambiguous visual cues and images, and confusion due to an inherently ambiguous text. It is due to this unavoidable confusion that the humanistic sciences cannot in principle achieve the mathematical exactness of the natural sciences and should not be expected to do so or condemned because they do not.

Sentidos sobre participación: un estudio de caso con niñas en condición de vulnerabilidad social

OpenAIRE

Morales Amézquita, Marleny Angélica

2011-01-01

Tesis (Maestría en Educación y Desarrollo Humano). Universidad de Manizales. Facultad de Ciencias Sociales y Humanas. CINDE, 2011 El presente informe final se deriva de la investigación “Sentidos de participación infantil: Un estudio de caso con niñas en condición de vulnerabilidad social”, cuyo propósito principal consistía en comprender tanto la participación, como la vulnerabilidad social desde una mirada de la niñez, a partir de un caso centrado en dos niñas, Laura y Antone...

Porphyrin-magnetite nanoconjugates for biological imaging

LENUS (Irish Health Repository)

Nowostawska, Malgorzata

2011-04-08

Abstract Background The use of silica coated magnetic nanoparticles as contrast agents has resulted in the production of highly stable, non-toxic solutions that can be manipulated via an external magnetic field. As a result, the interaction of these nanocomposites with cells is of vital importance in understanding their behaviour and biocompatibility. Here we report the preparation, characterisation and potential application of new "two-in-one" magnetic fluorescent nanocomposites composed of silica-coated magnetite nanoparticles covalently linked to a porphyrin moiety. Method The experiments were performed by administering porphyrin functionalised silica-coated magnetite nanoparticles to THP-1 cells, a human acute monocytic leukaemia cell line. Cells were cultured in RPMI 1640 medium with 25 mM HEPES supplemented with heat-inactivated foetal bovine serum (FBS). Results We have synthesised, characterised and analysed in vitro, a new multimodal (magnetic and fluorescent) porphyrin magnetic nanoparticle composite (PMNC). Initial co-incubation experiments performed with THP-1 macrophage cells were promising; however the PMNC photobleached under confocal microscopy study. β-mercaptoethanol (β-ME) was employed to counteract this problem and resulted not only in enhanced fluorescence emission, but also allowed for elongated imaging and increased exposure times of the PMNC in a cellular environment. Conclusion Our experiments have demonstrated that β-ME visibly enhances the emission intensity. No deleterious effects to the cells were witnessed upon co-incubation with β-ME alone and no increases in background fluorescence were recorded. These results should present an interest for further development of in vitro biological imaging techniques.

Planificación cognitiva en niños con déficit auditivo

OpenAIRE

Ángela González Vinasco; Natalia Herrera; Diana Carolina Marín Tobón; Tatiana Rojas Ospina

2008-01-01

Este estudio busca abordar y explorar la habilidad para planificar de los niños con déficit auditivo ante una Situación de Resolución de Problemas (SRP), por medio del uso de las Tecnologías de la Información y la Comunicación (TIC), como una herramienta para acceder, de manera objetiva, a los procesos cognitivos del niño con déficit auditivo, sin demandarle ningún tipo de lenguaje verbal, escrito o por medio de señas. Se analizó el desempeño de 11 niños con déficit auditivo que asisten al In...

Significado de la hipertensión arterial enmascarada en niños y adolescentes

OpenAIRE

Álvarez Pitti, Julio Carlos

2014-01-01

La Hipertensión Arterial Enmascarada (HTAe) en niños y adolescentes es una condición prevalente, persistente y con impacto clínico. Las características clínicas que presentan los jóvenes en riesgo de sufrir HTAe no están definidas. Además, hasta el momento, no ha sido establecido cuál es el riesgo de desarrollar hipertensión arterial persistente (HTAp) de los niños y adolescentes con HTAe, ni los factores de riesgo asociados a esta condición. Con el objetivo de estudiar estos aspectos, s...

Ratiometric Fluorescent Detection of Pb2+ by FRET-Based Phthalocyanine-Porphyrin Dyads.

Science.gov (United States)

Zhang, Dongli; Zhu, Mengliang; Zhao, Luyang; Zhang, Jinghui; Wang, Kang; Qi, Dongdong; Zhou, Yang; Bian, Yongzhong; Jiang, Jianzhuang

2017-12-04

Sensitive and selective detection of Pb 2+ is a very worthwhile endeavor in terms of both human health and environmental protection, as the heavy metal is fairly ubiquitous and highly toxic. In this study, we designed phthalocyanine-porphyrin (Pc-Por) heterodyads, namely, H 2 Pc-α-ZnPor (1) and H 2 Pc-β-ZnPor (2), by connecting a zinc(II) porphyrin moiety to the nonperipheral (α) or peripheral (β) position of a metal-free phthalocyanine moiety. Upon excitation at the porphyrin Soret region (420 nm), both of the dyads exhibited not only a porphyrin emission (605 nm) but also a phthalocyanine emission (ca. 700 nm), indicating the occurrence of intramolecular fluorescence resonance energy transfer (FRET) processes from the porphyrin donor to the phthalocyanine acceptor. The dyads can selectively bind Pb 2+ in the phthalocyanine core leading to a red shift of the phthalocyanine absorption and thus a decrease of spectral overlap between the porphyrin emission and phthalocyanine absorption, which in turn suppresses the intramolecular FRET. In addition, the binding of Pb 2+ can highly quench the emission of phthalocyanine by heavy-metal ion effects. The synergistic coupled functions endow the dyads with remarkable ratiometric fluorescent responses at two distinct wavelengths (F 605 /F 703 for 1 and F 605 /F 700 for 2). The emission intensity ratio increased as a linear function to the concentration of Pb 2+ in the range of 0-4.0 μM, whereas the detection limits were determined to be 3.4 × 10 -9 and 2.2 × 10 -8 M for 1 and 2, respectively. Furthermore, by comparative study of 1 and 2, the effects of distance and relative orientation between Pc and ZnPor fluorophores on the FRET efficiency and sensing performance were highlighted, which is helpful for further optimizing such FRET systems.

Exposición a pantallas, sobrepeso y desacondicionamiento físico en niños y niñas

OpenAIRE

Duque, Iván Leonardo; Parra, José Hernán

2012-01-01

Resumen: Antecedentes. El sobrepeso y la obesidad infantil son un problema grave de salud. La actividad física determina la capacidad cardiorespiratoria. Los datos relacionados con el sobrepeso, obesidad y exposición a pantallas no son concluyentes. Métodos. Encuestamos a niños y niñas de edades entre 10 y 12 años acerca del tiempo frente a pantallas. Adicionalmente realizamos mediciones antropométricas y funcionales. Resultados. Estudiamos a 325 niños y niñas. El tiempo promedio frente a pan...

Exposición a pantallas, sobrepeso y desacondicionamiento físico en niños y niñas

OpenAIRE

Iván Leonardo Duque; José Hernán Parra

2012-01-01

Antecedentes. El sobrepeso y la obesidad infantil son un problema grave de salud. La actividad física determina la capacidad cardiorespiratoria. Los datos relacionados con el sobrepeso, obesidad y exposición a pantallas no son concluyentes. Métodos. Encuestamos a niños y niñas de edades entre 10 y 12 años acerca del tiempo frente a pantallas. Adicionalmente realizamos mediciones antropométricas y funcionales. Resultados. Estudiamos a 325 niños y niñas. El tiempo promedio frente a pantallas fu...

Significados e implicaciones de la alfabetización tecnológica en el desarrollo de niños, niñas y adolescentes

Directory of Open Access Journals (Sweden)

María López

2014-08-01

Full Text Available Se analizan los significados y algunas implicaciones de la alfabetización tecnológica en el desarrollo de niños, niñas y adolescentes, con base en referentes teóricos que permiten contextualizar el objeto y actores de estudio en una perspectiva humana integral, la cual combina lo cognitivo con lo psico-social. La metodología utilizada consistió en el diseño de un programa de alfabetización tecnológica, dirigido a una población de 60 niños, niñas y adolescentes pertenecientes al Sector El Marite, Parroquia Venancio Pulgar del Municipio Maracaibo, en virtud de que se asumió que dichos actores se encuentran en situación de exclusión social, con escasas posibilidades económicas para el acceder a la infraestructura tecnológica. Se aplicaron tres pruebas específicas: la subescala de Claves A-B, la subescala de Figuras Incompletas y la subescala Laberintos, pertenecientes a la prueba WISC-R de Weschler, que mide habilidades como: percepción visual y motriz, atención, coordinación y memoria. Adicionalmente, se aplicaron técnicas de dibujo proyectivo para develar la concepción que los niños, niñas y adolescentes tienen con relación a la tecnología. También se aplicó la escala Conners, contentiva de 59 items que miden 13 categorías del comportamiento. Los resultados revelan, además de la efectividad del programa en cuanto al desarrollo de competencias para la interacción tecnológica, un impacto significativo en el desarrollo intelectual y socio-emocional de la población atendida. Se concluye, que los programas de alfabetización tecnológica deben trascender la perspectiva instrumentalista para ubicarse en una dimensión más humana que entiende la tecnología como un elemento de desarrollo e inclusión social.

La protección penal a niños y adolescentes víctimas de violencia familiar

OpenAIRE

Salazar Mariño, Carlos Rosendo

2014-01-01

La presente investigación titulada "La Protección Penal a Niños y Adolescentes Víctimas de Violencia Familiar" describe los problemas que presentan el sistema de administración de justicia penal respecto a la protección de los derechos de los niños, niñas y adolescentes que sufren violencia en el hogar. Tiene como objetivo principal analizar y describir la protección penal de Jos derechos de los niños, niñas y adolescentes víctimas de violencia familiar, conocer cómo se aplica los principios ...

MS2 bacteriophage as a delivery vessel of porphyrins for photodynamic therapy

Science.gov (United States)

Cohen, Brian A.; Kaloyeros, Alain E.; Bergkvist, Magnus

2011-02-01

Challenges associated with photodynamic therapy (PDT) include the packaging and site-specific delivery of therapeutic agents to the tissue of interest. Nanoscale encapsulation of PDT agents inside targeted virus capsids is a novel concept for packaging and site-specific targeting. The icosahedral MS2 bacteriophage is one potential candidate for such a packaging-system. MS2 has a porous capsid with an exterior diameter of ~28 nm where the pores allow small molecules access to the capsid interior. Furthermore, MS2 presents suitable residues on the exterior capsid for conjugation of targeting ligands. Initial work by the present investigators has successfully demonstrated RNA-based self-packaging of a heterocyclic PDT agent (meso-tetrakis(para-N-trimethylanilinium)porphine, TMAP) into the MS2 capsid. Packaging photoactive compounds in confined spaces could result in energy transfer between the molecules upon photoactivation, which could in turn reduce the production of radical oxygen species (ROS). ROS are key components in photodynamic therapy, and a reduced production could negatively impact the efficacy of PDT treatment. Here, findings are presented from an investigation of ROS generation of TMAP encapsulated within the MS2 capsid compared to free TMAP in solution. Monitoring of ROS production upon photoactivation via a specific singlet oxygen assay revealed the impact on ROS generation between packaged porphyrins as compared to free porphyrin in an aqueous solution. Follow on work will study the ability of MS2-packaged porphyrins to generate ROS in vitro and subsequent cytotoxic effects on cells in culture.

Molecular Structure and Electronic Properties of Porphyrin-Thiophene-Perylene Using Quantum Chemical Calculation

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Tatiya Chokbunpiam

2010-01-01

Full Text Available This study aimed to design a new series of compounds consisting of a porphyrin macrocycle linked to a perylene unit via a thiophenic bridge. The structural and electronic properties of the molecules, and the effects of mono- and di-substituents R on C3 and R′ on C4 of the thiophene ring were investigated using a quantum calculation approach. The results from the method validation revealed that using the density functional theory approach at B3LYP/6–31G(d data set was the optimal one, considering the accuracy attained and maintaining the computer time required within tractable limits. The results from the B3LYP/6–31G(d approach indicated that significant changes of the torsion angle between the molecular planes of the porphyrin and perylene rings, compared to that of the unsubstituted derivatives, were found in the di-substituted systems bearing R = R′ = −OCH3 and −NH2, and in a mono-substituted system having R = −H and R′=−NH2. The symmetric di-substitution does not provide a significantly lower HOMO-LUMO energy gap (ΔEg. Noticeable decreases in ΔEg were found only with the substitution patterns of: R, R′ = −OCH3, −H; −OH, −H; −N(CH32, −H; −H, −NH2. UV-visible spectra of all derivatives exhibited characteristic absorption maxima of the free bases of porphyrin and perylene.

Magnetron sputtered Cu{sub 3}N/NiTiCu shape memory thin film heterostructures for MEMS applications

Energy Technology Data Exchange (ETDEWEB)

Kaur, Navjot; Choudhary, Nitin [Indian Institute of Technology Roorkee, Roorkee, Functional Nanomaterials Research Lab, Department of Physics and Centre of Nanotechnology (India); Goyal, Rajendra N. [Indian Institute of Technology, Roorkee, Department of Chemistry (India); Viladkar, S. [Indian Institute of Technology Roorkee, Roorkee, Functional Nanomaterials Research Lab, Department of Physics and Centre of Nanotechnology (India); Matai, I.; Gopinath, P. [Indian Institute of Technology, Roorkee, Centre for Nanotechnology (India); Chockalingam, S. [Indian Institute of Technology, Guwahati, Department of Biotechnology (India); Kaur, Davinder, E-mail: dkaurfph@iitr.ernet.in [Indian Institute of Technology Roorkee, Roorkee, Functional Nanomaterials Research Lab, Department of Physics and Centre of Nanotechnology (India)

2013-03-15

In the present study, for the first time, Cu{sub 3}N/NiTiCu/Si heterostructures were successfully grown using magnetron sputtering technique. Nanocrystalline copper nitride (Cu{sub 3}N with thickness {approx}200 nm) thin films and copper nanodots were subsequently deposited on the surface of 2-{mu}m-thick NiTiCu shape memory thin films in order to improve the surface corrosion and nickel release properties of NiTiCu thin films. Interestingly, the phase transformation from martensite phase to austenite phase has been observed in Cu{sub 3}N/NiTiCu heterostructures with corresponding change in texture and surface morphology of top Cu{sub 3}N films. Field emission scanning electron microscopy and atomic force microscope images of the heterostructures reveals the formation of 20-nm-sized copper nanodots on NiTiCu surface at higher deposition temperature (450 Degree-Sign C) of Cu{sub 3}N. Cu{sub 3}N passivated NiTiCu films possess low corrosion current density with higher corrosion potential and, therefore, better corrosion resistance as compared to pure NiTiCu films. The concentration of Ni released from the Cu{sub 3}N/NiTiCu samples was observed to be much less than that of pure NiTiCu film. It can be reduced to the factor of about one-ninth after the surface passivation resulting in smooth, homogeneous and highly corrosion resistant surface. The antibacterial and cytotoxicity of pure and Cu{sub 3}N coated NiTiCu thin films were investigated through green fluorescent protein expressing E. coli bacteria and human embryonic kidney cells. The results show the strong antibacterial property and non cytotoxicity of Cu{sub 3}N/NiTiCu heterostructure. This work is of immense technological importance due to variety of BioMEMS applications.

Premedicación con clonidina para la analgesia posoperatoria en niños

Directory of Open Access Journals (Sweden)

2014-07-01

Conclusiones de los autores: Hubo sólo 11 ensayos relevantes que estudiaron a 742 niños con cirugía en los que la premedicación con clonidina se comparó con el placebo u otra farmacoterapia. A pesar de la heterogeneidad entre los ensayos, la premedicación con clonidina en una dosificación adecuada (4 μg/ kg tuvo un efecto beneficioso para el dolor posoperatorio en niños. Los efectos secundarios fueron mínimos, pero algunos de los estudios usaron la atropina como profilaxis con la intención de prevenir la bradicardia y la hipotensión. Se requiere más investigación para determinar en qué condiciones la premedicación con clonidina es más efectiva en el alivio del dolor posoperatorio en niños.

Evaluación del prelenguaje tras aplicación de programa de estimulación en niños con factores de riesgo perinatales

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Leydelys Castillo Valdés

2014-04-01

Full Text Available Introducción: en la formación del prelenguaje es fundamental la estimulación sensorial que recibe el niño. Objetivo: implementar un programa de estimulación para la prevención y el tratamiento oportuno de los trastornos del lenguaje en niños con factores de riesgo perinatales, de modo que permita un desarrollo adecuado de los elementos básicos de la comunicación oral partiendo de los resultados de la evaluación en cada sub-etapa del prelenguaje. Material y método: se realizó un estudio observacional, descriptivo, longitudinal, prospectivo en la consulta de Neurodesarrollo del Hospital General Docente "Abel Santamaría Cuadrado" de Pinar del Río, en el período 2010-2011; tomando los datos de la Historia Clínica Logofoniátrica procesados mediante el sistema estadístico InfStat 1.0. El universo estuvo integrado por 183 niños y la muestra por 142 niños que cumplieron los criterios de inclusión. Resultados: en la muestra se presentaron 68 factores de riesgo prenatales, 234 perinatales y 150 neonatales. En la evaluación al finalizar el prelenguaje el 94% de los niños tuvo un desarrollo del lenguaje acorde a su edad, el 4% un desarrollo normal retardado y un 2% se retrasó. Estos presentaron como causa secundaria Curso atípico del desarrollo, Hipoacusia neurosensorial bilateral profunda y Epilepsia. Predominó la buena eficacia al tratamiento. Conclusiones: de este estudio se concluye que con la puesta en práctica del programa de estimulación se logró que los niños alcanzaran un desarrollo del lenguaje en correspondencia a su edad, mejorando su calidad de vida.

