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1.
J Nanosci Nanotechnol ; 14(7): 5309-12, 2014 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-24758023

RESUMEN

To fabricate the platinum (Pt) counter electrode in dye-sensitized solar cells (DSSCs), rapid and low sintering process was carried out using nanosecond pulsed laser sintering (LS) method based on third harmonic (355 nm) of an Nd:YAG laser at room temperature. The surface morphology of LS-Pt on fluorine-doped tin oxide (FTO) electrode showed thin and compact structure, consisting of particles size of - 10-30 nm and thickness of below 30 nm. The DSSCs with the LS-Pt/FTO counter electrodes displayed the power conversion efficiency of 4.4% with short-circuit current = 9.07 mA/cm2, open-circuit voltage = 0.79 V and fill factor = 61.3.

2.
J Oral Maxillofac Surg ; 72(6): 1093.e1-11, 2014 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-24709514

RESUMEN

PURPOSE: Distant migration associated with sinus lifting procedures has not been investigated. In the present study, a case of distant migration of graft material was observed, and the potential mechanisms of migration were analyzed using material analysis and in vivo experiments. MATERIALS AND METHODS: The migrated graft material was biphasic calcium phosphate-based alloplastic material (BCP), and its physical properties were compared with those of xenogenic material (Bio-Oss). The comparisons of the physical properties were performed using scanning electronic microscopic, x-ray diffraction, and Fourier-transform infrared absorbance spectra analysis. The comparative graft migration study was performed using the subcutaneous pocket model in rats (n = 10). The clinical case was analyzed by histologic section and energy dispersive x-ray (EDX) microanalysis. RESULTS: The observed diffraction patterns from the Bio-Oss revealed characteristic diffractions for the hydroxyapatite phase, and those from the BCP revealed additional diffractions that could be assigned to the tricalcium phosphate phase. In the animal model, the graft migration distances observed in the BCP group were significantly greater than those observed in the Bio-Oss group (P = .012). In the clinical case, the lymphatic vessels of the submandibular gland contained foreign materials that were morphologically similar to those of the maxillary sinus. EDX microanalysis revealed that the particles in the lymphatic vessels exhibited calcium concentrations that were approximately 200 times greater than those in the adjacent glandular tissue. CONCLUSIONS: In the present study, BCP-based sinus grafts had migrated into the submandibular glandular area by way of the lymphatic chain in the presented clinical case.


Asunto(s)
Sustitutos de Huesos/efectos adversos , Migración de Cuerpo Extraño/etiología , Elevación del Piso del Seno Maxilar/efectos adversos , Animales , Fenómenos Químicos , Tejido Conectivo/patología , Modelos Animales de Enfermedad , Microanálisis por Sonda Electrónica , Cuerpos Extraños/patología , Tejido de Granulación/patología , Humanos , Hidroxiapatitas/efectos adversos , Hidroxiapatitas/química , Linfadenitis/etiología , Vasos Linfáticos/patología , Masculino , Microscopía Electrónica de Rastreo , Persona de Mediana Edad , Minerales/efectos adversos , Minerales/química , Tamaño de la Partícula , Ratas , Espectroscopía Infrarroja por Transformada de Fourier , Infecciones Estafilocócicas/microbiología , Tejido Subcutáneo/microbiología , Tejido Subcutáneo/cirugía , Glándula Submandibular/patología , Difracción de Rayos X
3.
J Oral Maxillofac Surg ; 72(1): 53-60, 2014 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-24331565

RESUMEN

PURPOSE: The objective of this study was to compare peri-implant bone formation among uncoated (UC), hydroxyapatite (HA), collagen plus HA (CH), and collagen, HA, plus bone morphogenetic protein-2 (BMP-2) implant groups. MATERIALS AND METHODS: Implants in the UC group had acid-etched surfaces. The surface coating was applied using the aerosol deposition method. The coated surfaces were examined by scanning electron microscopy, x-ray diffraction (XRD), and Fourier-transformed infrared absorption analysis. Subsequently, 6 implants from each group (total, 24 implants) were installed in the tibias of rabbits. The animals were sacrificed at 6 weeks after implant installation. Peri-implant bone formation and bone-to-implant contact (BIC) were measured in histologic sections. Significant differences among groups were evaluated using analysis of variance. RESULTS: Based on the measured XRD patterns, there was a characteristic HA phase (International Centre for Diffraction Data [ICDD], 086-0740) coated on the titanium (ICDD, 089-3725). Subsequent coating processes for collagen and BMP-2 did not display additional diffraction peaks, but maintained the diffraction patterns of the HA-coated titanium. The presence of collagen was verified by infrared absorption analysis. When comparing these modifications with UC surfaces, only the CH coating displayed significantly greater peri-implant bone formation and BIC (P = .003 and P < .001, respectively). Adding BMP-2 to the implant surface did not produce any advantage compared with the CH coating. CONCLUSIONS: In this study, the CH group displayed significantly greater new bone formation and BIC than the other groups. There was no significant difference among the other groups.


