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1.
J Clin Periodontol ; 45(12): 1440-1447, 2018 12.
Artículo en Inglés | MEDLINE | ID: mdl-30341963

RESUMEN

AIMS: To explore the associations between periodontal status and patient-reported outcomes (PROs) in a large cohort of patients based in non-specialist general dental practice. MATERIALS AND METHODS: Analysis was conducted using data from 14,620 patients, in 233 non-specialist dental practices across the UK. As part of routine clinical care, data on periodontal probing depths (PPD), alveolar bone loss (ABL), bleeding on probing (BoP) as well as PROs (oral pain/discomfort, dietary restrictions and dental appearance) were recorded using an online database. The associations between periodontal status and PROs were investigated using logistic regression analysis, adjusting for confounders. RESULTS: We found a positive association between worse periodontal health and the prevalence of PROs. After adjustment for confounders, 13.8% of patients in the healthiest category (PPD < 5 mm, ABL < 2 mm, no BoP) reported pain/discomfort, compared to 20.7% of patients in the worst category (PPD > 7 mm, ABL > 4 mm). A similar trend was seen with reporting a restricted diet and unhappiness with appearance. CONCLUSION: This study provides novel insights into the associations between periodontal status and PROs in a non-specialist, general dental practice, highlighting the benefits of prevention and management of periodontitis.


Asunto(s)
Pérdida de Hueso Alveolar , Periodontitis , Estudios de Cohortes , Estado de Salud , Humanos , Medición de Resultados Informados por el Paciente
2.
Inorg Chem ; 50(18): 9178-83, 2011 Sep 19.
Artículo en Inglés | MEDLINE | ID: mdl-21812394

RESUMEN

In the treatment of chronic iron overload disorders, ligands capable of complexing so-called "labile" (nonprotein bound) Fe are required to enter iron-loaded cells, sequester excess Fe, and then exit the cell (and the body) as an intact Fe complex. Despite the emergence of several ligand families that show high activity in mobilizing intracellular Fe, the mechanism and the locations of these subcellular labile Fe pools are still poorly understood. Our previous studies have unearthed a class of heterocyclic hydrazine-based chelators (e.g., benzoyl picolinoyl hydrazine, H(2)BPH) that show excellent activity at mobilizing Fe from Fe-loaded cells. Herein, we have grafted a fluorescent tag (rhodamine B) onto H(2)BPH to generate a ligand (L(1)) that is nonfluorescent in its uncomplexed form but becomes strongly fluorescent in complex with Fe(III). The free ligand and its 1:2 Fe complex [Fe(III)(L(1))(2)](3+) have both been fully characterized spectroscopically and with X-ray crystallography. Confocal fluorescent microscopy of HeLa cells incubated with [Fe(III)(L(1))(2)](3+) shows that the complex rapidly enters HeLa cells and localizes within endosomes/lysosomes.


Asunto(s)
Colorantes Fluorescentes/química , Hidrazinas/química , Quelantes del Hierro/química , Rodaminas/química , Permeabilidad de la Membrana Celular , Cristalografía por Rayos X , Endosomas/metabolismo , Colorantes Fluorescentes/metabolismo , Células HeLa , Humanos , Hidrazinas/metabolismo , Quelantes del Hierro/metabolismo , Ligandos , Lisosomas/metabolismo , Modelos Moleculares , Rodaminas/metabolismo
3.
J Am Chem Soc ; 131(33): 11788-800, 2009 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-19639996