Syntheses, spectroscopic and thermal analyses of cyanide bridged heteronuclear polymeric complexes: [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine or N-ethylethylenediamine; Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II))

Science.gov (United States)

Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla

2016-02-01

Polymeric tetracyanonickelate(II) complexes of the type [M(L)2Ni(CN)4]n (Ldbnd N-methylethylenediamine (men) or N-ethylethylenediamine (neen); Mdbnd Ni(II), Cu(II), Zn(II) or Cd(II)) have been prepared and characterized by FT-IR, Raman spectroscopy, thermal and elemental analysis techniques. Additionally, FT-IR and Raman spectral analyses of men and neen have experimentally and theoretically investigated in the range of 4000-250 cm-1. The corresponding vibration assignments of men and neen are performed by using B3LYP density functional theory (DFT) method together with 6-31 G(d) basis set. The spectral features of the complexes suggest that the coordination environment of the M(II) ions are surrounded by the two symmetry related men and neen ligands and the two symmetry related N atom of cyanide groups, whereas the Ni(II) atoms are coordinated with a square-planar to four C atoms of the cyanide groups. Polymeric structures of the complexes consist of one dimensional alternative chains of [M(L)2]2+ and [Ni(CN)4]2- moieties. The thermal decompositions in the temperature range 30-700 °C of the complexes were investigated in the static air atmosphere.

A new method for evaluating the conformations and normal modes of macromolecule vibrations with a reduced force field. 2. Application to nonplanar distorted metal porphyrins

Energy Technology Data Exchange (ETDEWEB)

Unger, E.; Beck, M.; Lipski, R.J.; Dreybrodt, W.; Medforth, C.J.; Smith, K.M.; Schweitzer-Stenner, R.

1999-11-11

The authors have developed a novel method for molecular mechanics calculations and normal-mode analysis. It is based on symmetry of local units that constitutes the given molecule. Compared with general valence force field calculations, the number of free parameters is reduced by 40--80% in the procedure. It was found to reproduce very well the vibrational frequencies and mode compositions of aromatic compounds and porphyrins, as shown by comparison with DFT calculations. A slightly altered force field obtained from Ni(II) porphin was then used to calculate the structure and the normal modes of several meso-substituted Ni(II) porphyrins which are known to be subject to significant ruffling and/or saddling distortions. This method satisfactorily reproduces their nonplanar structure and Raman band frequencies in the natural abundance and isotopic derivative spectra. The polarization properties of bands from out-of-plane modes are in accordance with the predicted nonplanar distortions. Moreover, some of the modes below 800 cm{sup {minus}1} which appear intense in the Raman spectra contain considerable contributions from both in-plane and out-of-plane vibrations, so that the conventional mode assignments become questionable. The authors also demonstrate that the intensity and polarization of some low-frequency Raman bands can be used as a (quantitative) marker to elucidate type and magnitude of out-of-plane distortions. These were recently shown to affect heme groups of hemoglobin, myoglobin, and, in particular, of cytochrome c.

Utilidad de la Escala de Conners en la identificación de síntomas de déficit de atención e hiperactividad en niños y niñas con retraso mental

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Luis Felipe Gomez Quiñonez

2013-12-01

Full Text Available Antecedentes: Los síntomas de déficit de atención e hiperactividad son muy frecuentes en niños y niña con retraso mental, sin embargo, no se ha informado la utilidad de la escala de Conners en la identificación de estos síntomas en esta población. Objetivo: Validar la escala de Conners para trastorno por déficit de atención e hiperactividad en niños y niñas con retraso mental de la consulta externa de un hospital psiquiátrico. Método: Fueron evaluados 34 niños y niñas con retraso mental en edad escolar. Los padres fueron entrevistados para identificar trastorno por déficit de atención e hiperactividad según los criterios de la Asociación Psiquiátrica Americana y diligenciaron la escala de Conners. Se determinó la sensibilidad, la especificidad, el valor predictivo positivo, el valor predictivo negativo y la concordancia por azar (kappa. Resultados: La escala de Conners mostró una sensibilidad de 89.5%, una especificidad de 80.0%, un valor predictivo positivo de 85.0%, un valor predictivo negativo de 85.7%y una prueba kappa de 0.70 (p <0.0001. Conclusiones: La escala de Conners es útil para identificar de SDAH con importancia clínica en niños y niñas con RM. Se necesita mayor investigación.

Confusion deepens over N.S. Mutsu

International Nuclear Information System (INIS)

Anon.

1984-01-01

The problem regarding the nuclear ship Mutsu has developed into a major political issue, and has been thrown into confusion, since a group in the ruling Liberal Democratic Party decided that the nuclear ship should be out of commission, and the construction of the new home port should be suspended. The commercial operation of nuclear ships is not expected soon, and the government plan to spend 60 billion to 100 billion yen for the construction of the new home port is questioned. The group to consider the nuclear ship urged the government to make serious effort to resume the experiment of the Mutsu as soon as possible, and the Nuclear Ship Council of the AEC considered the construction of the new home port as unavoidable, and emphasized the importance of nuclear ship development. This seemed to end the argument, but the above decision was made. Five major papers are also divided over the question of the Mutsu. Local people demand the government to observe the five-party agreement on the construction of the new home port at Sekinehama. Four top executives of the Liberal Democratic Party made a four-point decision, but it was so ambiguous that it may be interpreted in various ways. This decision threatens the existence of the AEC as the highest organ on the atomic energy policy of Japan. The role as an experimental nuclear ship should be fulfiled anyway. (Kako, I.)

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex

KAUST Repository

Aly, Shawkat Mohammede

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

Relación entre la televisión y la manifestación de problemas conductuales en niños preescolares

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Laura OLIVA ZÁRATE

2009-05-01

Full Text Available RESUMEN: En este estudio se realiza el análisis del uso de la televisión en niños de 4 a 5 años de edad y su relación con los problemas de conducta. Los instrumentos utilizados fueron el Cuestionario sobre el comportamiento de niños de 11/2-5 años de T. Achenbach y L. Rescorla (2002, aplicado a 535 padres de niños de 20 escuelas de nivel preescolar que resultaron de un muestreo representativo de la ciudad de Xalapa-México a fin de identificar problemas conductuales en los niños, el Cuestionario para padres sobre la televisión y su relación sobre los problemas de conducta, la Entrevista sobre preferencias televisivas en el niño preescolar y el Grupo de Discusión con Maestros de Educación Preescolar. El análisis realizado es descriptivo y multivariado, no encontrándose una relación directa entre el tiempo de visión y los programas televisivos respecto a los problemas de conducta en los niños, marcándose la influencia en el entorno familiar y el estrato socioeconómico.ABSTRACT: In this study the analysis of the use of the television in children of 4 to 5 years old and their relation with the behavior problems is made. The instruments were the Questionnaire of the children behavior of 11/2-5 years of T. Achenbach and L. Rescorla, applied to 535 parents of children of 20 schools that turned out from a representative sampling of the city of Xalapa-Mexico in order to identify behavior problems in the infants, the Questionnaire for parents on the television and its relation on the behavior problems, the Interview on televising preferences in the preschooler and the Group of Discussion with Teachers of Preeschool Education. The made analysis is as much descriptive as multivaried, not being a direct relation between the televising time of vision and programs with respect to the problems of conduct in the infants, marking itself the influence in the familiar surroundings and the socioeconomic layer.

Forward Current Transport Mechanisms of Ni/Au—InAlN/AlN/GaN Schottky Diodes

Science.gov (United States)

Wang, Xiao-Feng; Shao, Zhen-Guang; Chen, Dun-Jun; Lu, Hai; Zhang, Rong; Zheng, You-Dou

2014-05-01

We fabricate two Ni/Au-In0.17Al0.83N/AlN/GaN Schottky diodes on substrates of sapphire and Si, respectively, and investigate their forward-bias current transport mechanisms by temperature-dependent current-voltage measurements. In the temperature range of 300-485 K, the Schottky barrier heights (SBHs) calculated by using the conventional thermionic-emission (TE) model are strongly positively dependent on temperature, which is in contrast to the negative-temperature-dependent characteristic of traditional semiconductor Schottky diodes. By fitting the forward-bias I-V characteristics using different current transport models, we find that the tunneling current model can describe generally the I-V behaviors in the entire measured range of temperature. Under the high forward bias, the traditional TE mechanism also gives a good fit to the measured I-V data, and the actual barrier heights calculated according to the fitting TE curve are 1.434 and 1.413 eV at 300K for InAlN/AlN/GaN Schottky diodes on Si and the sapphire substrate, respectively, and the barrier height shows a slightly negative temperature coefficient. In addition, a formula is given to estimate SBHs of Ni/Au—InAlN/AlN/GaN Schottky diodes taking the Fermi-level pinning effect into account.

Estrategias de afrontamiento e inadaptación en niños y adolescentes

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Francisco M. Morales

2010-12-01

Full Text Available El objetivo general del presente trabajo es estudiar la relación entre el empleo de estrategias de afrontamiento, ajuste psicológico y manifestación de comportamientos desadaptados. El enfoque adoptado es situacional, considerando la estrategia en relación con la situación particular, en concreto, se han evaluado las estrategias de afrontamiento del estrés utilizadas por escolares andaluces de educación primaria en relación con cuatro tipos de estresores: escolar, familiar, relaciones con los iguales y salud. Participaron 402 niños entre 9 y 12 años. Los instrumentos utilizados fueron: el IIEC (Inventario Infantil de Estresores Cotidianos, el ESAN (Estrategias situacionales de afrontamiento en niños y en niñas y el BASC (Sistema de Evaluación de la conducta en niños y adolescentes. Los resultados demuestran un uso diferencial de estrategias de afrontamiento según el problema o situación planteada. El análisis de las estrategias de afrontamiento revela además que el empleo de estrategias de afrontamiento de aproximación a los problemas se asocia a un mayor grado de ajuste y adaptación mientras que un mayor empleo de estrategias de tipo evitativo se asocia con menos ajuste y comportamientos más desadaptativos.

Synthesis and characterization of a novel series of meso (nitrophenyl and meso (carboxyphenyl substituted porphyrins

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Schiavon Marco A.

2000-01-01

Full Text Available The anionic 5,10,15-tris(4-carboxyphenyl, 20-mono(2-nitrophenyl porphyrin (1, 5,10(or 15-bis(4-carboxyphenyl, 15(or 10,20-bis(2-nitrophenylporphyrin (2 and 5-mono(4-carboxyphenyl, 10,15,20-tris(2-nitrophenylporphyrin (3 were sinthesized directly by reaction of pyrrole with substituted benzaldehydes in nitrobenzene/propionic acid media. The benzaldehydes molar ratio was controlled to optimize the synthesis and purification of the desired porphyrins. This new series of porphyrins was characterised by TLC, mass spectrometry (FAB MS, ¹H NMR, UV/Vis, IR and electrochemistry. 5,10,15,20-Tetrakis(4-carboxyphenylporphyrin (4 and 5,10,15,20-Tetrakis(2-nitrophenylporphyrin (5 were also characterised for comparative purposes, completing the series The electrochemical reduction was investigated for the free base and corresponding iron(III porphyrins on glassy carbon and mercury electrodes. The reduction potentials showed the expected dependence on the number of electron-withdrawing nitro groups present on the porphyrin ring providing additional evidences for the characterisation of the synthesised compounds.

Evaluación de la inteligencia de niños con discapacidad visual: estudio exploratorio de la adecuación de ítems

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CAROLINA ROSA CAMPOS

2017-05-01

Full Text Available El objetivo de este estudio fue comparar el desempeño cognitivo de niños con discapacidad visual y con visión normal y analizar la influencia del grupo y escolaridad por medio de la Batería de Evaluación de la Inteligencia para Niños con Discapacidad Visual (baic-dv, buscando justificar la importancia de instrumentos específicos para la población objetivo. El instrumento fue aplicado a 14 niños con discapacidad visual de 7 a 12 años (m = 10,28; dp = 1,58, seis de sexo femenino, diez clasificados con baja visión (ocho con discapacidad congénita; dos con discapacidad adquirida y cuatro con ceguera (dos con ceguera adquirida; dos con ceguera congénita; y en 17 niños con visión normal (m = 9,94 años; dp = 1,43; todas de sexo femenino. Se evaluó el total de aciertos, tiempo de ejecución e influencia de variables. Los resultados indicaron mejor desempeño de los niños de visión normal y de los niños con discapacidad congénita. Los niños con baja visión tuvieron mejor desempeño que los niños ciegos. Se evidenció la influencia de escolaridad en la subprueba Verbal y de sexo en la subprueba de memoria. Se concluyó la importancia de un instrumento específico para niños con discapacidad visual, dada la escasez de instrumentos destinados a este fin en la literatura científica brasilera

Confusões e ambigüidades na classificação de eventos adversos em pesquisa clínica Confusiones y ambigüedades en la clasificación de eventos adversos en investigación clínica Confusions and ambiguities in the classification of adverse events in the clinical research

Directory of Open Access Journals (Sweden)

Gabriela Marodin

2009-09-01

Full Text Available É comum considerar ambíguo como sinônimo de confuso. Em uma informação confusa, várias informações têm um mesmo significado. Na informação ambígua, ao contrário, vários significados são atribuídos a uma mesma palavra. Informações excessivas também geram ambiguidade, daí a necessidade de concisão e clareza na linguagem. O termo evento adverso (EA é definido como qualquer ocorrência médica inconveniente, sofrida por um sujeito da pesquisa em investigação clínica. A confusão e a ambiguidade no uso de palavras podem gerar conseqüências importantes na valorização de EAs. O objetivo deste estudo, de natureza teórica, é harmonizar o vocabulário utilizado na caracterização dos riscos e na comunicação de EAs na pesquisa clínica. Os EAs podem ser classificados quanto à previsibilidade, frequência, gravidade, causalidade e seriedade. Muitas vezes, em documentos regulatórios, os EAs são definidos em função da seriedade e causalidade. A harmonização do vocabulário na comunicação de EAs é fundamental para evitar a utilização equivocada de palavras com sentido confuso, ou ambíguo.Es común considerar ambiguo como siendo sinónimo de confuso. En una información confusa, varias informaciones tienen un mismo significado. En la información ambigua, al contrario, varios significados son atribuidos a una misma palabra. Informaciones excesivas también generan ambigüedad, por esa razón es necesario ser conciso y claro en el lenguaje. El término evento adverso (EA es definido como cualquier ocurrencia médica inconveniente, sufrida por un sujeto participante del estudio, en investigación clínica. La confusión y la ambigüedad en el uso de las palabras pueden generar consecuencias importantes en la valorización de los EAs. El objetivo de este estudio, de naturaleza teórica, es armonizar el vocabulario utilizado en la caracterización de los riesgos y en la comunicación de los EAs en la investigación cl

La desintegración familiar: impacto en el desarrollo emocional de los niños

OpenAIRE

Sonia María Castillo Costa; Zoila Gladys Merino Armijos

2018-01-01

El presente artículo pretende generar espacios de reflexión en torno a la desintegración familiar y el impacto en el desarrollo emocional de los niños, tiene como  objetivo mejorar la relación y la comunicación padre-hijos/as, los más afectados son los niños al desintegrarse el hogar por diferentes factores, cuando el comportamiento de los niños/as se ve alterado al no existir una orientación que ayude a normalizar el problema. La desintegración familiar provoca problemas psicológicos de...

Inclusión social y educación integral a niños con discapacidad centro de educación Melvin Jones.

OpenAIRE

Granda Reyes, Raquel Eliana; Gavino González, Julia Dolores

2017-01-01

Este trabajo de investigación, sobre la inclusión social y educación integral a los niños y niñas y adolescentes, que sufren de algún tipo de discapacidad y que asisten al Centro de Educación Melvin Jones, se analizó el marco teórico, conceptual, las normas y leyes que respaldan esta investigación, como la Constitución de la República del Ecuador y la Ley Orgánica de Discapacidades. Se trataron temas como los derechos humanos la inclusión y exclusión social, la pobreza, desigualdad, y los gr...

Backscattering analysis of AuGe-Ni ohmic contacts of n-GaAs

International Nuclear Information System (INIS)

Nassibian, A.G.; Kalkur, T.S.; Sutherland, G.J.; Cohen, D.

1985-01-01

AuGe-Ni is widely used for the fabrication of ohmic contacts to n-GaAs. The alloying behaviour of evaporated AuGe-Ni alloyed by furnace and Scanning Electron Beam, is characterised by Rutherford backscattering with 2MeV 4 He ions. Since the formation of alloyed AuGe-Ni contacts involves redistribution and diffusion of Ga, As, Ni, Ge and Au, it is difficult to separate the corresponding yields due to gold, Ga As, Ni and Ge in the spectrum. The technique used in the investigation involves assumption of depth distribution of elements and computing the resultant spectrum

Intervención psicomotriz en niños con trastorno por déficit de atención con hiperactividad

OpenAIRE

Herguedas Esteban, María del Carmen

2016-01-01

El trastorno por déficit de atención con hiperactividad (TDAH) es una de las principales causas de fracaso escolar. Los niños con este trastorno deben ser atendidos en una escuela inclusiva que permita responder a las necesidades de todos los alumnos. Se ha desarrollado un trabajo de investigación cuyos objetivos eran: evaluar las alteraciones psicomotoras de los niños con TDAH; elaborar un programa educativo de intervención psicomotriz para niños con TDAH; aplicar dicho programa en un gru...