Asunto(s)
Proteína Morfogenética Ósea 2/química , Materiales Biocompatibles Revestidos/química , Colágeno Tipo I/química , Implantes Dentales , Diseño de Prótesis Dental , Durapatita/química , Osteogénesis/fisiología , Grabado Ácido Dental/métodos , Aerosoles , Animales , Materiales Dentales/química , Ensayo de Materiales , Microscopía Electrónica de Rastreo , Oseointegración/fisiología , Conejos , Espectroscopía Infrarroja por Transformada de Fourier , Propiedades de Superficie , Tibia/patología , Tibia/cirugía , Titanio/química , Difracción de Rayos X
4.
Phys Chem Chem Phys ; 12(27): 7648-53, 2010 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-20523949

RESUMEN

Aromatic pi-pi interaction in the presence of a metal atom has been investigated experimentally and theoretically with the model system of bis(eta(6)-benzene)chromium-benzene cluster (Cr(Bz)(2)-Bz) in which a free solvating benzene is non-covalently attached to the benzene moiety of Cr(Bz)(2). One-photon mass-analyzed threshold ionization (MATI) spectroscopy and first principles calculations are employed to identify the structure of Cr(Bz)(2)-Bz which adopts the parallel-displaced configuration. The decrease in ionization potential for Cr(Bz)(2)-Bz compared with Cr(Bz)(2), resulting from the increase of the cation-pi stabilization energy upon ionization, is consistent with the parallel-displaced structure of the cluster. Theoretical calculations give the detailed cluster structures with associated energetics, thus revealing the nature of pi-pi-metal or pi-pi-cation interactions at the molecular level.


Asunto(s)
Benceno/química , Cromo/química , Metales/química , Compuestos Organometálicos/química , Algoritmos , Cationes/química , Modelos Químicos , Solventes/química , Análisis Espectral
5.
J Chem Phys ; 132(12): 124304, 2010 Mar 28.
Artículo en Inglés | MEDLINE | ID: mdl-20370120

RESUMEN

The A (2)A(1)<--X (2)B(1) transitions of H(2)S(+) above the barrier to linearity have been investigated with the energy resolution high enough to identify individual rotational transition lines for the first time. The rotational cooling of the cation is achieved either by the direct ionization or mass-analyzed threshold ionization (MATI) technique employed in the vacuum-ultraviolet laser excitation of the jet-cooled H(2)S. Subsequent photoexcitation leads to the H(2)S(+)-->H(2)+S(+) dissociation and the S(+) product yield taken as a function of the excitation energy gives the photofragment excitation (PHOFEX) spectra. The combined use of MATI and PHOFEX techniques greatly simplifies the spectrum allowing the accurate identification of the rotationally resolved bands which is otherwise a formidable task due to the intrinsic complexity of the A (2)A(1)<--X (2)B(1) transition. Highly excited states of A(0,7,0), A(0,8,0), and A(0,9,0) vibronic levels with different K quantum numbers which are located above the barrier to linearity are thoroughly investigated. The bent-to-quasilinear transition of H(2)S(+) above the barrier to linearity shows the characteristics of the Renner-Teller effect, showing the large A rotational constant and strong intensity borrowing of the highly vibrationally excited ground levels such as X(0,23,0) or X(0,24,0) in the dipole-allowed excitation. Spectroscopic parameters of term values, rotational, and spin-orbit coupling constants are precisely determined in this work, providing the most quantitative spectroscopic structure of the H(2)S(+) to date. Quantum-state dependent photodissociation dynamics are also discussed from spectral features of PHOFEX.