RESUMEN

Photoinduced relaxation processes of five structurally characterized Pseudomonas aeruginosa Re(I)(CO)(3)(alpha-diimine)(HisX) (X = 83, 107, 109, 124, 126)Cu(II) azurins have been investigated by time-resolved (ps-ns) IR spectroscopy and emission spectroscopy. Crystal structures reveal the presence of Re-azurin dimers and trimers that in two cases (X = 107, 124) involve van der Waals interactions between interdigitated diimine aromatic rings. Time-dependent emission anisotropy measurements confirm that the proteins aggregate in mM solutions (D(2)O, KP(i) buffer, pD = 7.1). Excited-state DFT calculations show that extensive charge redistribution in the Re(I)(CO)(3) --> diimine (3)MLCT state occurs: excitation of this (3)MLCT state triggers several relaxation processes in Re-azurins whose kinetics strongly depend on the location of the metallolabel on the protein surface. Relaxation is manifested by dynamic blue shifts of excited-state nu(CO) IR bands that occur with triexponential kinetics: intramolecular vibrational redistribution together with vibrational and solvent relaxation give rise to subps, approximately 2, and 8-20 ps components, while the approximately 10(2) ps kinetics are attributed to displacement (reorientation) of the Re(I)(CO)(3)(phen)(im) unit relative to the peptide chain, which optimizes Coulombic interactions of the Re(I) excited-state electron density with solvated peptide groups. Evidence also suggests that additional segmental movements of Re-bearing beta-strands occur without perturbing the reaction field or interactions with the peptide. Our work demonstrates that time-resolved IR spectroscopy and emission anisotropy of Re(I) carbonyl-diimine complexes are powerful probes of molecular dynamics at or around the surfaces of proteins and protein-protein interfacial regions.


Asunto(s)
Azurina/metabolismo , Compuestos Organometálicos/metabolismo , Pseudomonas aeruginosa , Absorción , Anisotropía , Azurina/química , Sitios de Unión , Transporte de Electrón , Electrones , Modelos Moleculares , Conformación Proteica , Teoría Cuántica , Renio/metabolismo , Espectroscopía Infrarroja por Transformada de Fourier , Propiedades de Superficie , Factores de Tiempo
4.
Am J Case Rep ; 20: 219-223, 2019 Feb 19.
Artículo en Inglés | MEDLINE | ID: mdl-30778021

RESUMEN

BACKGROUND Fibroepithelial polyps are benign lesions of mesodermal origin, which have been reported in the head and neck area. The aim of this study is to describe the management of an oropharyngeal fibroepithelial polyp causing stridor. CASE REPORT A 39-year-old male presented with 24 hours of stridor and dysphagia. Flexible laryngoscopy revealed a pedunculated sessile polyp on the posterior oropharynx. The mass was excised using bipolar diathermy and histopathology revealed a fibroepithelial polyp. The differential diagnoses for stridor are extensive. Although uncommon, a fibroepithelial polyp should be considered. CONCLUSIONS We present a rare case of a fibroepithelial polyp causing stridor and imminent airway obstruction. We recommend the use of SponTaneous Respiration using IntraVEnous anaesthesia and High-flow nasal oxygen (STRIVE Hi) for general anaesthesia and resection of pharyngeal polyps.


Asunto(s)
Obstrucción de las Vías Aéreas/etiología , Enfermedades de la Laringe/diagnóstico , Pólipos/diagnóstico , Adulto , Disnea/etiología , Humanos , Enfermedades de la Laringe/cirugía , Masculino , Pólipos/cirugía , Ruidos Respiratorios/etiología
5.
J Am Chem Soc ; 130(33): 10970-6, 2008 Aug 20.
Artículo en Inglés | MEDLINE | ID: mdl-18661993

RESUMEN

Temporally and spectrally resolved confocal microscopy has been used to explore the behavior of pyronine intercalated zeolite L crystals at different loadings. The low pyronine loading of 0.6% exhibits photophysical behavior similar to that of the free molecule in solution, indicating molecules are isolated from each other in the crystal channels. The higher loading of 20% results in a dye gradient along the channel axis, and the presence of an additional red-shifted spectroscopic transition, with shorter lifetimes. The new band is assigned to an inline arrangement of the molecules undergoing a J-aggregate-type coupling, a process so far not observed in subnanometer channels.