Synthesis and photobactericidal properties of a neutral porphyrin grafted onto lignocellulosic fibers

Energy Technology Data Exchange (ETDEWEB)

Nzambe Ta keki, Jean Kerim; Ouk, Tan-Sothéa [Laboratoire de chimie des substances naturelles, Université de Limoges, 123 avenue Albert Thomas, 87060 Limoges (France); Zerrouki, Rachida [Laboratoire de chimie des substances naturelles, Université de Limoges, 123 avenue Albert Thomas, 87060 Limoges (France); Centre de Recherche sur les Matériaux Lignocellulosiques, Université du Québec à Trois-Rivières, 3351 boul. des Forges, C.P. 500, Trois-Rivières, QC G9A 5H7 (Canada); Faugeras, Pierre-Antoine; Sol, Vincent [Laboratoire de chimie des substances naturelles, Université de Limoges, 123 avenue Albert Thomas, 87060 Limoges (France); Brouillette, François [Centre de Recherche sur les Matériaux Lignocellulosiques, Université du Québec à Trois-Rivières, 3351 boul. des Forges, C.P. 500, Trois-Rivières, QC G9A 5H7 (Canada)

2016-05-01

Photodynamic antimicrobial chemotherapy (PACT), as one of the promising alternative antimicrobial treatment, has received great attention in recent years. In this work, a new antimicrobial material has been elaborated by grafting a neutral porphyrin, the metallated 5-(4-azidophenyl)-10,15,20-triphenylporphyrin, onto lignocellulosic fibers by using the Copper (I)-Catalyzed Alkyne-Azide 1,3-dipolar Cycloaddition (CuAAC) reaction. The cross-linked porphyrin-Kraft pulp material was characterized by infrared and by XPS spectroscopy analyses, which proved the covalent linkage between the porphyrin and propargylated Kraft pulp fibers. The antimicrobial activity of this material was tested under visible light irradiation with a low light dose (9.5 J/cm{sup 2}) against Staphylococcus aureus and Pseudomonas aeruginosa. The two bacterial strains deposited on the resulting photosensitizing Kraft pulp are efficiently killed after illumination. Such materials could find applications in industrial, household and medical environments as an alternative to overcome the widespread microbial multiresistance to classical treatments. - Highlights: • Elaboration of new antimicrobial paper • Grafting of porphyrin on lignocellulosic fibers using click chemistry • Modification of Kraft pulp fibers, using water as solvent.

Solvent effects on the fluorescence and effective three-photon absorption of a Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin

Science.gov (United States)

Wan, Yong; Xue, Yuxiong; Sheng, Ning; Rui, Guanghao; Lv, Changgui; He, Jun; Gu, Bing; Cui, Yiping

2018-06-01

The fluorescence and effective three-photon absorption (3PA) properties of Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin] (labeled Zn(II)-porphyrin) dissolved in three different polar solvents were systematically investigated. The electrochemical and photophysical properties of Zn(II)-porphyrin were investigated by 1H NMR spectra, IR spectra, mass spectroscopy, and electronic absorption spectra. The fluorescence emission of Zn(II)-porphyrin in three different solvents excited at the wavelengths of 420 nm (Soret band) and 550 nm (Q-band) were analyzed. By performing Z-scan experiments with femtosecond laser pulses at a wavelength of 800 nm, the effective 3PA process of Zn(II)-porphyrin in three different solvents was observed and the underlying mechanism was discussed in detail. It is found that the fluorescence spectra slightly depend on the polarity of the solvent. Interestingly, the effective 3PA properties of Zn(II)-porphyrin strongly depend on the solvent polarity. The lower the solvent polarity is, the larger effective 3PA cross-section is. Low polar solvents are beneficial to applications of Zn(II)-porphyrin in optical limiting, photodynamic therapy, etc.

Equilibrium geometries, electronic and magnetic properties of small AunNi- (n = 1-9) clusters

Science.gov (United States)

Tang, Cui-Ming; Chen, Xiao-Xu; Yang, Xiang-Dong

2014-05-01

Geometrical, electronic and magnetic properties of small AunNi- (n = 1-9) clusters have been investigated based on density functional theory (DFT) at PW91P86 level. An extensive structural search shows that the relative stable structures of AunNi- (n = 1-9) clusters adopt 2D structure for n = 1-5, 7 and 3D structure for n = 6, 8-9. And the substitution of a Ni atom for an Au atom in the Au-n+1 cluster obviously changes the structure of the host cluster. Moreover, an odd-even alternation phenomenon has been found for HOMO-LUMO energy gaps, indicating that the relative stable structures of the AunNi- clusters with odd-numbered gold atoms have a higher relative stability. Finally, the natural population analysis (NPA) and the vertical detachment energies (VDE) are studied, respectively. The theoretical values of VDE are reported for the first time to our best knowledge.

The (n, $\\gamma$) reaction in the s-process branching point $^{59}$Ni

CERN Multimedia

We propose to measure the $^{59}$Ni(n,$\\gamma$)$^{56}$Fe cross section at the neutron time of flight (n TOF) facility with a dedicated chemical vapor deposition (CVD) diamond detector. The (n, ) reaction in the radioactive $^{59}$Ni is of relevance in nuclear astrophysics as it can be seen as a rst branching point in the astrophysical s-process. Its relevance in nuclear technology is especially related to material embrittlement in stainless steel. There is a strong discrepancy between available experimental data and the evaluated nuclear data les for this isotope. The aim of the measurement is to clarify this disagreement. The clear energy separation of the reaction products of neutron induced reactions in $^{59}$Ni makes it a very suitable candidate for a rst cross section measurement with the CVD diamond detector, which should serve in the future for similar measurements at n_TOF.

Gadolinium-porphyrins: new potential magnetic resonance imaging contrast agents for melanoma detection

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Daryoush Shahbazi-Gahrouei

2006-11-01

Full Text Available BACKGROUND: Two new porphyrin-based magnetic resonance imaging (MRI contrast agents, Gd-hematoporphyrin (Gd-H and Gd-tetra-carboranylmethoxyphenyl-porphyrin (Gd-TCP were synthesized and tested in nude mice with human melanoma (MM-138 xenografts as new melanoma contrast agents. METHODS: Subcutaneous xenografts of human melanoma cells (MM-138 were studied in 30 (five groups of six nude mice. The effect of different contrast agents (Gd-TCP, Gd-H, GdCl3 and Gd-DTPA on proton relaxation times was measured in tumors and other organs. T1 values, signal enhancement and the Gd concentration for different contrast agent solutions were also investigated. RESULTS: The porphyrin agents showed higher relaxivity compared to the clincal agent, Gd-DTPA. A significant 16% and 21% modification in T1 relaxation time of the water in human melanoma tumors grafted in the nude mice was revealed 24 hours after injection of Gd-TCP and Gd-H, respectively. The percentage of injected Gd localized to the tumor measured by inductively coupled plasma atomic emission spectrometry (ICP-AES was approximately 21% for Gd-TCP and 28% for Gd-H which were higher than that of Gd-DTPA (10%. CONCLUSIONS: The high concentration of Gd in the tumor is indicative of a selective retention of the compounds and indicates that Gd-TCP and Gd-H are promising MR imaging contrast agents for melanoma detection. Gd-porphyrins have considerable promise for further diagnostic applications in magnetic resonance imaging. KEY WORDS: MRI, porphyrin-based contrast agent, hematoporphyrin, melanoma.

Porphyrin molecules boost the sensitivity of epitaxial graphene for NH3 detection

Science.gov (United States)

Iezhokin, I.; den Boer, D.; Offermans, P.; Ridene, M.; Elemans, J. A. A. W.; Adriaans, G. P.; Flipse, C. F. J.

2017-02-01

The sensitivity of quasi-free standing epitaxial graphene for NH3 detection is strongly enhanced by chemical functionalization with cobalt porphyrins resulting in a detection limit well below 100 ppb. Hybridization between NH3 and cobalt porphyrins induces a charge transfer to graphene and results in a shift of the graphene Fermi-level as detected by Hall measurements and theoretically explained by electronic structure calculations.

Highly spectrum-selective ultraviolet photodetector based on p-NiO/n-IGZO thin film heterojunction structure.

Science.gov (United States)

Li, H K; Chen, T P; Hu, S G; Li, X D; Liu, Y; Lee, P S; Wang, X P; Li, H Y; Lo, G Q

2015-10-19

Ultraviolet photodetector with p-n heterojunction is fabricated by magnetron sputtering deposition of n-type indium gallium zinc oxide (n-IGZO) and p-type nickel oxide (p-NiO) thin films on ITO glass. The performance of the photodetector is largely affected by the conductivity of the p-NiO thin film, which can be controlled by varying the oxygen partial pressure during the deposition of the p-NiO thin film. A highly spectrum-selective ultraviolet photodetector has been achieved with the p-NiO layer with a high conductivity. The results can be explained in terms of the "optically-filtering" function of the NiO layer.

Cutaneous porphyrins exhibit anti-stokes fluorescence that is detectable in sebum (Conference Presentation)

Science.gov (United States)

Tian, Giselle; Zeng, Haishan; Zhao, Jianhua; Wu, Zhenguo; Al Jasser, Mohammed; Lui, Harvey; Mclean, David I.

2016-02-01

Porphyrins produced by Propionibacterium acnes represent the principal fluorophore associated with acne, and appear as orange-red luminescence under the Wood's lamp. Assessment of acne based on Wood's lamp (UV) or visible light illumination is limited by photon penetration depth and has limited sensitivity for earlier stage lesions. Inducing fluorescence with near infrared (NIR) excitation may provide an alternative way to assess porphyrin-related skin disorders. We discovered that under 785 nm CW laser excitation PpIX powder exhibits fluorescence emission in the shorter wavelength range of 600-715 nm with an intensity that is linearly dependent on the excitation power. We attribute this shorter wavelength emission to anti-Stokes fluorescence. Similar anti-Stokes fluorescence was also detected focally in all skin-derived samples containing porphyrins. Regular (Stokes) fluorescence was present under UV and visible light excitation on ex vivo nasal skin and sebum from uninflamed acne, but not on nose surface smears or sebum from inflamed acne. Co-registered CW laser-excited anti-Stokes fluorescence and fs laser-excited multi-photon fluorescence images of PpIX powder showed similar features. In the skin samples because of the anti-Stokes effect, the NIR-induced fluorescence was presumably specific for porphyrins since there appeared to be no anti-Stokes emission signals from other typical skin fluorophores such as lipids, keratins and collagen. Anti-Stokes fluorescence under NIR CW excitation is more sensitive and specific for porphyrin detection than UV- or visible light-excited regular fluorescence and fs laser-excited multi-photon fluorescence. This approach also has higher image contrast compared to NIR fs laser-based multi-photon fluorescence imaging. The anti-Stokes fluorescence of porphyrins within sebum could potentially be applied to detecting and targeting acne lesions for treatment via fluorescence image guidance.

Transforming a Targeted Porphyrin Theranostic Agent into a PET Imaging Probe for Cancer

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Jiyun Shi, Tracy W.B. Liu, Juan Chen, David Green, David Jaffray, Brian C. Wilson, Fan Wang, Gang Zheng

2011-01-01

Full Text Available Porphyrin based photosensitizers are useful agents for photodynamic therapy (PDT and fluorescence imaging of cancer. Porphyrins are also excellent metal chelators forming highly stable metallo-complexes making them efficient delivery vehicles for radioisotopes. Here we investigated the possibility of incorporating 64Cu into a porphyrin-peptide-folate (PPF probe developed previously as folate receptor (FR targeted fluorescent/PDT agent, and evaluated the potential of turning the resulting 64Cu-PPF into a positron emission tomography (PET probe for cancer imaging. Noninvasive PET imaging followed by radioassay evaluated the tumor accumulation, pharmacokinetics and biodistribution of 64Cu-PPF. 64Cu-PPF uptake in FR-positive tumors was visible on small-animal PET images with high tumor-to-muscle ratio (8.88 ± 3.60 observed after 24 h. Competitive blocking studies confirmed the FR-mediated tracer uptake by the tumor. The ease of efficient 64Cu-radiolabeling of PPF while retaining its favorable biodistribution, pharmacokinetics and selective tumor uptake, provides a robust strategy to transform tumor-targeted porphyrin-based photosensitizers into PET imaging probes.

Core Knowledge Confusions among University Students

Science.gov (United States)

Lindeman, Marjaana; Svedholm, Annika M.; Takada, Mikito; Lonnqvist, Jan-Erik; Verkasalo, Markku

2011-01-01

Previous studies have demonstrated that university students hold several paranormal beliefs and that paranormal beliefs can be best explained with core knowledge confusions. The aim of this study was to explore to what extent university students confuse the core ontological attributes of lifeless material objects (e.g. a house, a stone), living…

Efficient photoelectrochemical water splitting by a doping-controlled GaN photoanode coated with NiO cocatalyst

International Nuclear Information System (INIS)

Kang, Jin-Ho; Kim, Soo Hee; Ebaid, Mohamed; Lee, June Key; Ryu, Sang-Wan

2014-01-01

Efficient photoelectrochemical (PEC) water splitting was demonstrated by a doping-controlled GaN photoanode coated with NiO cocatalyst. Highly doped n-GaN was sandwiched between undoped GaN layers to effectively collect electrons through ohmic contact. With zero external bias, the photocurrent density of the optimized doping profile was ∼3.5 times higher than that of the undoped GaN reference. However, the increased doping concentration degraded the photoanode stability, which was attributed to crystalline defects generated in the highly doped n-GaN. NiO cocatalyst improved the long-term stability of the photoanode because of GaN/NiO band alignment, enhancing hole transport into NiO and suppressing PEC corrosion mediated by hole crowding in GaN. This work established a design strategy for increasing the photocurrent as well as improving stability during water splitting with a GaN-based photoanode

Cartografías de la actividad de atención directa a niños, niñas y adolescentes en situación de calle en Montevideo, Uruguay

Directory of Open Access Journals (Sweden)

Daniel Fagundez

2015-08-01

Full Text Available Este artículo presenta resultados de una investigación realizada sobre el estudio de la actividad de atención directa a niños, niñas y adolescentes (NNA en situación de calle. En Uruguay son atendidos 1100 NNA por diferentes dispositivos gestionados y controlados por el Estado. Esto representa un alto nivel de atención de una población extremadamente vulnerable. Los educadores sociales y psicólogos son las principales profesiones que participan de la atención directa, constituyendo un modelo educativo hibrido entre varios enfoques disciplinares. El estudio se realizó a partir de un seguimiento de un equipo de atención directa a esta población en Montevideo, Uruguay, mediante la metodología etnográfica y cartográfica. Los resultados plantean la complejidad por la cual los trabajadores atraviesan, en una actividad que tiene una alta carga de frustración y creatividad. Se discute sobre la implicación de los educadores entre ser agentes técnicos del Estado y ejercer una ética desde la educación social y desde una perspectiva de los derechos del niño.

Nitrogen Cycle Evaluation (NiCE) Chip for the Simultaneous Analysis of Multiple N-Cycle Associated Genes.

Science.gov (United States)

Oshiki, Mamoru; Segawa, Takahiro; Ishii, Satoshi

2018-02-02

Various microorganisms play key roles in the Nitrogen (N) cycle. Quantitative PCR (qPCR) and PCR-amplicon sequencing of the N cycle functional genes allow us to analyze the abundance and diversity of microbes responsible in the N transforming reactions in various environmental samples. However, analysis of multiple target genes can be cumbersome and expensive. PCR-independent analysis, such as metagenomics and metatranscriptomics, is useful but expensive especially when we analyze multiple samples and try to detect N cycle functional genes present at relatively low abundance. Here, we present the application of microfluidic qPCR chip technology to simultaneously quantify and prepare amplicon sequence libraries for multiple N cycle functional genes as well as taxon-specific 16S rRNA gene markers for many samples. This approach, named as N cycle evaluation (NiCE) chip, was evaluated by using DNA from pure and artificially mixed bacterial cultures and by comparing the results with those obtained by conventional qPCR and amplicon sequencing methods. Quantitative results obtained by the NiCE chip were comparable to those obtained by conventional qPCR. In addition, the NiCE chip was successfully applied to examine abundance and diversity of N cycle functional genes in wastewater samples. Although non-specific amplification was detected on the NiCE chip, this could be overcome by optimizing the primer sequences in the future. As the NiCE chip can provide high-throughput format to quantify and prepare sequence libraries for multiple N cycle functional genes, this tool should advance our ability to explore N cycling in various samples. Importance. We report a novel approach, namely Nitrogen Cycle Evaluation (NiCE) chip by using microfluidic qPCR chip technology. By sequencing the amplicons recovered from the NiCE chip, we can assess diversities of the N cycle functional genes. The NiCE chip technology is applicable to analyze the temporal dynamics of the N cycle gene

Familia, Comunidad e Instituciones. Atención Integral a Niñas y Niños en Situación de Discapacidad.

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Lina Pinzón

2009-10-01

Full Text Available La discapacidad es asumida en la mayoría de las sociedades como una barrera o limitación humana. Las mayores, radican en el conjunto de actitudes sociales e imágenes prototípicas que limitan e inhiben la participación y la igualdad. Esto se fundamenta en una interpretación de factores externos inherentes al problema y no en una comprensión de sus posibilidadesde desempeño personal. Ha de considerarse que la limitación no debería imponer una ruptura con la persona. La discapacidad se produce en la interacción de la persona con su medio. En el presente artículo se realiza un análisis del tema de niñas y niños en condición de discapacidad en el Centro de Atención Integral Colombo Suizo de la ciudad de Tunja y la corresponsabilidad de la familia, la comunidad y las instituciones, en los procesos de atención integral. El documento está estructurado en tres partes; la primera aborda teóricamente los conceptos de discapacidad, responsabilidad familiar, institucional y comunitaria,y el marco legal relacionado con el tema. En la segunda parte, se mencionan los elementos de análisis y finalmente se establece una reflexión acerca de la corresponsabilidad en la atención integral de la discapacidad como condición humana de ellas y ellos.

TDAH: repercusión en la vida del niño. Diseño de una intervención de enfermería en el programa de atención al niño sano

OpenAIRE

Elizalde Muñoz, Ana

2014-01-01

El Trastorno por déficit de atención con o sin hiperactividad (TDAH) es uno de los trastornos psiquiátricos más prevalentes en la edad infantil. Estos niños se caracterizan por presentar grandes dificultades a la hora de regular su nivel de actividad, inhibir sus impulsos y mantener la atención. Debido a este trastorno distintos ámbitos de la vida del niño se ven afectados. En este trabajo se pretende conocer cómo afecta el TDAH en la salud física y psicológica del niño, en la vida familiar y...

Mineralogy of halloysites and their interaction with porphyrine

Czech Academy of Sciences Publication Activity Database

Vašutová, V.; Bezdička, Petr; Lang, Kamil; Hradil, David

2013-01-01

Roč. 57, č. 3 (2013), s. 243-250 ISSN 0862-5468 Institutional support: RVO:61388980 Keywords : organoclays * mineralogy * porphyrine * CEC Subject RIV: CA - Inorganic Chemistry Impact factor: 0.434, year: 2013

Electrochemical behavior of low phosphorus electroless Ni-P-Si3N4 composite coatings

International Nuclear Information System (INIS)

Balaraju, J.N.; Ezhil Selvi, V.; Rajam, K.S.