6.
J Phys Chem A ; 112(31): 7191-9, 2008 Aug 07.
Artículo en Inglés | MEDLINE | ID: mdl-18636705

RESUMEN

Conformational isomers of alkanethiols are isolated in the molecular beam, and the conformer-specific ionization dynamics have been investigated using vacuum ultraviolet mass-analyzed threshold ionization (MATI) spectroscopy. Only a single conformer of ethanethiol is observed to give the adiabatic ionization potential (IP) of 9.2922 +/- 0.0007 eV for the gauche conformer. For isopropanethiol, IP is found to be 9.1426 +/- 0.0006 for the trans conformer and 9.1559 +/- 0.0006 eV for the gauche conformer. Only two major conformational isomers are identified for 1-propanethiol, giving an IP of 9.1952 +/- 0.0006 for the trans-gauche conformer and 9.2008 +/- 0.0006 eV for the gauche-gauche conformer. The tert-butanethiol, as expected, has a single conformer with an IP of 9.0294 +/- 0.0006 eV. For 1-butanethiol, there are a number of conformers, and the assignment of the MATI bands to each conformer turns out to be nontrivial. The spectral simulation using the Franck-Condon analysis based on the density functional theory (DFT) calculations has been used for the identification of each conformational isomer in the MATI spectrum. Each conformer undergoes its unique structural change upon ionization, as revealed in the vibration resolved MATI spectrum, providing the powerful method for the spectral identification of a specific conformational isomer. The conformer specificity in the ionization-driven structural change reflects the role of the electron of the highest occupied molecular orbital (HOMO) in the conformational preference.

7.
J Phys Chem A ; 112(23): 5060-3, 2008 Jun 12.
Artículo en Inglés | MEDLINE | ID: mdl-18484714

RESUMEN

Two different conformational isomers of propanal, cis and gauche, are investigated by the vacuum-UV mass-analyzed threshold ionization (VUV-MATI) spectroscopy to give accurate adiabatic ionization potentials of 9.9997 +/- 0.0006 eV and 9.9516 +/- 0.0006 eV, respectively. cis-Propanal, which is the more stable conformer in the neutral state, becomes less stable in the cation compared to gauche-propanal. Vibrational structures revealed in the MATI spectra indicate that cis and gauche isomers undergo their unique structural changes upon ionization. The ionization of gauche-propanal induces a geometrical change along the conformational coordinate, suggesting that the steric effect in the ground state is diminished upon ionization. Natural bonding orbital (NBO) calculations provide the extent of hyperconjugation in each conformational isomer of propanal.

8.
J Phys Chem A ; 112(31): 7125-7, 2008 Aug 07.
Artículo en Inglés | MEDLINE | ID: mdl-18620373

RESUMEN

Ar clustering dynamics around the metal-benzene sandwich complex, bis(eta (6)-benzene)chromium: Cr(Bz) 2, is found to occur in two distinct regimes. The shift of the ionization potential (IP) upon the addition of Ar is measured to be 151 cm (-1), and it is constant until the number of Ar solvents ( n) becomes 6. The IP shift per Ar is found to be suddenly decreased to 82 cm (-1) for the clusters of n = 7-12. The cluster distribution indicates that the n = 6 cluster is most populated in the molecular beam. These experimental findings with the aid of ab initio calculation indicate that the first six Ar solvent molecules are attached to top and bottom of Cr(Bz) 2 to give the robust structure for the Cr(Bz) 2-Ar 6 cluster whereas the next six Ar molecules are gathered on the side of the solute core to give the highly symmetric structure of the Cr(Bz) 2-Ar 12 cluster.

9.
Phys Chem Chem Phys ; 10(26): 3883-7, 2008 Jul 14.
Artículo en Inglés | MEDLINE | ID: mdl-18688387

RESUMEN

One-photon mass-analyzed threshold ionization (MATI) spectroscopy of jet-cooled oxazole and thiazole has been carried out to give the precise adiabatic ionization energies of 9.5959+/-0.0006 and 9.3633+/-0.0009 eV, respectively. The structural change upon ionization has been revealed in the vibrationally resolved one-photon MATI spectra. Simulations based on the Franck-Condon analysis using the molecular structures calculated by the density functional theory reproduce the experiment very well for both molecules. The ionization-driven structural change of thiazole is quite different from that of oxazole in terms of the detailed geometrical shape, ascribed to the difference in the pi-conjugation nature of two molecules. The role of oxygen and sulfur in the stabilization of heterocyclic systems is discussed through the inspection of the calculated molecular orbitals involved in the photoionization.


Asunto(s)
Frío , Compuestos Heterocíclicos/química , Oxazoles/química , Oxígeno/química , Fotones , Azufre/química , Tiazoles/química , Iones/química , Modelos Moleculares , Conformación Molecular , Análisis Espectral , Vibración
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