Asunto(s)
Nanopartículas/química , Nanopartículas/ultraestructura , Zeolitas/química , Cationes/química , Colorantes/química , Microscopía Confocal , Microscopía Electrónica de Rastreo , Microscopía Fluorescente , Modelos Moleculares , Estructura Molecular , Tamaño de la Partícula , Pironina/química , Factores de Tiempo , Zeolitas/síntesis química
6.
J Phys Chem B ; 110(12): 6020-6, 2006 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-16553412

RESUMEN

Novel gold nanoparticles, passivated by monolayers of benzenethiol, biphenylthiol, and similar derivatives, have been synthesized and characterized using UV/vis, NMR, and Fourier transform infrared (FTIR) spectroscopies. The nanoparticle sizes have been evaluated using transmission electron microscopy and UV/vis spectroscopy; they show diameters between 2.1 and 4.7 nm, depending on the method of synthesis and the monolayer protecting group. Femtosecond transient absorption measurements show that the nanoparticles possess optical properties on the boundary between molecular and nanoparticle behavior. The smaller systems based on benzenethiol exhibit long-lived excited states with lifetimes on the order of a few nanoseconds, resembling those of small gold molecular type clusters. The larger nanoparticles protected with biphenylthiol and benzylthiol groups relax much more rapidly on a picosecond time scale, similarly to related citrate stabilized systems reported in the literature.

7.
Chem Commun (Camb) ; (41): 4324-6, 2006 Nov 04.
Artículo en Inglés | MEDLINE | ID: mdl-17047855

RESUMEN

2.1 nm benzenethiol monolayer protected gold clusters undergo solvent dependant photoinduced deposition with potential applications in the field of nanoparticle film formation.

8.
Prim Dent Care ; 11(2): 37-9, 2004 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-15119092

RESUMEN

UNLABELLED: An oral health scoring system (Oral Health Score: OHS) has been designed to provide a numerical measure of the overall state of a patients oral health by means of a series of simple clinical examinations. OBJECTIVE: To assess, by means of a questionnaire, patients opinions of the value of the OHS. METHODS: Eight general dental practitioners who used the OHS were asked to participate in the project. The participating dentists were requested to explain the aims of the project to 50 patients. Patients who agreed to participate were asked to complete a questionnaire after a visit during which the OHS was used. These patients were provided with a reply-paid envelope for the return of the questionnaire. RESULTS: Completed usable questionnaires were received from 315 patients. Of respondents, 97% considered that the OHS gave them a better understanding of the condition of their mouth and 98% considered that the OHS was a good method for communication between dentist and patient. CONCLUSION: The results of the present study indicate that, within the study group, the OHS is considered by a large majority of patients to be a good method for communication of the patient's oral health between dentist and patient.


Asunto(s)
Actitud Frente a la Salud , Estado de Salud , Salud Bucal , Encuestas de Salud Bucal , Humanos , Pacientes/psicología , Proyectos Piloto , Índice de Severidad de la Enfermedad , Encuestas y Cuestionarios
10.
Protein Eng Des Sel ; 24(9): 751-63, 2011 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-21616931

RESUMEN

Constrained binding peptides (peptide aptamers) may serve as tools to explore protein conformations and disrupt protein-protein interactions. The quality of the protein scaffold, by which the binding peptide is constrained and presented, is of crucial importance. SQT (Stefin A Quadruple Mutant-Tracy) is our most recent development in the Stefin A-derived scaffold series. Stefin A naturally uses three surfaces to interact with its targets. SQT tolerates peptide insertions at all three positions. Peptide aptamers in the SQT scaffold can be expressed in bacterial, yeast and human cells, and displayed as a fusion to truncated pIII on phage. Peptides that bind to CDK2 can show improved binding in protein microarrays when presented by the SQT scaffold. Yeast two-hybrid libraries have been screened for binders to the POZ domain of BCL-6 and to a peptide derived from PBP2', specific to methicillin-resistant Staphylococcus aureus. Presentation of the Noxa BH3 helix by SQT allows specific interaction with Mcl-1 in human cells. Together, our results show that Stefin A-derived scaffolds, including SQT, can be used for a variety of applications in cellular and molecular biology. We will henceforth refer to Stefin A-derived engineered proteins as Scannins.