2010-01-01

In the present investigation the electroless Ni-P-Si 3 N 4 composite coatings were prepared by using a low phosphorus bath containing submicron size silicon nitride particles. Plain Ni-P deposits were also prepared for comparison. The phosphorus contents present in electroless plain Ni-P and Ni-P-Si 3 N 4 coatings are 3.7 and 3.4 wt.%, respectively. Scanning electron microscope (SEM) images obtained for composite coatings (cross-sections) showed that the second phase particles are uniformly distributed throughout the thickness of the deposits. It was found that nodularity increased with particle codeposition in Ni-P matrix. To find out the electrochemical behavior of plain Ni-P and composite coatings, potentiodynamic polarization and electrochemical impedance (EIS) studies were carried out in 3.5 wt.% sodium chloride solution in non-deaerated condition. Second phase particle incorporation in Ni-P matrix indicated a marginal decrease in corrosion current density compared to the plain Ni-P deposits. This was further confirmed by EIS studies and SEM analysis of the corroded samples.

Electron energy loss spectroscopy of CH3N2CH3 adsorbed on Ni(100), Ni(111), Cr(100), Cr(111)

International Nuclear Information System (INIS)

Schulz, M.A.

1985-07-01

A study of the adsorption of CH 3 N 2 CH 3 on Ni(100), Ni(111), Cr(100), and Cr(111) using high resolution electron energy loss spectroscopy (EELS) is presented. Under approximately the same conditions of coverage, the vibrational spectra of CH 3 N 2 CH 3 on these four surfaces are quite distinct from one another, implying that the CH 3 N 2 CH 3 -substrate interaction is very sensitive to the physical and electronic structure of each surface. In addition to the room temperature studies, the evolution of surface species on the Ni(100) surface in the temperature range 300 to 425 K was studied. Analysis of the Ni(100) spectra indicates that molecular adsorption, probably through the N lone pair, occurs at room temperature. Spectra taken after annealing the CH 3 N 2 CH 3 -Ni(100) surfaces indicate that CH and CN bond scission occurred at the elevated temperatures. Decomposition of CH 3 N 2 CH 3 takes place on the Ni(111), Cr(100), and Cr(111) surfaces at room temperature, as evidenced by the intensity of the carbon-metal stretch in the corresponding spectra. Possible identities of coadsorbed dissociation products are considered. The stable coverage of surface species on all four surfaces at 300 K is less than one monolayer. A general description of an electron energy loss (EEL) spectrometer is given. Followed by a more specific discussion of some recent modifications to the EEL monochromator assembly used in this laboratory. Both the previous configuration of our monochromator and the new version are briefly described, as an aid to understanding the motivation for the changes as well as the differences in operation of the two versions. For clarity, the new monochromator design is referred to as variable pass, while the previous design is referred to as double pass. A modified tuning procedure for the new monochromator is also presented. 58 refs., 11 figs

Excitation energy transfer in ruthenium (II)-porphyrin conjugates led to enhanced emission quantum yield and 1O2 generation

International Nuclear Information System (INIS)

Pan, Jie; Jiang, Lijun; Chan, Chi-Fai; Tsoi, Tik-Hung; Shiu, Kwok-Keung; Kwong, Daniel W.J.; Wong, Wing-Tak; Wong, Wai-Kwok; Wong, Ka-Leung

2017-01-01

Porphyrins are good photodynamic therapy (PDT) agents due to its flexibility for modifications to achieve tumor localization and photo-cytotoxicity against cancer. Yet they are not perfect. In a Ru(polypyridyl)-porphyrin system, the Ru(polypyridyl) moiety improves the water solubility and cell permeability. Consider the similar excited state energies between Ru(polypyridyl) and porphyrin moieties; a small perturbation (e.g. Zn(II) metalation) would lead to a marked change in the energy migration process. In this work, we have synthesized a series of porphyrins conjugated with Ru(polypyridyl) complexes using different linkers and investigated their photophysical properties, which included singlet oxygen quantum yield and their in vitro biological properties, resulting from linker variation and porphyrin modification by Zn(II) metalation. - Graphical abstract: Four amphiphilic ruthenium(II)-porphyrin complexes were prepared that display energy transfer conversion with zinc coordination, lysosome specific target, low dark toxicity and efficient photodynamic therapy.

Juegos de niñas y juegos de niños: Estudio sobre la representación del juego infantil a través del dibujo

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Francisco Moragón-Alcañiz

2016-01-01

Full Text Available El objetivo del estudio consistió en describir la forma en que niños y niñas de primer ciclo de educación primaria representan el juego infantil a través del dibujo. La recolección de datos se realizó en dos sesiones separadas por una semana, acompañada de narraciones orales de los participantes para cada dibujo. Una vez transcritas las entrevistas se codificaron las categorías más importantes a saber: Tipo de juego, dominio de actividad física, edad, género, dimensión social y lugar. Los dibujos de niños representan actividades deportivas y competitivas en espacios al aire libre en compañía de niños. Por el contrario, los dibujos de niñas representan actividades sedentarias o de baja intensidad realizadas bajo techo en compañía de niñas y mujeres adultas. En conclusión, el dibujo infantil puede favorecer la comprensión del juego infantil con el fin de mostrar alternativas a aquellos modelos de cultura física dominantes impuestos desde la primera infancia.

Conceptualización de nociones espaciales en niños y niñas no oyentes

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Luz Elena Patiño-Giraldo

2011-01-01

Full Text Available En este artículo presento algunos resultados obtenidos en relación con los niveles de conceptualización alcanzados por dos grupos de niños, niñas y jóvenes no oyentes usuarios de la Lengua de Señas Colombiana, en una ciudad intermedia de Colombia, acerca de algunas nociones espaciales relacionadas con las Ciencias Sociales. El estudio se fundamenta en el reconocimiento de la Lengua de Señas local como la lengua natural de las personas no oyentes, pero debo clarificar que los sujetos participantes en el estudio tuvieron una fuerte incidencia de procesos educativos desde una perspectiva oralista. La estrategia metodológica del estudio se caracteriza por ser exploratoria y policíclica, con aspectos cualitativos y cuantitativos (en continuas fases cuyos resultados fueron modificando el problema de investigación.

Ultrafast electron injection at the cationic porphyrin-graphene interface assisted by molecular flattening

KAUST Repository

Aly, Shawkat Mohammede; Parida, Manas R.; Alarousu, Erkki; Mohammed, Omar F.

2014-01-01

The steady-state and femtosecond (fs) time-resolved data clearly demonstrate that the charge transfer (CT) process at the porphyrin-graphene carboxylate (GC) interfaces can be tuned from zero to very sufficient and ultrafast by changing the electronic structure of the meso unit and the redox properties of the porphyrin cavity. This journal is © the Partner Organisations 2014.

Graphene and Carbon-Nanotube Nanohybrids Covalently Functionalized by Porphyrins and Phthalocyanines for Optoelectronic Properties.

Science.gov (United States)

Wang, Aijian; Ye, Jun; Humphrey, Mark G; Zhang, Chi

2018-04-01

In recent years, there has been a rapid growth in studies of the optoelectronic properties of graphene, carbon nanotubes (CNTs), and their derivatives. The chemical functionalization of graphene and CNTs is a key requirement for the development of this field, but it remains a significant challenge. The focus here is on recent advances in constructing nanohybrids of graphene or CNTs covalently linked to porphyrins or phthalocyanines, as well as their application in nonlinear optics. Following a summary of the syntheses of nanohybrids constructed from graphene or CNTs and porphyrins or phthalocyanines, explicit intraconjugate electronic interactions between photoexcited porphyrins/phthalocyanines and graphene/CNTs are introduced classified by energy transfer, electron transfer, and charge transfer, and their optoelectronic applications are also highlighted. The major current challenges for the development of covalently linked nanohybrids of porphyrins or phthalocyanines and carbon nanostructures are also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of Exciplex Formation Between Cu-Porphyrin and Calf-thymus DNA as Revealed by Saturation Resonance Raman Spectroscopy

NARCIS (Netherlands)

Shvedko, A.G.; Kruglik, S.; Kruglik, S.G.; Ermolenkov, V.V.; Turpin, P.Y.; Greve, Jan; Otto, Cornelis

1999-01-01

The excited-state complex (exciplex) formation that results from the photoinduced interaction of water-soluble cationic copper(II) 5,10,15,20-tetrakis[4-(N-methylpyridyl)]porphyrin [Cu(TMpy-P4)] with calf-thymus DNA has been studied in detail by resonance Raman (RR) spectroscopy using both ~10 ns

La comunicación participativa como herramienta generadora de ciudadanía activa en la niñez

OpenAIRE

Sánchez Castiblanco, John Richard

2016-01-01

La presente tesis doctoral tiene como propósito analizar y evaluar el uso de la comunicación como una herramienta de participación y empoderamiento de la niñez, que a su vez posibilite la formación y el desarrollo de la ciudadanía activa de las niñas y los niños. Toma como objeto de estudio una intervención sociocomunicativa que se realizó con un grupo de niñas y niños de una zona vulnerable de la periferia de la ciudad de Bogotá. Esta intervención se basó en un proyecto de televisión con la ...

La integración de niños y niñas a familias adoptivas en argentina, conexiones legítimas

Directory of Open Access Journals (Sweden)

Mariela Pena

2016-01-01

Full Text Available Actualmente en la Argentina muchas familias se conforman mediante la adopción de niños y niñas. Estas relaciones son expresadas en un lenguaje de parentesco a través de sentidos, valoraciones y prácticas concretas que van modificándose a lo largo del tiempo. Aquí nos interrogamos por los procesos a través de los cuales se incorpora al niño o niña al nuevo grupo de parentesco, a partir del trabajo de campo con sujetos adultos que han adoptado a menores durante la última década en Buenos Aires. Exploramos sus relatos en torno al "encuentro" con el hijo o hija adoptivo, las nociones de pertenencia y la construcción de sus vínculos familiares "pasados". Sugerimos líneas de contacto con estudios etnográficos en otros contextos y a su vez proponemos tensiones y connotaciones locales para la intención de estas familias de dotar sus conexiones de legitimidad y "veracidad".

La integración de niños y niñas a familias adoptivas en argentina, conexiones legítimas

Directory of Open Access Journals (Sweden)

Mariela Pena

2016-02-01

Full Text Available Actualmente en la Argentina muchas familias se conforman mediante la adopción de niños y niñas. Estas relaciones son expresadas en un lenguaje de parentesco a través de sentidos, valoraciones y prácticas concretas que van modificándose a lo largo del tiempo. Aquí nos interrogamos por los procesos a través de los cuales se incorpora al niño o niña al nuevo grupo de parentesco, a partir del trabajo de campo con sujetos adultos que han adoptado a menores durante la última década en Buenos Aires. Exploramos sus relatos en torno al “encuentro” con el hijo o hija adoptivo, las nociones de pertenencia y la construcción de sus vínculos familiares “pasados”. Sugerimos líneas de contacto con estudios etnográficos en otros contextos y a su vez proponemos tensiones y connotaciones locales para la intención de estas familias de dotar sus conexiones de legitimidad y “veracidad”.

Caracterización emocional de niños escolares hospitalizados con enfermedades crónicas

Directory of Open Access Journals (Sweden)

Omar Cruz Martín

Full Text Available Introducción: las emociones son un proceso de evaluación cognitiva sobre el contexto, los recursos de afrontamiento y los posibles resultados de esos procesos. Incluyen factores fisiológicos, cognitivos, sociales y comportamentales, son estados psíquicos transitorios que dan colorido a la vida de los seres humanos. Pueden ser positivas o negativas, las primeras potencian la salud, mientras que las segundas tienden a disminuirla. Objetivo: caracterizar del bienestar emocional de niños con enfermedades crónicas ingresados en el hospital pediátrico de Villa Clara. Métodos: se realizó un estudio descriptivo transversal con 18 niños y sus familiares, seleccionados intencionalmente. Se aplicó entrevista a niños y padres, observación no participante, dibujo libre, inventario diagnóstico para medir ansiedad rasgo y estado en niños y el inventario de depresión para niños-abreviado. Resultados: predominaron las emociones negativas ansiedad, miedo, tristeza y preocupación. Las emociones positivas resultaron en extremo escasas. Conclusiones: en los niños estudiados en el Hospital Pediátrico "José Luis Miranda", de la provincia de Villa Clara, se constató la presencia de afectaciones al bienestar emocional, con presencia de depresión y de ansiedad como estados. Los síntomas que más frecuentemente presentaron los niños fueron: temores e inseguridad, intranquilidad, dependencia, ira, impulsividad, dificultad para expresar cariño, aburrimiento y preocupaciones.

Situación de derechos de los niños, niñas y adolescentes trabajadores callejeros nocturnos en Medellín

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John Fernando Ramírez Villegas

2014-07-01

Full Text Available En este artículo se expone de manera general la problemática que enfrentan los niños, niñas y adolescentes -cuya sigla reconoceremos como NNA- trabajadores callejeros nocturnos de Medellín (Colombia. A partir de una investigación cualitativa con enfoque fenomenológico hermenéutico se logra observar e interpretar sus vivencias a la vez que se identifican mejor sus necesidades. La edad de los NNA a los que se les aplicó una entrevista y una guía de observación oscilaba entre los 9 y 14 años. El procesamiento de la información obtenida se realizó empleando el análisis de contenido, generando así algunas categorías desde los mismos datos. Dentro de los resultados se encontró que ellos tienen sus propias concepciones sobre la noche, el dinero, ser pobre, sus derechos, la libertad, la seguridad y la verdad, todas permeadas por una sociedad que ha sido indiferente a las necesidades de esta población, asimismo, este artículo genera una reflexión sobre el trabajo infantil en Colombia y reitera la necesidad de atender esta problemática social.

Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

International Nuclear Information System (INIS)

Viana, A.S.; Leupold, S.; Montforts, F.-P.; Abrantes, L.M.

2005-01-01

A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 x 10 -10 mol cm -2 and a thickness of 13 A, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water

NANOSTRUCTURED TiO2 SENSITIZED WITH PORPHYRINS FOR SOLAR WATER-SPLITTING

Directory of Open Access Journals (Sweden)

MARCELA-CORINA ROŞU

2011-03-01

Full Text Available Nanostructured TiO2 sensitized with porphyrins for Solar water-splitting.The production of hydrogen from water using solar light is very promising for generations of an ecologically pure carrier contributing to a clean, sustainable and renewable energy system. The selection of specific photocatalyst material for hydrogen production in photoelectrochemical cells (PECs is based on some important characteristics of semiconductor, such as photo-corrosion and chemical corrosion stability, photocatalytic potential, high sensitivity for UV-visible light. In the present paper, different nanocrystalline TiO2 photoanodes have been prepared via wet-chemical techniques followed by annealing treatment and sensitized with porphyrins and supramolecular complexes of porphyrins. The so obtained photocatalysts were characterized with UV-VIS absorption spectroscopy and spectrofluorimetry. The purpose of these experiments is to show if the prepared materials possess the necessary photocatalytic characteristics and if they can be used with success in H2 production from water decomposition in PECs.

Radioboletín informativo para niños

OpenAIRE

Jorge Valdés

2015-01-01

En "Auge y caída de los vÍdeo juegos" el autor señala que las tecnologías digitales cambian aceleradamente. Cada cambio impacta en el entorno de la sociedad y la cultura ¿Cómo adaptarse a estos retos? ¿Cómo controlarlos? se responde en el artículo. Otro artículo hace alusión a la conmemoración de los 10 años de la Declaración del Nuevo Orden Internacional de la Información y Comunicación - NOIIC-. Radio boletín informativo para niños cita las recomendaciones dadas en el Seminario realizado po...

Porphyrin formation and its regulation in Arthrobacter

NARCIS (Netherlands)

Kortstee, G.J.J.

1969-01-01

Porphyrins (tetrapyrroles) are the basic compounds of a number of substances functioning in living organisms as carriers of oxygen (hemoglobin), carriers of electrons (cytochromes) or as a trap for radiant energy (chlorophyll). In these active forms the tetrapyrroles contain a metal and are

Helical chirality induction of expanded porphyrin analogues

Indian Academy of Sciences (India)

of this figure-eight conformation in relation to the num- ber of π-electrons attracts ... porphyrin moieties.7a–d In this context, application of ... become problematic. Lindsey .... cell. [a]. CD sign (λmax/nm). UV-vis θ/ abs. Ligand of 1st Cotton effect.

Corrosion behavior of nanostructured Ni-Si{sub 3}N{sub 4} composite films: A study of electrochemical impedance spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Li, J.M.; Cai, C.; Xue, M.Z.; Liu, Y.G. [School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, Shanghai (China); Yin, J.Y.; Zhang, Z. [Department of Chemistry, Zhejiang University, Hangzhou (China); Key Laboratory for Light Alloy Materials Technology, JiaXing (China); Li, J.F. [School of Materials Science and Engineering, Central South University, Changsha (China); Yang, J.F. [State Key Laboratory for Mechanical Behavior of Materials, Xi' an Jiaotong University (China)

2012-07-15

Ni-Si{sub 3}N{sub 4} nanocomposite films with both the consecutive Ni crystallites and dispersed Si{sub 3}N{sub 4} particles in the nanometer range have been fabricated using DC electroplating technique, and characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), and X-ray diffraction (XRD). The corrosion resistance of the Ni-Si{sub 3}N{sub 4} nanocomposite film has been compared to that of pure Ni coating through polarization. Meanwhile, the corrosion process of Ni-Si{sub 3}N{sub 4} nanocomposite film in neutral 3.5% NaCl solution has been investigated using electrochemical impedance spectroscopy (EIS). The results show that the Ni-Si{sub 3}N{sub 4} nanocomposite film is more resistant to corrosion than the pure Ni coating. The corrosion of Ni-Si{sub 3}N{sub 4} nanocomposite film is controlled by electrochemical step, and the whole corrosion process is divided into two sequential stages. The main corrosion type of Ni-Si{sub 3}N{sub 4} nanocomposite films in neutral 3.5% NaCl solution is pitting. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

The structure and properties of ZrN-Ni-Co-coatings on the edges steel knives of wood-cutting tools

International Nuclear Information System (INIS)

Chaevskij, V.V.; Grishkevich, A.A.; Zhilinskij, V.V.; Kuleshov, A.K.

2015-01-01

Modes were selected and formed electroplated Ni-Co-coatings, ion-plasma Zr N-coatings as well as combined Zr N-Ni-Co-coating on the edges steel (type R6M5) knives of wood-cutting milling tools. Formed electroplated Ni-Co-layers are not mixed with the steel substrate and the Zr N-coating. Microhardness of combined Zr N-Ni-Co-coatings is to 1,2-1,5 times more than microhardness of steel base and bare steel. When cutting laminated chipboard by steel knives of milling tool with a Ni-Co- and Zr N-Ni-Co-coatings under laboratory conditions, abrasive surface wear type of edges knives is observed. Calculating bulk wear of edges knives with Zr N-Ni-Co-coatings showed reduction of more than 3 times value in comparison with knives with Ni-Co-coatings. Pilot testing of tool modified with combined Zr N-Ni-Co-coatings at OJSC 'Minskdrev' when cutting pine confirmed relevance of the tests carried out, as well as showed an increase in durability period of cutters to 30% compared with bare tool. (authors)

Controlled carrier screening in p-n NiO/GaN piezoelectric generators by an Al2O3 insertion layer

Science.gov (United States)

Johar, Muhammad Ali; Jeong, Dae Kyung; Afifi Hassan, Mostafa; Kang, Jin-Ho; Ha, Jun-Seok; Key Lee, June; Ryu, Sang-Wan

2017-12-01

The performance of a piezoelectric generator (PG) depends significantly on the internal screening process inside the device. As piezoelectric charges appear on both ends of the piezoelectric crystal, internal screening starts to decrease the piezoelectric bias. Therefore, the piezoelectric energy generated by external stress is not fully utilized by external circuit, which is the most challenging aspect of high-efficiency PGs. In this work, the internal screening effect of a NiO/GaN p-n PG was analyzed and controlled with an Al2O3 insertion layer. Internal screening in the p-n diode PG was categorized into free-carrier screening in neutral regions and junction screening due to charge drift across the junction. It was observed that junction screening could be significantly suppressed by inserting an Al2O3 layer and that effect was dominant in a leaky diode PG. With this implementation, the piezoelectric bias of the NiO/GaN PG was improved by a factor of ~100 for high-leakage diodes and a factor of ~1.6 for low-leakage diodes. Consequently, NiO/Al2O3/GaN PGs under a stress of 5 MPa provided a piezoelectric bias of 12.1 V and a current density of 2.25 µA cm-2. The incorporation of a highly resistive Al2O3 layer between p-NiO and n-GaN layers in NiO/GaN heterojunctions provides an efficient means of improving the piezoelectric performance by controlling the internal screening of the piezoelectric field.

Porphyrins from Messel oil shale (Eocene, Germany): Structure elucidation, geochemical and biological significance, and distribution as a function of depth

Energy Technology Data Exchange (ETDEWEB)

Ocampo, R.; Bauder, C.; Callot, H.J.; Albrecht, P. (Univ. Louis Pasteur, Strasbourg (France))

1992-02-01

The extraction and isolation procedures of twenty nickel porphyrins (seven alkylporphyrins, thirteen carboxylic acids) from lacustrine Messel shale (Eocene, Germany), as well as the unequivocal structural assignments (obtained using 200 and 400 MHz nuclear magnetic resonance (NMR), nuclear Overhauser effect, mass spectrometry, and total or partial synthesis of six reference compounds) are described. Ten porphyrins could be specifically correlated with biological precursors: algal chlorophyll c (4), bacteriochlorophylls d (3), and heme (3), while the remaining ones may arise from several chlorophylls. The structures of these fossil pigments mostly confirm the classical Treibs scheme,' including the origin of some porphyrins from nonchlorophyll sources. They also show that, even in a very immature sediment, deep modifications occur, including, in particular, extensive degradation of chlorophyll E ring. The composition of the porphyrin fractions of Messel oil shale was also studied as a function of depth. A porphyrin acids/alkylporphyrins ratio varying from 0.35 to 24.8 demonstrated that the apparent homogeneity of the shale is not reflected on the molecular scale. This was confirmed when the abundance of the twenty individual porphyrins of known structure was measured along the core. Significant correlations between individual porphyrins were found: fossils of bacteriochlorophylls d, homolog pairs of porphyrins (3-H/3-ethyl), etc.

Porphyrins from Messel oil shale (Eocene, Germany): Structure elucidation, geochemical and biological significance, and distribution as a function of depth

Science.gov (United States)

Ocampo, Rubén; Bauder, Claude; Callot, Henry J.; Albrecht, Pierre

1992-02-01

The extraction and isolation procedures of twenty nickel porphyrins (seven alkylporphyrins, thirteen carboxylic acids) from lacustrine Messel shale (Eocene, Germany), as well as the unequivocal structural assignments (obtained using 200 and 400 MHz nuclear magnetic resonance (NMR), nuclear Overhauser effect, mass spectrometry and total or partial synthesis of six reference compounds) are described. Ten porphyrins could be specifically correlated with biological precursors: algal chlorophyll c (4), bacteriochlorophylls d (3) and heme (3), while the remaining ones may arise from several chlorophylls. The structures of these fossil pigments mostly confirm the classical "Treibs scheme," including the origin of some porphyrins from nonchlorophyll sources. They also show that, even in a very immature sediment, deep modifications occur, including, in particular, extensive degradation of chlorophyll E ring. The composition of the porphyrin fractions of Messel oil shale was also studied as a function of depth. A porphyrin acids/alkylporphyrins ratio varying from 0.35 to 24.8 demonstrated that the apparent homogeneity of the shale is not reflected on the molecular scale. This was confirmed when the abundance of the twenty individual porphyrins of known structure was measured along the core. Significant correlations between individual porphyrins were found: fossils of bacteriochlorophylls d, homolog pairs of porphyrins (3-H/3-ethyl), etc.

REGIOSELECTIVE OXIDATIONS OF EQUILENIN DERIVATIVES CATALYZED BY A RHODIUM (III) PORPHYRIN COMPLEX-CONTRAST WITH THE MANGANESE (III) PORPHYRIN. (R826653)

Science.gov (United States)

AbstractEquilenin acetate and dihydroequilenin acetate were oxidized with iodosobenzene and a rhodium(III) porphyrin catalyst. The selectivity of the reactions differs from that with the corresponding Mn(III) catalyst, or from that of free radical chain oxidation.

Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

Energy Technology Data Exchange (ETDEWEB)

Huang, Guan, E-mail: huangg66@126.com; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

2017-04-30

Graphical abstract: A biomimetic catalyst of iron-tetrakis(4-sulfonatophenyl)porphyrin immobilized on powdered chitosan achieves efficient cyclohexane oxidation with high ketone and alcohol yields. - Highlights: • Fe (TPPS)/pd-CTS is an excellent catalyst for cyclohexane oxidation. • Amino ligation alters the electron cloud density around the iron cation. • Amino coordination likely reduces the activation energy of Fe (TPPS). • The catalyst achieved 22.9 mol% yields of cyclohexanone and cyclohexanol. - Abstract: This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O{sub 2}. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

Local Electronic Structure of a Single-Layer Porphyrin-Containing Covalent Organic Framework

KAUST Repository

Chen, Chen

2017-12-20

We have characterized the local electronic structure of a porphyrin-containing single-layer covalent organic framework (COF) exhibiting a square lattice. The COF monolayer was obtained by the deposition of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMA) and 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) onto a Au(111) surface in ultrahigh vacuum followed by annealing to facilitate Schiff-base condensations between monomers. Scanning tunneling spectroscopy (STS) experiments conducted on isolated TAPP precursor molecules and the covalently linked COF networks yield similar transport (HOMO-LUMO) gaps of 1.85 ± 0.05 eV and 1.98 ± 0.04 eV, respectively. The COF orbital energy alignment, however, undergoes a significant downward shift compared to isolated TAPP molecules due to the electron-withdrawing nature of the imine bond formed during COF synthesis. Direct imaging of the COF local density of states (LDOS) via dI/dV mapping reveals that the COF HOMO and LUMO states are localized mainly on the porphyrin cores and that the HOMO displays reduced symmetry. DFT calculations reproduce the imine-induced negative shift in orbital energies and reveal that the origin of the reduced COF wave function symmetry is a saddle-like structure adopted by the porphyrin macrocycle due to its interactions with the Au(111) substrate.

Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan

Science.gov (United States)

Huang, Guan; Liu, Yao; Cai, Jing Li; Chen, Xiang Feng; Zhao, Shu Kai; Guo, Yong An; Wei, Su Juan; Li, Xu

2017-04-01

This study investigates how ligands modulate metalloporphyrin activity with the goal of producing a practical biomimetic catalyst for use in the chemical industry. We immobilized iron porphyrinate [iron-tetrakis-(4-sulfonatophenyl)-porphyrin; Fe(III) (TPPS)] on powdered chitosan (pd-CTS) to form an immobilized catalyst Fe(III) (TPPS)/pd-CTS, which was characterized using modern spectroscopic techniques and used for catalytic oxidation of cyclohexane with O2. Amino coordination to iron porphyrin in Fe(III) (TPPS)/pd-CTS altered the electron cloud density around the iron cation, probably by reducing the activation energy of Fe(III) (TPPS) and raising the reactivity of the iron ion catalytic center, thereby improving the catalytic efficiency. One milligram of Fe(III) (TPPS) catalyst can be reused three times for the oxidation reaction to yield an average of 22.9 mol% of cyclohexanone and cyclohexanol.

Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

KAUST Repository

Xia, Wei

2015-02-05

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

Concerning the Deactivation of Cobalt(III)-Based Porphyrin and Salen Catalysts in Epoxide/CO 2 Copolymerization

KAUST Repository

Xia, Wei; Salmeia, Khalifah A.; Vagin, Sergei I.; Rieger, Bernhard

2015-01-01

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Functioning as active catalysts for propylene oxide (PO) and carbon dioxide copolymerization, cobalt(III)-based salen and porphyrin complexes have drawn great attention owing to their readily modifiable nature and promising catalytic behavior, such as high selectivity for the copolymer formation and good regioselectivity with respect to the polymer microstructure. Both cobalt(III)-salen and porphyrin catalysts have been found to undergo reduction reactions to their corresponding catalytically inactive cobalt(II) species in the presence of propylene oxide, as evidenced by UV/Vis and NMR spectroscopies and X-ray crystallography (for cobalt(II)-salen). Further investigations on a TPPCoCl (TPP=tetraphenylporphyrin) and NaOMe system reveal that such a catalyst reduction is attributed to the presence of alkoxide anions. Kinetic studies of the redox reaction of TPPCoCl with NaOMe suggests a pseudo-first order in cobalt(III)-porphyrin. The addition of a co-catalyst, namely bis(triphenylphosphine)iminium chloride (PPNCl), into the reaction system of cobalt(III)-salen/porphyrin and PO shows no direct stabilizing effect. However, the results of PO/CO2 copolymerization by cobalt(III)-salen/porphyrin with PPNCl suggest a suppressed catalyst reduction. This phenomenon is explained by a rapid transformation of the alkoxide into the carbonate chain end in the course of the polymer formation, greatly shortening the lifetime of the autoreducible PO-ring-opening intermediates, cobalt(III)-salen/porphyrin alkoxides. CO2 saves: The deactivation of cobalt(III)-porphyrin and salen catalysts in propylene oxide/carbon dioxide copolymerization is systematically investigated, revealing a proposed mechanism for the catalyst reduction (see scheme).

Fusion or confusion in obsessive compulsive disorder.

Science.gov (United States)

O'Connor, Kieron; Aardema, Frederick

2003-08-01

Inferential confusion occurs when a person mistakes an imagined possibility for a real probability and might account for some types of thought-action and other fusions reported in obsessive-compulsive disorder. Inferential confusion could account for the ego-dystonic nature of obsessions and their recurrent nature, since the person acts "as if" an imagined aversive inference is probable and tries unsuccessfully to modify this imaginary probability in reality. The clinical implications of the inferential confusion model focus primarily on the role of the imagination in obsessive-compulsive disorder rather than on cognitive beliefs.

Evidence for porphyrins bound, via ester bonds, to the Messel oil shale kerogen by selective chemical degradation experiments

Science.gov (United States)

Huseby, B.; Ocampo, R.

1997-09-01

High amounts of nickel mono- and di-acid porphyrins were released from Messel oil shale kerogen (Eocene, Germany) by selective chemical degradation (acid and base hydrolysis). The released porphyrin fractions were quantified (UV-vis) and their constituents isolated and characterized at the molecular level (UV-vis, MS, NMR). The mono-acid porphyrin fraction released contained four compounds of similar abundance which arise from an obvious chlorophyll or bacteriochlorophyll precursor. The di-acid porphyrin fraction was, however, dominated by far by one compound, mesoporphyrin IX, which must have originated from heme-like precursors (heme, cytochromes, etc.). These results show unambigously that the released mono- and di-acid porphyrins were linked to the macromolecular kerogen network via ester bonds and suggest that precursor heme-like pigments could be selectively and/or more readily incorporated into the macromolecular kerogen network than precursor chlorophylls and bacteriochlorophylls.

Characterization and Modeling I(V of the Gate Schottky Structures HEMTs Ni/Au/AlInN/GaN

Directory of Open Access Journals (Sweden)

N. Benyahya

2014-05-01

Full Text Available In this paper, we have studied the Schottky contact of Ni/Au/AlInN/GaN HEMTs. The current–voltage Igs (Vgs of Ni/Au/AlInN/GaN structures were investigated at room temperature. The electrical parameters such as ideality factor (2.3, barrier height (0.72 eV and series resistance (33 W were evaluated from I(V data, the threshold voltage (-2.42 V, the 2D gas density (1.35 ´ 1013 cm-2 and barrier height (0.94 eV were evaluated from C(V data.

Construcción de identidad de la niñez en contextos de ruralidad en la comuna de Concepción, Chile

Directory of Open Access Journals (Sweden)

Beatriz Aguirre Pastén

2017-01-01

Full Text Available Los estudios sobre la nueva ruralidad dan cuenta de las grandes transformaciones a las que se enfrentan el mundo rural y los sujetos que habitan dichos territorios. En este ámbito de estudio, resulta interesante acercarse a las construcciones de significados que se atribuyen a la niñez en comunidades rurales de la comuna de Concepción en la zona sur de Chile, entregando así un espacio de reflexión teórica tanto a los cambios de lo rural como a la vivencia infantil; dimensiones que han sido frecuentemente “invisibilizadas” por los estudios sociales. Mediante una metodología cualitativa -específicamente con un estudio de caso instrumental-, este estudio se planteó como objetivo, recoger las distinciones del mundo rural y los rasgos de su construcción identitaria y cultural, indagando en las percepciones y experiencias de niños y niñas y describir patrones culturales, necesidades, problemas sociales, habilidades y fortalezas que los caracterizan. Se destaca entre los principales resultados la coexistencia de patrones culturales rurales-tradicionales junto a elementos modernizadores-urbanos que tensionan la cotidianeidad, y los procesos de construcción identitaria lo que interpela la definición de marcos teóricos utilizados para la comprensión de la ruralidad. La evidencia muestra que los niños y niñas de zonas rurales viven en condición desmejorada respecto de aquellos que habitan zonas urbanas, sin embargo, se destaca que en los contextos rurales existe para los niños y niñas aspectos protectores y potenciadores de conductas resilientes.

Evaluation of the (n,p) cross sections for natural Ni and its isotopes {sup 58,60,61,62,64}Ni

Energy Technology Data Exchange (ETDEWEB)

Gonggui, Ma; Shiming, Wang; Kun, Zhang [Sichuan Univ., Chengdu (China). Inst. of Nuclear Science and Technology

1996-06-01

Nickel is a very important structure material in nuclear engineering. The neutron activation cross section of the (n,p) reaction is very important for fusion reactor from the view point of monitoring neutron field. The cross sections {sup 58,60,61,62,64}Ni(n,p){sup 58,60,61,62,64}Co were evaluated based on measured data and theoretical calculation from threshold to 20 MeV. The present evaluations agree well with the measured data of Ni isotopes. (6 figs.).

Hydrogels synthesised through photoinitiator-free photopolymerisation technique for delivering drugs including a tumour-tracing porphyrin

International Nuclear Information System (INIS)

Ng, Loo-Teck; Swami, Salesh; Gordon-Thomson, Clare

2006-01-01

Hydrogels were synthesised using the photoinitiator-free photopolymerisation technique involving interactions between donor/acceptor pairs for delivering drugs of different molecular weights including a porphyrin used as a tumour-tracing agent. N-(5-hydroxy) pentylmaleimide, an acceptor, formed hydrogels with N-vinyl-2-pyrrolidinone, 2-hydroxyethyl methacrylate and N-vinylcaprolactum. Glucosamine, an effective H-donor in enhancing polymerisation as shown by Differential Photocalorimetric results, was found unsuitable for hydrogel preparation. Drugs of different molecular weights releasing at the same rate was discussed. The hydrogels were found to have no toxic effects and were biocompatible with a human keratinocyte cell line

Radiolabeled porphyrin versus gallium-67 citrate for the detection of human melanoma in athymic mice

International Nuclear Information System (INIS)

Maric, N.; Chan, S. Ming; Hoffer, P.B.; Duray, P.