Asunto(s)
Aptámeros de Péptidos/química , Aptámeros de Péptidos/metabolismo , Cistatina A/química , Cistatina A/metabolismo , Ingeniería de Proteínas/métodos , Secuencia de Aminoácidos , Aptámeros de Péptidos/genética , Línea Celular Tumoral , Dicroismo Circular , Quinasa 2 Dependiente de la Ciclina/química , Quinasa 2 Dependiente de la Ciclina/genética , Cistatina A/genética , Humanos , Datos de Secuencia Molecular , Mutación , Análisis por Matrices de Proteínas , Proteínas Proto-Oncogénicas c-bcl-2/química , Proteínas Proto-Oncogénicas c-bcl-2/genética , Alineación de Secuencia , Relación Estructura-Actividad , Técnicas del Sistema de Dos Híbridos
11.
Biophys Chem ; 152(1-3): 170-7, 2010 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-20970240

RESUMEN

The Strep tag is a peptide sequence that is able to mimic biotin's ability to bind to streptavidin. Sequences of Strep tags from 0 to 5 have been appended to the N-terminus of a model protein, the Stefin A Quadruple Mutant (SQM) peptide aptamer scaffold, and the recombinant fusion proteins expressed. The affinities of the proteins for streptavidin have been assessed as a function of the number of tags inserted using a variety of labelled and label-free bioanalytical and surface based methods (Western blots, microarray assays and surface plasmon resonance spectroscopy). The binding affinity increases with the number of tags across all assays, reaching nanomolar levels with 5 inserts, an observation assigned to a progressive increase in the probability of a binding interaction occurring. In addition a novel interfacial FRET based assay has been developed for generic Strep tag interactions, which utilises a conventional microarray scanner and bypasses the requirement for expensive lifetime imaging equipment. By labelling both the tagged StrepX-SQM(2) and streptavidin targets, the conjugate is primed for label-free FRET based displacement assays.


Asunto(s)
Oligopéptidos/química , Proteínas Recombinantes de Fusión/análisis , Marcadores de Afinidad/química , Secuencia de Aminoácidos , Aptámeros de Péptidos/química , Biotina/química , Biotina/metabolismo , Cistatina A/química , Cistatina A/genética , Cistatina A/metabolismo , Transferencia Resonante de Energía de Fluorescencia , Unión Proteica , Proteínas Recombinantes de Fusión/química , Proteínas Recombinantes de Fusión/genética , Estreptavidina/química , Estreptavidina/metabolismo , Resonancia por Plasmón de Superficie
12.
Protein Eng Des Sel ; 23(5): 403-13, 2010 May.
Artículo en Inglés | MEDLINE | ID: mdl-20179045

RESUMEN

Non-antibody scaffold proteins are used for a range of applications, especially the assessment of protein-protein interactions within human cells. The search for a versatile, robust and biologically neutral scaffold previously led us to design STM (stefin A triple mutant), a scaffold derived from the intracellular protease inhibitor stefin A. Here, we describe five new STM-based scaffold proteins that contain modifications designed to further improve the versatility of our scaffold. In a step-by-step approach, we introduced restriction sites in the STM open reading frame that generated new peptide insertion sites in loop 1, loop 2 and the N-terminus of the scaffold protein. A second restriction site in 'loop 2' allows substitution of the native loop 2 sequence with alternative oligopeptides. None of the amino acid changes interfered significantly with the folding of the STM variants as assessed by circular dichroism spectroscopy. Of the five scaffold variants tested, one (stefin A quadruple mutant, SQM) was chosen as a versatile, stable scaffold. The insertion of epitope tags at varying positions showed that inserts into loop 1, attempted here for the first time, were generally well tolerated. However, N-terminal insertions of epitope tags in SQM had a detrimental effect on protein expression.


Asunto(s)
Cistatina A/genética , Modelos Moleculares , Mutación/genética , Ingeniería de Proteínas/métodos , Relación Estructura-Actividad , Sustitución de Aminoácidos , Dicroismo Circular , Cistatina A/química , Escherichia coli , Inmunoprecipitación , Análisis por Micromatrices , Mutagénesis , Pliegue de Proteína
14.
Chemistry ; 14(23): 6912-23, 2008.
Artículo en Inglés | MEDLINE | ID: mdl-18604857