1987-01-01

We performed the biodistribution and imaging studies of 111 In and 67 Ga labeled tetra(4-N-methylpyridyl) porphine, (T4NMPYP), and compared it to that of 67 Ga citrate in athymic mice bearing a human melanoma xenograft. The biodistribution results of both 111 In and 67 Ga labeled T4NMPYP (3, 6, 24, and 48 hours) were similar but differed from that of 67 Ga citrate (48 hours). The optimum tumor uptake of both radiolabeled porphyrins was at 6 hours postinjection and was lower than the tumor uptake of 67 Ga citrate at 48 hours postinjection. Kidney was the only organ showing higher uptake of radiolabeled porphyrin compared to that of 67 Ga citrate. The imaging studies performed with 111 In T4NMPYP and 67 Ga citrate correspond to the biodistribution results. Osteomyelitis present in one mouse showed good localization of 111 In T4NMPYP. 15 refs., 3 figs., 5 tabs

Aspectos éticos en la investigación cualitativa con niños

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Luisa Fernanda Moscoso Loaiza

2018-01-01

Full Text Available La incorporación de los niños como participantes de estudios investigativos es una práctica más frecuente en la actualidad debido a la necesidad de conocer y entender su visión acerca de las experiencias de vida, lo que plantea nuevos retos y responsabilidades que se centran principalmente en las consideraciones éticas y metodológicas de la investigación. Este artículo describe los aspectos éticos que deben ser tenidos en cuenta en la investigación cualitativa con niños. Es un artículo de revisión con búsqueda sistemática en bases de datos, incluyendo artículos científicos, libros y literatura gris. Asimismo, se abordan las consideraciones éticas que se encuentran implicadas desde la vinculación de los niños como participantes, hasta la obtención de la información y la socialización de los resultados. Para la investigación se seleccionó la información relevante en torno a ocho temas conforme al proceso investigativo. Con esto se evidenció que la cuestión ética constituye un aspecto central en el momento de iniciar y desarrollar cualquier estudio investigativo, por lo que está presente desde su planteamiento hasta su finalización. Pudo concluirse que el cumplimiento de los criterios de rigor metodológico, como la dependencia, credibilidad, transferibilidad y confirmación, asegura la calidad de la investigación cualitativa con niños, y esto permite la adecuada aplicación de los principios éticos de beneficencia y no maleficencia, justicia, autonomía y confidencialidad.

Differential Antioxidant Responses and Perturbed Porphyrin Biosynthesis after Exposure to Oxyfluorfen and Methyl Viologen in Oryza sativa.

Science.gov (United States)

Pham, Nhi-Thi; Kim, Jin-Gil; Jung, Sunyo

2015-07-21

We compared antioxidant responses and regulation of porphyrin metabolism in rice plants treated with oxyfluorfen (OF) or methyl viologen (MV). Plants treated with MV exhibited not only greater increases in conductivity and malondialdehyde but also a greater decline in Fv/Fm, compared to plants treated with OF. MV-treated plants had greater increases in activities of superoxide dismutase (SOD) and catalase (CAT) as well as transcript levels of SODA and CATA than OF-treated plants after 28 h of the treatments, whereas increases in ascorbate peroxidase (APX) activity and transcript levels of APXA and APXB were greater in OF-treated plants. Both OF- and MV-treated plants resulted in not only down-regulation of most genes involved in porphyrin biosynthesis but also disappearance of Mg-porphyrins during the late stage of photooxidative stress. By contrast, up-regulation of heme oxygenase 2 (HO2) is possibly part of an efficient antioxidant response to compensate photooxidative damage in both treatments. Our data show that down-regulated biosynthesis and degradation dynamics of porphyrin intermediates have important roles in photoprotection of plants from perturbed porphyrin biosynthesis and photosynthetic electron transport. This study suggests that porphyrin scavenging as well as strong antioxidative activities are required for mitigating reactive oxygen species (ROS) production under photooxidative stress caused by OF and MV.

Adaptación de la escala de empatía de Bryant, B. (1982 para niños, niñas y adolescentes en Costa Rica

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Kathia Alvarado Calderón

2011-01-01

Full Text Available Este artículo presenta la adaptación de la Escala de Empatía para niños y adolescentes (IECA de Bryant, B. en su versión al castellano en un grupo de niños y niñas de edad escolar del Cantón de Montes de Oca en San José, Costa Rica. Este instrumento es de auto-reporte y mide la respuesta empática a partir de una serie de enunciados redactados de manera neutra o donde el protagonista de la acción es de sexo femenino o masculino. Los participantes fueron 444 niños y niñas, 232 varones y 212 mujeres, con edades entre 10 y 12 años. Se utilizó el análisis estadístico de los datos para obtener criterios de confiabilidad de los resultados. Este instrumento es de alta divulgación a nivel internacional, pero no así en Costa Rica, de allí la importancia de evaluarlo con población nacional. Con este estudio se confirma que el IECA (versión castellana es un instrumento confiable en la evaluación de la respuesta empática, de importancia en el desarrollo de comportamientos prosociales, por lo que se recomienda su utilización.

(Con)fusing contours

NARCIS (Netherlands)

Lier, R.J. van; Wit, T.C.J. de; Koning, A.R.

2005-01-01

We have created patterns in which illusory Kanizsa squares are positioned on top of a background grid of bars. When the illusory contours and physical contours are misaligned, the resulting percept appears to be rather confusing (van Lier et al, 2004 Perception 33 Supplement, 77). Observers often

Porphyrin-based Photocatalytic Nanolithography

Energy Technology Data Exchange (ETDEWEB)

Bearinger, J P; Stone, G; Dugan, L C; Dasher, B E; Stockton, C; Conway, J W; Kuenzler, T; Hubbell, J A

2009-06-08

Nanoarray fabrication is a multidisciplinary endeavor encompassing materials science, chemical engineering and biology. We form nanoarrays via a new technique, porphyrin-based photocatalytic nanolithography (PCNL). The nanoarrays, with controlled features as small as 200 nm, exhibit regularly ordered patterns and may be appropriate for (a) rapid and parallel proteomic screening of immobilized biomolecules, (b) protein-protein interactions and/or (c) biophysical and molecular biology studies involving spatially dictated ligand placement. We demonstrate protein immobilization utilizing nanoarrays fabricated via PCNL on silicon substrates, where the immobilized proteins are surrounded by a non-fouling polymer background.

Conceptions about the mind-body problem and their relations to afterlife beliefs, paranormal beliefs, religiosity, and ontological confusions.

Science.gov (United States)

Riekki, Tapani; Lindeman, Marjaana; Lipsanen, Jari

2013-01-01

We examined lay people's conceptions about the relationship between mind and body and their correlates. In Study 1, a web survey (N = 850) of reflective dualistic, emergentistic, and monistic perceptions of the mind-body relationship, afterlife beliefs (i.e., common sense dualism), religiosity, paranormal beliefs, and ontological confusions about physical, biological, and psychological phenomena was conducted. In Study 2 (N = 73), we examined implicit ontological confusions and their relations to afterlife beliefs, paranormal beliefs, and religiosity. Correlation and regression analyses showed that reflective dualism, afterlife beliefs, paranormal beliefs, and religiosity were strongly and positively related and that reflective dualism and afterlife beliefs mediated the relationship between ontological confusions and religious and paranormal beliefs. The results elucidate the contention that dualism is a manifestation of universal cognitive processes related to intuitions about physical, biological, and psychological phenomena by showing that especially individuals who confuse the distinctive attributes of these phenomena tend to set the mind apart from the body.

Conceptions about the mind-body problem and their relations to afterlife beliefs, paranormal beliefs, religiosity, and ontological confusions

Science.gov (United States)

Riekki, Tapani; Lindeman, Marjaana; Lipsanen, Jari

2013-01-01

We examined lay people’s conceptions about the relationship between mind and body and their correlates. In Study 1, a web survey (N = 850) of reflective dualistic, emergentistic, and monistic perceptions of the mind-body relationship, afterlife beliefs (i.e., common sense dualism), religiosity, paranormal beliefs, and ontological confusions about physical, biological, and psychological phenomena was conducted. In Study 2 (N = 73), we examined implicit ontological confusions and their relations to afterlife beliefs, paranormal beliefs, and religiosity. Correlation and regression analyses showed that reflective dualism, afterlife beliefs, paranormal beliefs, and religiosity were strongly and positively related and that reflective dualism and afterlife beliefs mediated the relationship between ontological confusions and religious and paranormal beliefs. The results elucidate the contention that dualism is a manifestation of universal cognitive processes related to intuitions about physical, biological, and psychological phenomena by showing that especially individuals who confuse the distinctive attributes of these phenomena tend to set the mind apart from the body. PMID:25247011

Self-organization of porphyrin units induced by magnetic field during sol-gel polymerization.

Science.gov (United States)

Lerouge, Frédéric; Cerveau, Geneviève; Corriu, Robert J P; Stern, Christine; Guilard, Roger

2007-04-21

The use of a magnetic field as a controlling factor during the hydrolysis-polycondensation of porphyrin precursors substituted by Si(OR)(3) groups, induces a self-organization of porphyrin moieties due to the stacking of these units in the hybrid material and this study also confirms the effect of the magnetic field in the nano- and micrometric organization during the kinetically controlled polycondensation process.

Impact of Economic Hardship and Financial Threat on Suicide Ideation and Confusion.

Science.gov (United States)

Fiksenbaum, Lisa; Marjanovic, Zdravko; Greenglass, Esther; Garcia-Santos, Francisco

2017-07-04

The present study tested the extent to which perceived economic hardship is associated with psychological distress (suicide ideation and confusion) after controlling for personal characteristics. It also explored whether perceived financial threat (i.e., fearful anxious-uncertainty about the stability and security of one's personal financial situation) mediates the relationship between economic hardship and psychological distress outcomes. The theoretical model was tested in a sample of Canadian students (n = 211) and was validated in a community sample of employed Portuguese adults (n = 161). In both samples, the fit of the model was good. Parameter estimates indicated that greater experience of economic hardship increased with financial threat, which in turn increased with levels of suicide ideation and confusion. We discuss the practical implications of these results, such as for programs aimed at alleviating the burden of financial hardship, in our concluding remarks.

Degradación de recubrimientos ZrO2-CaO/NiAlMo por oxidación isoterma

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Utrilla, V.

2006-12-01

Full Text Available This paper analyses the degradation of a ceramic top coating 70%ZrO2 – 30%CaO deposited onto a stainless steel AISI 304 by thermal spray, using Ni-6%Al-5%Mo as overlay coating. These thermal barrier coatings were heat treated for 48, 120 and 288 h at 800 ºC to evaluate the degradation of these materials by isothermal oxidation. The microstructure evolution during oxidation was analysed by environmental scanning electron microscopy, transmission electron microscopy, X ray microanalysis and X ray diffraction. A thermally grown oxide layer was observed between the overlay coating and the ceramic top coating after oxidation. This layer was formed by a mixed Al and Ni oxides.En este trabajo se estudia la degradación de un recubrimiento 70%ZrO2 – 30%CaO crecido por proyección térmica de oxiacetileno sobre un acero inoxidable austenítico AISI 304 y empleando una leación de Ni-6%Al-5%Mo como capa de anclaje. Los recubrimientos se trataron térmicamente en aire a 800 ºC durante 48, 120 y 288 horas para evaluar la degradación de estos materiales por oxidación isotérmica. La evolución de la microestructura de las barreras como consecuencia del proceso de oxidación se analizó mediante microscopía electrónica de barrido ambiental, microscopía electrónica de transmisión, microanálisis de rayos X (EDX y difracción de rayos X. Durante la oxidación de los recubrimientos creció una capa intermedia de óxidos (“thermally grown oxides”, TGO entre el anclaje metálico y el recubrimiento cerámico formada por una mezcla de óxidos de Al y Ni.

Niğde Türk Ocağı’nın Kuruluşu ve İlk Faaliyetleri (1924-1926 The Establishment And First Activities Of Niğde Türk Ocağı (1924-1926

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Nevzat TOPAL

2013-09-01

Full Text Available “Türk Ocakları” which had been established in 1911 was re-organized after national conflict. “Niğde Türk Ocağı” was one of the establishments organized after national conflict. We evaluated the establisments and first activities of “Ocak” from the news of some newspapers we could obtain which had been published in Niğde. It was impossible to find a full collection of Niğde newspapers in libraries and archives. So, no researches were made about the activities and establishment of “Niğde Türk Ocağı”. It was possible to mark the activities and establishment of “Ocak” from the newspapers and documents that we could obtain by Mehmet Yılmaz Savaşçın who was the son of selected chairman of “Niğde Türk Ocağı” in 1925 Hasan Hüsnü (Savaşçın.According to documents and newspapers we had, “Niğde Türk Ocağı” was established at September 1924. First chairman of administrative board was C. Şehabeddin (Tüzün. There is a misbelief about this person for he can be the famous poet C. Şehabeddin. But in this study it was discovered that Şehabeddin had worked as lawyer in Niğde. The administrative board changed at the congress in January 9 1925 after Şehabettin Bey’s short (about six months regimen. Hasan Hüsnü (Savaşçın was selected as the chairman of second administrative board. According to identity certificate which was only for members of “Türk Ocakları” the first numbered member was Hüsnü Bey. Hüsnü Bey had organized and functionalized the “Ocak” in a short time. “Niğde Türk Ocağı” supported to cultural life of Niğde with its activities. The establishment and first activities of “Niğde Türk Ocağı” was evaluated for the first time by our limited documents. Fiili olarak 1911 senesinde kurulan Türk Ocakları Milli Mücadele sonrasında yeniden teşkilatlanmaya gitmiştir. Niğde Türk Ocağı Milli Mücadele sonrası kurulan teşkilatlardan birisidir. Ocağın

Situación de derechos de los niños, niñas y adolescentes trabajadores callejeros nocturnos en Medellín

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John Fernando Ramírez Villegas

2014-12-01

Full Text Available En este artículo se expone de manera general la problemática que enfrentan los niños, niñas y adolescentes —cuya sigla reconoceremos como NNA— trabajadores callejeros nocturnos de Medellín (Colombia. A partir de una investigación cualitativa con enfoque fenomenológico hermenéutico se logra observar e interpretar sus vivencias a la vez que se identifican mejor sus necesidades. La edad de los NNA a los que se les aplicó una entrevista y una guía de observación oscilaba entre los 9 y 14 años. El procesamiento de la información obtenida se realizó empleando el análisis de contenido, generando así algunas categorías desde los mismos datos. Dentro de los resultados se encontró que ellos tienen sus propias concepciones sobre la noche, el dinero, ser pobre, sus derechos, la libertad, la seguridad y la verdad, todas permeadas por una sociedad que ha sido indiferente a las necesidades de esta población, asimismo, este artículo genera una reflexión sobre el trabajo infantil en Colombia y reitera la necesidad de atender esta problemática social.

Rehabilitación temprana en niños y adolescentes con lesión medular adquirida

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G. Gabriela Hidalgo, Dra.

2014-03-01

Full Text Available La lesión medular adquirida en niños y adolescentes genera un importante impacto tanto a nivel físico como psicológico y se asocia a distintos grados de discapacidad que afecta al paciente, su familia y al entorno que los rodea. En esta población se observan algunas causas, características clínicas y complicaciones propias, distintas a las del adulto. La rehabilitación se debe iniciar en las unidades de manejo intensivo con la prevención de complicaciones, una vez estabilizado el paciente se recomienda la hospitalización en un servicio especializado de rehabilitación. Los objetivos del tratamiento se pueden plantear en forma integral utilizando la Clasificación Internacional del Funcionamiento la Discapacidad y la Salud, y varían de acuerdo a la edad, nivel de desarrollo y necesidades individuales. La intervención está a cargo de un equipo interdisciplinario y considera al niño y su familia como actores principales en el proceso de rehabilitación.

Juegos en la estimulación a la psicomotricidad en niños y niñas con necesidades educativas especiales

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Yanet Simón- Benzant

2017-11-01

Full Text Available Se presentan juegos que permiten la estimulación de la motricidad como elemento indispensable para el desarrollo del niño con necesidades educativas especiales, lo que permitirá favorecer el movimiento psicomotor con el fin de mejorar las capacidades intelectuales, afectivas y sociales permitiendo la adquisición de los nuevos aprendizajes, llevando al niño a la formación de las estructuras cognitivas de atención, memoria, percepción, lenguaje y a los niveles de pensamiento superiores que le irán permitiendo interpretar las nociones de espacialidad, temporalidad y velocidad, entre otras, al mismo tiempo que su movimiento se hace más autónomo, consciente a través de la expresión y el lenguaje.

Derechos de los niños y ciudadanía en el sistema de protección

OpenAIRE

Ramiro Vazquez, Julia; Gómez Gómez, Francisco

2014-01-01

Los derechos de participación de los niños y de las niñas y su ciudadanía se han erigido como un elemento central en los discursos y políticas para los derechos de la infancia. No obstante, con menor frecuencia se advierten dichos debates aplicados a los contextos de cuidados y protección, pese a que estos se han articulado históricamente desde la idea de ciudadanía. La presente investigación examina los derechos de participación y ciudadanía de los niños y las niñas en el marco de la prot...

Comparación del lenguaje funcional entre niños de educación especial y niños normales

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Juan José BUENO AGUILAR

2009-11-01

Full Text Available El lenguaje del niño tiene unas características específicas y singulares que lo diferencian del lenguaje adulto. En este artículo abordamos el estudio del lenguaje de los niños de dos grupos: normales y con Necesidades Educativas Especiales (N.E.E. en centros específicos, desde la perspectiva del modelo funcional. La funcionalidad lingüística es un modelo de análisis que nos permite reflexionar sobre el lenguaje, ya que estudia el lenguaje en uso partiendo de la realidad concreta del acto lingüístico centrándose en la pragmática del discurso y analizando el lenguaje cómo lo utiliza el individuo. En este modelo, la intencionalidad comunicativa es el eje que marca la esencia de los análisis de los actos de habla. La función es el principio básico de organización lingüística del significado con identidad propia. Autores como Austin (1982, Bates (1976, Clemente y Valmaseda (1985, Dale (1980, Dore (1978, Halliday (1975, 1977, 1982, 1985, Hymes (1972, Jakobson (1974, Searle (1980, Tough (1981, 1987, entre otros, abordan el análisis del lenguaje desde esta perspectiva.

Ön Isıtma Sıcaklığının Ni3Al/NiAl/NiTi Bileşiklerinden Oluşan Fonksiyonel Derecelendirilmiş Malzemenin Yapısına Etkisinin İncelenmesi

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Musa Kılıç

2015-12-01

Full Text Available Bu çalışmada, Ni3Al/NiAl/NiTi bileşiklerinden oluşan fonksiyonel derecelenmiş malzeme(FDM kendi kendine ilerleyen yüksek sıcaklık sentezlemesi (KKIYSS tekniği ile üretilmiştir. Bu üç farklı bileşiği oluşturacak tozlar hassas bir şekilde tartıldıktan sonra mekanik olarak karıştırılmış ve 200 MPa basınçla preslenmiştir. Preslenen numuneler, 200, 300 ve 400 °C ön ısıtma sıcaklıklarında yüksek voltajlı tutuşturma yöntemi (YVTY ile argon gazı atmosferinde ateşlenerek üretimi gerçekleştirilmiştir. Üretilen bu fonksiyonel derecelenmiş malzemelerin mikroyapıları optik mikroskop, Taramalı Elektron Mikroskobu (SEM ve X-Işınları Kırınım Cihazı (XRD ile incelenmiş. Sonuç olarak, KKIYSS yöntemi ile her üç ön ısıtma sıcaklığında da fonksiyonel derecelenmiş malzeme başarıyla üretilmiş ve istenen metaller arası bileşikler elde edilmiş ancak arakesitlerde daha fazla ergime ve boşluk ile birlikte ana fazlar dışında fazların da oluştuğu görülmüştür.

Interculturalidad y derecho a la educación de la niñez indígena jornalera migrante

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Lourdes Consuelo Pacheco Ladrón de Guevara

2016-01-01

Full Text Available Niños y niñas de pueblos indígenas trabajan en campos agrícolas de acuerdo con su edad y género aunque deberían estar en la escuela recibiendo educación de calidad en su propia lengua. Desde 1999, con la Modalidad Educativa Intercultural para la Población Infantil Migrante se estableció la interculturalidad como orientación educativa para la niñez indígena agrícola migrante, que se retomó posteriormente en el Programa Educación Primaria para Niñas y Niños Migrantes. En este artículo se analizan las acciones sobrea educación intercultural dirigida a esta población a partir del análisis de las acciones establecidas por parte del sector educativo.

A novel self-assembly with zinc porphyrin coordination polymer for enhanced photocurrent conversion in supramolecular solar cells

International Nuclear Information System (INIS)

Cao, Jing; Liu, Jia-Cheng; Deng, Wen-Ting; Li, Ren-Zhi; Jin, Neng-Zhi

2013-01-01

Graphical abstract: An innovative type of self-assembly based on acetohydrazide zinc porphyrin coordination polymer has been prepared in supramolecular solar cells. - Highlights: • A novel assembly with acetohydrazide porphyrin coordination polymer. • The assembly based on porphyrin is prepared as parallel sample. • Coordination polymer-based assembly shows enhanced photoelectronic behavior. • A series of different organic acid ligands as anchoring groups are prepared. - Abstract: In this work, a novel acetohydrazide zinc porphyrin-based coordination polymer (CP)-isonicotinic acid self-assembly by metal-ligand axial coordination to modify the nano-structured TiO 2 electrode surface has been investigated in photoelectrochemical device. Compared to the assembly based on corresponding zinc porphyrin combined with isonicotinic acid by metal-ligand axial coordination, CP-isonicotinic acid assembly exhibits a significantly enhanced photoelectronic behavior. In addition, a series of different organic acid ligands were prepared to probe the impact of their structures on the photoelectronic performances of their corresponding assemblies-sensitized cells. This study affords a novel type of self-assembly to functionalize the nanostructured TiO 2 electrode surface in supramolecular solar cells

Formación de un cordón litoral en Máncora-Perú, a raíz de El Niño de 1983

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1993-01-01

Full Text Available FORMATION D'UN CORDON LITTORAL A MANCORA, PEROU, APRÈS LE EL NIÑO DE 1983. On a prôné que les cordons littoraux fossiles de Colán, au nord du Pérou, pourraient s'être formés au cours d’événements très forts de phénomènes El Niño (Mega-Niño. Ce travail présente des informations sur la formation à Máncora, Pérou, d’un nouveau cordon suite à un événement extraordinaire El Niño en 1983, certainement le plus fort enregistré depuis la conquête espagnole. Cette formation est présentée comme une preuve de ce qui a été prôné pour Colán. Se ha postulado que los cordones litorales fósiles de Colán, en el norte del Perú, podrían haber sido formados durante eventos muy intensos del fenómeno El Niño (Mega-Niños. El presente trabajo documenta la formación en Máncora, Perú, de un nuevo cordón como consecuencia del evento extraordinario de El Niño de 1983, probablemente el más fuerte registrado en los últimos siglos desde la conquista española. Se presenta esta formación como evidencia de lo postulado para los cordones de Colán. ON THE FORMATION OF A NEW BEACH RIDGE IN MANCORA, PERU, AFTER EL NIÑO OF 1983. It has been postulated that the fossil discrete coastal ridges in Colán, Perú, were formed during extremely strong El Niño events of the past (Mega-Niños. This paper reports the formation of a new beach ridge in Máncora, Perú, after the extraordinary El Niño of 1983, probably the strongest El Niño registered in the last centuries, after the spanish conquest. The formation of this ridge is presented as evidence of what was postulated for the beach ridges of Colán.

Situación del derecho a la educación, en los componentes de aceptabilidad y adaptabilidad, de niñas y niños víctimas del conflicto armado, en instituciones educativas públicas de Medellín

OpenAIRE

Arias Orozco, Edgar

2010-01-01

Ubicación en Biblioteca USB Medellín (San Benito): CD-1801t Caracterizar el estado actual de garantía del derecho a la educación, en los componentes de aceptabilidad y adaptabilidad, de las niñas y niños víctimas del conflicto armado en la ciudad de Medellín, a partir de la interpretación crítica de las prácticas institucionales y de las experiencias y percepciones que tienen diferentes actores educativos del problema.

Photodynamic Efficiency of Porphyrins Encapsulated into Polysilsesquioxanes

Czech Academy of Sciences Publication Activity Database

Rychtáriková, Renata; Šabata, Stanislav; Hetflejš, Jiří; Kuncová, Gabriela

2012-01-01

Roč. 66, č. 4 (2012), s. 269-277 ISSN 0366-6352 R&D Projects: GA MŠk ME 892; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40720504 Keywords : porphyrin * immobilization * specific surface area Subject RIV: CC - Organic Chemistry Impact factor: 0.879, year: 2012

The confusion technique untangled: its theoretical rationale and preliminary classification.

Science.gov (United States)

Otani, A

1989-01-01

This article examines the historical development of Milton H. Erickson's theoretical approach to hypnosis using confusion. Review of the literature suggests that the Confusion Technique, in principle, consists of a two-stage "confusion-restructuring" process. The article also attempts to categorize several examples of confusion suggestions by seven linguistic characteristics: (1) antonyms, (2) homonyms, (3) synonyms, (4) elaboration, (5) interruption, (6) echoing, and (7) uncommon words. The Confusion Technique is an important yet little studied strategy developed by Erickson. More work is urged to investigate its nature and properties.

PORPHYRIN METABOLISM AND LIVER FUNCTION IN THE BANTU

African Journals Online (AJOL)

method for the detection of urinary coproporphyrin, Mentz5 calculated that ... defect in porphyrin metabolism which is commonly found in the Bantu could be ..... wood,61 traces of uroporphyrin may be excreted in normal urine. As much as 5 ...

An Intelligent Clustering Based Methodology for Confusable ...

African Journals Online (AJOL)

Journal of the Nigerian Association of Mathematical Physics ... The system assigns patients with severity levels in all the clusters. ... The system compares favorably with diagnosis arrived at by experienced physicians and also provides patients' level of severity in each confusable disease and the degree of confusability of ...

Differential Antioxidant Responses and Perturbed Porphyrin Biosynthesis after Exposure to Oxyfluorfen and Methyl Viologen in Oryza sativa

Directory of Open Access Journals (Sweden)

Nhi-Thi Pham

2015-07-01

Full Text Available We compared antioxidant responses and regulation of porphyrin metabolism in rice plants treated with oxyfluorfen (OF or methyl viologen (MV. Plants treated with MV exhibited not only greater increases in conductivity and malondialdehyde but also a greater decline in Fv/Fm, compared to plants treated with OF. MV-treated plants had greater increases in activities of superoxide dismutase (SOD and catalase (CAT as well as transcript levels of SODA and CATA than OF-treated plants after 28 h of the treatments, whereas increases in ascorbate peroxidase (APX activity and transcript levels of APXA and APXB were greater in OF-treated plants. Both OF- and MV-treated plants resulted in not only down-regulation of most genes involved in porphyrin biosynthesis but also disappearance of Mg-porphyrins during the late stage of photooxidative stress. By contrast, up-regulation of heme oxygenase 2 (HO2 is possibly part of an efficient antioxidant response to compensate photooxidative damage in both treatments. Our data show that down-regulated biosynthesis and degradation dynamics of porphyrin intermediates have important roles in photoprotection of plants from perturbed porphyrin biosynthesis and photosynthetic electron transport. This study suggests that porphyrin scavenging as well as strong antioxidative activities are required for mitigating reactive oxygen species (ROS production under photooxidative stress caused by OF and MV.

Isolation of an oxomanganese(V) porphyrin intermediate in the reaction of a manganese(III) porphyrin complex and H2O2 in aqueous solution.

Science.gov (United States)

Nam, Wonwoo; Kim, Inwoo; Lim, Mi Hee; Choi, Hye Jin; Lee, Je Seung; Jang, Ho G

2002-05-03

The reaction of [Mn(TF(4)TMAP)](CF(3)SO(3))(5) (TF(4)TMAP=meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl)porphinato dianion) with H(2)O(2) (2 equiv) at pH 10.5 and 0 degrees C yielded an oxomanganese(V) porphyrin complex 1 in aqueous solution, whereas an oxomanganese(IV) porphyrin complex 2 was generated in the reactions of tert-alkyl hydroperoxides such as tert-butyl hydroperoxide and 2-methyl-1-phenyl-2-propyl hydroperoxide. Complex 1 was capable of epoxidizing olefins and exchanging its oxygen with H(2) (18)O, whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF(4)TMAP)](5+) with various oxidants in the pH range 3-11, the O-O bond cleavage of hydroperoxides was found to be sensitive to the hydroperoxide substituent and the pH of the reaction solution. Whereas the O-O bond of hydroperoxides containing an electron-donating tert-alkyl group is cleaved homolytically, an electron-withdrawing substituent such as an acyl group in m-chloroperoxybenzoic acid (m-CPBA) facilitates O-O bond heterolysis. The mechanism of the O-O bond cleavage of H(2)O(2) depends on the pH of the reaction solution: O-O bond homolysis prevails at low pH and O-O bond heterolysis becomes a predominant pathway at high pH. The effect of pH on (18)O incorporation from H(2) (18)O into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF(4)TMAP)](5+) and KHSO(5) in buffered H(2) (18)O solutions. A high proportion of (18)O was incorporated into the CBZ-10,11-oxide product at all pH values but this proportion was not affected significantly by the pH of the reaction solution.

Trastorno obsesivo compulsivo en niños y adolescentes: una actualización. Primera parte

OpenAIRE

Vargas Álvarez, Luis Alberto; Palacios Cruz, Lino; González Thompson, Guillermo; de la Peña Olvera, Francisco

2008-01-01

El trastorno obsesivo compulsivo se ha reportado en los últimos tiempos con mayor prevalencia en la edad pediátrica que lo reportado anteriormente, esto se debe probablemente a una mejor caracterización de su presentación en niños y adolescentes y al desarrollo de mejores métodos de evaluación. Los criterios diagnósticos son los mismos para niños, adolescentes y adultos. Debido a su bajo nivel de conciencia, los niños pueden no considerar sus obsesiones como exageradas o ilógicas por lo que e...

One-step synthesis of N-doped activated carbon with controllable Ni nanorods for ethanol oxidation

International Nuclear Information System (INIS)

Shi, Wenjuan; Gao, Haiyan; Yu, Jianguo; Jia, Miaomiao; Dai, Tangming; Zhao, Yongnan; Xu, Jingjing; Li, Guodong

2016-01-01

N-doped activated carbons with controllable Ni nanorods (NiNC) catalysts were fabricated by a facile one-pot method for electrocatalytic oxidation of ethanol. The effects of carbon source and Ni precursor for the different microstructures of the forming Ni are discussed in this work. The sucrose and chloride ion are the key factors for forming nanorod-like nickel catalyst. The sizes of Ni nanorods can be controlled by the reactant ratios and influence the catalytic performance for ethanol oxidation. The doped N atoms are also used to improve the catalytic performance for ethanol oxidation. The NiNC–3 catalyst with the proper content and size of Ni exhibits an improved catalytic activity toward ethanol oxidation with a 5 times current density and 16 times rate constant in comparison with the NiNC–1 catalysts. A current density of 47.5 mA cm −2 is generated on NiNC–3 electrode. Furthermore, current density retention of 80.7% suggests an excellent cyclic stability after 1500 cycle on the NiNC–3 electrode. All of these elevated performances can be attributed to the relatively uniform nanorods size, as well as the excellent electrical conductivity and stability of the carbon support.

Humillación y justicia en niños en condiciones de pobreza

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Gottfried SCHWEIGER

2015-02-01

Full Text Available Los niños merecen muchas cosas diferentes en términos de justicia. En este trabajo argumentaremos que una de las cosas que requieren son relaciones positivas (confianza en ellos mismos, autorrespeto y autoestima y también defenderemos que lo anterior implica que no deben ser humillados. Esto nos permitirá rechazar la pobreza como injusta y concluir que debería ser disminuida. Esta tesis será defendida en tres pasos diferentes: presentaremos y examinaremos tres tipos de relaciones positivas con uno mismo (autoconfianza, autorrespeto y autoestima; (2 continuaremos examinando el concepto de humillación y argumentando que los actos de humillación son injustos incluso cuando las víctimas no los experimenten como humillantes; (3 por último, propondremos cinco argumentos a favor de que vivir en la pobreza es una forma de humillación para los niños. Los cinco argumentos que defenderé en la última sección son: (a la pobreza se conecta con otras formas de injusticia; (b es inmerecida y arbitraria para los niños afectados, que no pueden considerarse en ningún caso responsables de la misma; (c la pobreza está extendida entre la infancia; (d la pobreza se les impone a los niños por ser miembros de un grupo social más amplio; (e la pobreza es una humillación duradera y no un incidente ocasional.

First Example of a Lipophilic Porphyrin-Cardanol Hybrid Embedded in a Cardanol-Based Micellar Nanodispersion

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Giuseppe Vasapollo

2012-10-01

Full Text Available Cardanol is a natural and renewable organic raw material obtained as the major chemical component by vacuum distillation of cashew nut shell liquid. In this work a new sustainable procedure for producing cardanol-based micellar nanodispersions having an embedded lipophilic porphyrin itself peripherally functionalized with cardanol substituents (porphyrin-cardanol hybrid has been described for the first time. In particular, cardanol acts as the solvent of the cardanol hybrid porphyrin and cholesterol as well as being the main component of the nanodispersions. In this way a “green” micellar nanodispersion, in which a high percentage of the micellar system is derived from renewable “functional” molecules, has been produced.

Una mirada a la situación de la niñez en el Valle del Cauca

OpenAIRE

Ana María Osorio; Luis Fernando Aguado

2010-01-01

En este documento identificamos un conjunto de indicadores a nivel departamental y municipal (en la medida en que la información lo permite) con perspectiva de niñez, indicadores que facilitan analizar el bienestar y cumplimiento de los derechos de los niños y niñas en distintas áreas: salud, educación, alimentación, vivienda digna, y la exposición a riesgos tempranos como el trabajo y la maternidad. La construcción de indicadores a nivel municipal que reflejan el bienestar y/o el...

Tratamiento de la onicofagia en niños. Revisión sistemática

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Claudia Cecilia Restrepo Serna

2011-01-01

Full Text Available Objetivo: Realizar una revisión sistemática para evaluar y analizar la evidencia científica disponible en terapias para la onicofagia en niños. Materiales y métodos: La literature se analizó a partir de Medline, Pubmed, ovid, EBSCO, ISI, Cochrane Library, Lylacs, Scielo, Scirus and the Internet, published from March 1985 to 2008. Se analizaron estudios de intervención o comparativos, ensayo clínico, metanálisis o estudio multicéntrico que incluyeran todas las terapias disponibles para resolver la Onicofagia en niños y niñas. Los niños y niñas incluidos en los estudios, debían presentar ausencia de otro tipo de hábitos y/o alteraciones neurológicas. Los estudios incluídos requerían haber hecho un diagnóstico inicial de Onicofagia a través de anamnesis y de ayudas diagnósticas. Resultados: De los 92 estudios revisados, uno cumplió los criterios de calidad. Los estudios seleccionados soportan las técnicas psicológicas para el tratamiento de la Onicofagia, más no el uso de aparatos intraorales o farmacoterapia en niños y niñas. Conclusión: Muy pocos estudios acerca de la terapia para la Onicofagia cumplen los criterios de calidad requeridos para la práctica basada en la evidencia. Aunque el estudio seleccionado cumplió con los criterios de calidad, no es suficiente para afirmar que existe adecuada evidencia para el tratamiento de la Onicofagia en niños y niñas, por lo que se requieren futuros estudios que comparen los diferentes tipos de terapia.

Análisis exploratorio de la percepción en niños preescolares sobre la interacción recíproca con sus madres

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Pedro Solís-Cámara R.

2014-01-01

Full Text Available Aunque los avances conceptuales y las evidencias empíricas con niños en edad escolar y adolescentes sugieren que las percepciones de los niños son relevantes para comprender las interacciones recíprocas padres - hijos, el estado de conocimiento es prácticamente nulo en niños preescolares. El principal objetivo de este estudio buscó explorar la percepción de niños preescolares sobre las relaciones con sus madres y analizar si los puntajes diferenciales de la percepción de los niños indican diferencias en la competencia parental, así como en otros factores que tienen relación con su crianza. Método. La muestra estuvo conformada por 50 mamás que contestaron los autorreportes y sus niños (n = 50 que contestaron una prueba pictórica de percepción de las relaciones con sus madres. Resultados. Los resultados indicaron que las percepciones de los niños sobre las interacciones adecuadas o inadecuadas fueron congruentes con los puntajes de los cuestionarios, en particular, con la competencia parental, el estrés y el bienestar subjetivo maternos y con la adaptación psicosocial, el estrés y los problemas de comportamiento de los niños, así como con el temperamento de ambos. Conclusión. Se discuten los resultados y sus implicaciones para establecer congruencia entre el avance conceptual y las evidencias empíricas sobre las interacciones recíprocas.

Excitation energy transfer in ruthenium (II)-porphyrin conjugates led to enhanced emission quantum yield and {sup 1}O{sub 2} generation

Energy Technology Data Exchange (ETDEWEB)

Pan, Jie; Jiang, Lijun; Chan, Chi-Fai [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Tsoi, Tik-Hung [Department of Applied Biology and Chemical Technology, Hung Hom, Hong Kong Special Administrative Region (Hong Kong); Shiu, Kwok-Keung; Kwong, Daniel W.J. [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Wong, Wing-Tak [Department of Applied Biology and Chemical Technology, Hung Hom, Hong Kong Special Administrative Region (Hong Kong); Wong, Wai-Kwok, E-mail: wkwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong); Wong, Ka-Leung, E-mail: klwong@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong Special Administrative Region (Hong Kong)

2017-04-15

Porphyrins are good photodynamic therapy (PDT) agents due to its flexibility for modifications to achieve tumor localization and photo-cytotoxicity against cancer. Yet they are not perfect. In a Ru(polypyridyl)-porphyrin system, the Ru(polypyridyl) moiety improves the water solubility and cell permeability. Consider the similar excited state energies between Ru(polypyridyl) and porphyrin moieties; a small perturbation (e.g. Zn(II) metalation) would lead to a marked change in the energy migration process. In this work, we have synthesized a series of porphyrins conjugated with Ru(polypyridyl) complexes using different linkers and investigated their photophysical properties, which included singlet oxygen quantum yield and their in vitro biological properties, resulting from linker variation and porphyrin modification by Zn(II) metalation. - Graphical abstract: Four amphiphilic ruthenium(II)-porphyrin complexes were prepared that display energy transfer conversion with zinc coordination, lysosome specific target, low dark toxicity and efficient photodynamic therapy.

XAFS Debye-Waller Factors Temperature-Dependent Expressions for Fe+2-Porphyrin Complexes

Science.gov (United States)

Dimakis, Nicholas; Bunker, Grant

2007-02-01

We present an efficient and accurate method for directly calculating single and multiple scattering X-ray absorption fine structure (XAFS) thermal Debye-Waller factors for Fe+2 -porphiryn complexes. The number of multiple scattering Debye-Waller factors on metal porphyrin centers exceeds the number of available parameters that XAFS experimental data can support during fitting with simulated spectra. Using the Density Functional Theory (DFT) under the hybrid functional of X3LYP, phonon normal mode spectrum properties are used to express the mean square variation of the half-scattering path length for a Fe+2 -porphiryn complex as a function of temperature for the most important single and multiple scattering paths of the complex thus virtually eliminating them from the fitting procedure. Modeled calculations are compared with corresponding values obtained from DFT-built and optimized Fe+2 -porphyrin bis-histidine structure as well as from experimental XAFS spectra previously reported. An excellent agreement between calculated and reference Debye-Waller factors for Fe+2-porphyrins is obtained.

XAFS Debye-Waller Factors Temperature-Dependent Expressions for Fe+2-Porphyrin Complexes

International Nuclear Information System (INIS)

Dimakis, Nicholas; Bunker, Grant

2007-01-01

We present an efficient and accurate method for directly calculating single and multiple scattering X-ray absorption fine structure (XAFS) thermal Debye-Waller factors for Fe+2 -porphiryn complexes. The number of multiple scattering Debye-Waller factors on metal porphyrin centers exceeds the number of available parameters that XAFS experimental data can support during fitting with simulated spectra. Using the Density Functional Theory (DFT) under the hybrid functional of X3LYP, phonon normal mode spectrum properties are used to express the mean square variation of the half-scattering path length for a Fe+2 -porphiryn complex as a function of temperature for the most important single and multiple scattering paths of the complex thus virtually eliminating them from the fitting procedure. Modeled calculations are compared with corresponding values obtained from DFT-built and optimized Fe+2 -porphyrin bis-histidine structure as well as from experimental XAFS spectra previously reported. An excellent agreement between calculated and reference Debye-Waller factors for Fe+2-porphyrins is obtained

Studies of alkyl porphyrin distributions in organic-rich sediments using LC-MS

International Nuclear Information System (INIS)

Eckardt, C.B.; Carter, J.F.; Keely, B.J.; Maxwell, J.R.; Kilpatrick, G.

1992-01-01

In recent years, structure elucidation of a wide variety of sedimentary tetrapyrroles has provided clear molecular evidence for the presence of primary photosynthetic communities in palaeo water columns. The reported structures indicate an origin from algal chlorophylls c for certain components, while an origin from photosynthetic bacteria is apparent from the carbon skeletons of other components. In particular, the structures of ≤C 34 porphyrin carboxylic acids in the Eocene Messel shale indicate an origin from Chloroblum bacteria. Since such bacteria are strict anaerobes, the presence of these species is evidence for anoxic conditions extending into the photic zone of Messel lake. By analogy, the presence in the more widely-occurring alkyl porphyrin distributions of components >C 33 would also suggest a Chlorobium chlorophyll origin. Hence, in this paper, the authors studied by LC-MS, the distributions of alkyl porphyrins in selected sediments and searched for the presence of such components, in order to determine photic zone anoxia in the respective palaeo environments

To what extent can charge localization influence electron injection efficiency at graphene-porphyrin interfaces?

KAUST Repository

Parida, Manas R.

2015-04-28

Controlling the electron transfer process at donor- acceptor interfaces is a research direction that has not yet seen much progress. Here, with careful control of the charge localization on the porphyrin macrocycle using β -Cyclodextrin as an external cage, we are able to improve the electron injection efficiency from cationic porphyrin to graphene carboxylate by 120% . The detailed reaction mechanism is also discussed.

La comprensión verbal y la lectura en niños con y sin retraso lector

Directory of Open Access Journals (Sweden)

Luisa Fernanda Bohórquez Montoya

2014-01-01

Full Text Available Describir diferencias entre el desempeño en tareas de lectura y de comprensión verbal en niños con y sin retraso lector, así como la relación entre ambos tipos de desempeños. Método. Se utilizaron tareas de lectura de la Evaluación neuropsicológica infantil (ENI y el Índice de Comprensión Verbal (ICV de la escala de inteligencia Wechsler (WISC-IV para niños. Los participantes fueron 40 niños de ambos sexos, entre 7 y 9 años de edad, quienes cursaban entre 2° y 4° grado de primaria en un colegio de estrato socioeconómico bajo de la ciudad de Cali, con un coeficiente intelectual (CI promedio de 86. Los participantes fueron divididos en dos grupos, 20 niños que presentaban retraso lector y 20 niños con un desarrollo lector típico, según los puntajes obtenidos en las tareas de lectura de la ENI. Resultados. Se encontraron diferencias en el rendimiento de ambos grupos de niños evaluados, así como una correlación significativa entre el ICV y el subdominio de comprensión de la ENI. Conclusión. Estos resultados son acordes con la hipótesis de que el desarrollo del lenguaje oral es uno de los principales facilitadores en la adquisición del aprendizaje de la lectura, puesto que en la medida en que el niño comprende la semántica oral, estará con mejor preparación para dotar de significado lo leído.

Detection of a weak ring current in a nonaromatic porphyrin nanoring using magnetic circular dichroism.

Science.gov (United States)

Kowalska, Patrycja; Peeks, Martin D; Roliński, Tomasz; Anderson, Harry L; Waluk, Jacek

2017-12-13

We compare the absorption and magnetic circular dichroism (MCD) spectra of a series of porphyrin oligomers - dimer, tetramer, and hexamer - bound in a linear or cyclic fashion. The MCD signal is extremely weak for low energy transitions in the linear oligomers, but it is amplified when the cyclic porphyrin hexamer binds a template, restricting rotational freedom. The appearance of Faraday A terms in the MCD spectra demonstrates the presence of a magnetic moment, and thus, uncompensated electronic current. The value of the excited state magnetic moment estimated from the A term is very low compared with those of monomeric porphyrins, which confirms the nonaromatic character of the cyclic array and the lack of a global ring current in the ground state of the neutral nanoring. DFT calculations predict the absorption and MCD patterns reasonably well, but fail to reproduce the MCD sign inversion observed in substituted monomeric zinc porphyrins ("soft" chromophores). Interestingly, a correct sign pattern is predicted by INDO/S calculations. Analysis of the MCD spectra of the monomeric porphyrin unit allowed us to distinguish between two close-lying lowest energy transitions, which some previous assignments placed further apart. The present results prove the usefulness of MCD not only for deconvolution and assignment of electronic transitions, but also as a sensitive tool for detecting electronic ring currents.

Assembly of individual TiO2-C60/porphyrin hybrid nanoparticles for enhancement of photoconversion efficiency

International Nuclear Information System (INIS)

Jang, Jae Kwon; Park, Se Ho; Song, Hyunjoon; Park, Joon T; Kim, Chulwoo; Ko, Jaejung; Seo, Won Seok

2011-01-01

Rational organization of porphyrin and C 60 on the electrode surface in photovoltaic structures is essential to yield high quantum efficiency. In the present work, individual TiO 2 nanoparticles were modified by introducing C 60 and porphyrin units on the surface, and then electrophoretically deposited on an ITO/SnO 2 electrode. The morphology of the photoactive layer on the electrode was significantly different from that of the layer produced as a result of separate deposition of C 60 and porphyrin. The maximum incident photon to current efficiency of the resulting electrode approached 88% at 410 nm, which is the highest value among molecule-based photovoltaic cells reported to date. This indicates that molecular assembly of the C 60 and porphyrin units on the individual nanoparticles through strong chemical attachment is a key factor in improving effective electron transfer between the photoactive units and the electrodes.

Niñas y niños involucrados en procesos de sustracción familiar en México

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Edith Carrillo

2011-01-01

Full Text Available Mi propósito central en este artículo es aportar elementos para la reflexión respecto a la situación que enfrentan las niñas y los niños que se ven involucrados en procesos de sustracción familiar, es decir, en contextos de conflicto por su custodia. Para ello, analicé la configuración de la sustracción familiar a partir de las narrativas de los progenitores y progenitoras, y de los funcionarios y funcionarias de la administración pública, ubicadas en las instancias que tienen injerencia en esta problemática. Con este artículo busco enfatizar que, si bien los hijos e hijas o nietos y nietas son el supuesto centro de esta disputa, son en realidad los sujetos menos tomados en cuenta en esta situación, ya que lo que se pone en juego y lo que determina este conflicto no es su bienestar o "interés superior", sino el establecimiento del orden de género y de las relaciones de poder en los ámbitos públicos y privados.

Conductas alimentarias y su relación con el desarrollo psicomotor y conductual en los niños y niñas de 1 a 3 años, de los Centros Infantiles del Buen Vivir urbanos, del Cantón Cuenca

OpenAIRE

Gutiérrez Campoverde, Dora Cecilia

2014-01-01

En condiciones sociales, familiares y biológicas apropiadas, se espera que el desarrollo psicomotor, la conducta y la conducta alimentaria de los niños y niñas sean adecuadas dentro de la diversidad e individualidad. Esta investigación transversal realizada en niños y niñas de 1 a 3 años de los Centros Infantiles del Buen Vivir urbanos del Cantón Cuenca (N=627/n=360) que evaluó la conducta alimentaria con el cuestionario corto para el Nivel I de Atención Primaria, el desarrollo psicomotor con...

Emulating porphyrins with a rippled multivacancy graphene system

Science.gov (United States)

Mombrú, Dominique; Faccio, Ricardo; Mombrú, Alvaro W.

2018-04-01

The interaction between a complex porphyrin-like system formed by an iron atom and multivacant graphene layer and O2, CO and CO2 molecules is studied, using Density Functional Theory (DFT) calculations. The multivacancy graphene system used for this study, consists in the removal of a 1,4-dimethybenzene-like moiety, in a 6 × 6 supercell. This removal and the structural optimization subsequently performed, yield to a biaxial vacancy, where the location of an iron atom embedded in it, lead to a system with resemblance to iron-porphyrin systems. This similar structure could be used to form complexes where gas molecules are allowed to interact with these iron-octavacant graphene systems. The study focuses on the structure of the system and the net magnetic moment for different gas molecules: O2, CO2 and CO. Rippling in the vacant graphene is enhanced through this interaction.

La desintegración familiar: impacto en el desarrollo emocional de los niños

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Sonia María Castillo Costa

2018-03-01

Full Text Available El presente artículo pretende generar espacios de reflexión en torno a la desintegración familiar y el impacto en el desarrollo emocional de los niños, tiene como  objetivo mejorar la relación y la comunicación padre-hijos/as, los más afectados son los niños al desintegrarse el hogar por diferentes factores, cuando el comportamiento de los niños/as se ve alterado al no existir una orientación que ayude a normalizar el problema. La desintegración familiar provoca problemas psicológicos de orden emocional y afectivo, que afectan su desempeño escolar: baja autoestima, repiten grados académicos, bajo rendimiento, deserción escolar, alteraciones de la conducta social, problemas de aprendizaje y se afecta las relaciones interpersonales dentro y fuera del aula de clase; sin embargo, en estos casos hay riesgos emocionales, no se respetan los derechos de la niñez. Los cambios emocionales de los niños, es síntoma de que algo sucede anormal, porque reflejan a través de actitudes y sentimientos. Concluyéndose que las causas de la desorganización familiar es por prevalecer adicciones por uno de sus padres, por la pobreza extrema y violencia familiar; y, existe una alta coincidencia entre las causas que originan la agresividad y las manifestaciones conductuales, observándose comportamiento impulsivo, baja autoestima y agresividad.

La construcción simbólica y cultural de los programas infantiles en los niños y niñas de edad escolar

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José Chica Pincay

2016-06-01

Full Text Available Este artículo presenta el resultado de un análisis narrativo icónico en dos establecimientos educativos de la ciudad de Guayaquil con la finalidad de reconocer cómo se construyen los imaginarios sociales desde una temprana edad. Mediante una encuesta aplicada a 228 niños y niñas, de 5 a 8 años de edad, pertenecientes a la escuela TEPEYAC del movimiento Fe y Alegría, y la escuela fiscal Catalina Miranda. Los resultados obtenidos adquieren un marco referencial propio para una interpretación en el contexto sociocultural mediático que hasta incluso vincula el efecto psicosocial de los niños y niñas. En consecuencia, 10 simbólico televisivo reduce la visión cultural nuestra, es decir la enajenación de los programas infantiles conquista el mundo infantil, a pesar que en la actualidad hay una tendencia pionera e inteligible de la televisión pública por alcanzar políticas de comunicación nacional a través de programas especiales que integre al público infantil, no obstante este publico opta por un modelo de programa infantil ajeno a nuestro contexto nacional. Evidentemente los significados culturales mediáticos revisten de un poder simbólico capaz de dirigir las acciones sociales de los niños y niñas de edad escolar.

Hipertensión pulmonar a moderada altura en niños

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Gabriel F. Díaz, MD

2012-07-01

Full Text Available Se reporta la carencia de estudios sobre la relación entre hipertensión pulmonar y altura en niños y, con base en la fisiología de esta última, se hace énfasis en la importancia de la hipoxia hipobárica, que desempeña un papel determinante en la etio y biopatogénesis de la hipertensión pulmonar del habitante de la altura. En cuanto a la biopatogénesis, se señala la importancia de la hiperreactividad del lecho vascular pulmonar y su correcta evaluación. De igual forma, se resumen las patologías relacionadas con hipertensión pulmonar en el niño habitante de la altura y, finalmente, en lo que respecta al tratamiento de la hipertensión pulmonar del habitante de la altura, se resalta, a través de la evolución de casos clínicos, la importancia de vivir a baja altura sobre el nivel del mar.

La comunicación expresiva en niños con multidiscapacidad sin lenguaje verbal

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María Alejandra GRAZONA

2011-04-01

Full Text Available La investigación estuvo centrada en niños con multidiscapacidad que se comunican a través de canales no visuales y no verbales. A partir de la pregunta central respecto a: ¿Cómo dan a conocer el contenido de sus mensajes los niños con multidiscapacidad que no poseen lenguaje verbal?, implementamos un estudio con dos fases complementarias y de convergencia metodológica. La primera, amparada en el paradigma positivista, en la que realizamos un acercamiento objetivo a la realidad y por medio de la operacionalización de los conceptos teóricos. en la segunda fase, profundizamos a través de la Metodología de estudio de Caso (9 en total y con un anclaje en el paradigma fenomenológico-interpretativo. El objetivo perseguido fue: Conocer las formas comunicativas de niños con multidiscapacidad sin lenguaje verbal, por ello privilegiamos el análisis en profundidad a partir de la utilización de diferentes técnicas que permitieron el acercamiento a los niños en ambientes naturales y triangular la información para proporcionar fiabilidad y validez. Las mencionadas etapas permitieron obtener un conocimiento holístico de las formas comunicativas idiosincráticas utilizadas por los niños con multidiscapacidad, que, a modo de bisagra, constituyen su fenotipo comunicativo.

Situación de salud y nutrición de niños indígenas y niños no indígenas de la Amazonia peruana

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