RESUMEN

Two multifunctional photoactive complexes [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+)=N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy=2,2'-bipyridine) were synthesized, characterized, and their redox and photonic properties were investigated by cyclic voltammetry; ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions; and time-resolved resonance Raman spectroscopy. The first reduction step of either complex occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans-->cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDpe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3)-->MeDpe(+ 3)MLCT (MLCT=metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximately 42 (73 %) and approximately 430 ps (27 %). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3)-->MeDpe(+) and Re(CO)(3)-->bpy (3)MLCT states, from which a MeDpe(+) localized intraligand (3)pipi* excited state ((3)IL) is populated with lifetimes of approximately 0.6 and approximately 10 ps, respectively. The (3)IL state undergoes a approximately 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle structural variations. The complex [Re(MeDpe(+))(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.


Asunto(s)
2,2'-Dipiridil/química , Compuestos Organometálicos/química , Compuestos de Piridinio/química , Renio/química , Electroquímica , Isomerismo , Estructura Molecular , Oxidación-Reducción , Fotoquímica , Espectrofotometría , Espectrometría Raman , Factores de Tiempo
15.
Inorg Chem ; 45(24): 9789-97, 2006 Nov 27.
Artículo en Inglés | MEDLINE | ID: mdl-17112276

RESUMEN

UV-vis absorption and picosecond time-resolved IR (TRIR) spectra of amido and phosphido complexes fac-[Re(ER2)(CO)3(bpy)] (ER2 = NHPh, NTol2, PPh2, bpy = 2,2'-bipyridine, Tol = 4-methylphenyl) were investigated in conjunction with DFT and TD-DFT calculations in order to understand their ground-state electronic structure, low-lying electronic transitions and excited-state character and dynamics. The HOMO is localized at the amido/phosphido ligand. Amide and phosphide ligands are sigma-bonded to Re, the pi interaction being negligible. Absorption spectra show a weak band at low energies (1.7-2.1 eV) that arises from essentially pure ER(2) --> bpy ligand-to-ligand charge transfer (LLCT). The lowest excited state is the corresponding triplet, (3)LLCT. Low triplet energies and large distortions diminish the excited-state lifetimes to 85 and 270 ps for NHPh and NTol(2), respectively, and to ca. 30 ps for PPh2. nu(CO) vibrations undergo only very small ( bpy MLCT character, is a unique feature of the amido/phoshido complexes, whose lowest excited state can be viewed as containing a highly unusual aminyl/phosphinyl radical-cationic ligand. For comparison, the amino and phosphino complexes fac-[Re(NHPh(2))(CO)3(bpy)]+ and fac-[Re(PPh3)(CO)3(bpy)]+ are shown to have the usual Re --> bpy (3)MLCT lowest excited states, characterized by upshifted nu(CO) bands.

16.
J Am Chem Soc ; 128(13): 4365-70, 2006 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-16569013

RESUMEN

The triplet metal-to-ligand charge transfer ((3)MLCT) dynamics of two structurally characterized Re(I)(CO)(3)(phen)(HisX)-modified (phen = 1,10-phenanthroline; X = 83, 109) Pseudomonas aeruginosa azurins have been investigated by picosecond time-resolved infrared (TRIR) spectroscopy in aqueous (D(2)O) solution. The (3)MLCT relaxation dynamics exhibited by the two Re(I)-azurins are very different from those of the sensitizer [Re(I)(CO)(3)(phen)(im)](+) (im = imidazole). Whereas the Re(I)(CO)(3) intramolecular vibrational relaxation in Re(I)(CO)(3)(phen)(HisX)Az (4 ps) is similar to that of [Re(I)(CO)(3)(phen)(im)](+) (2 ps), the medium relaxation is much slower ( approximately 250 vs 9.5 ps); the 250-ps relaxation is attributable to reorientation of D(2)O molecules as well as structural reorganization of the rhenium chromophore and nearby polar amino acids in each of the modified proteins.


Asunto(s)
Azurina/química , Renio/química , Metaloproteínas/química , Modelos Moleculares , Péptidos/química , Fenantrolinas/química , Conformación Proteica , Pseudomonas aeruginosa/química , Soluciones , Espectrofotometría Infrarroja , Agua/química
17.
J Phys Chem A ; 109(13): 3000-8, 2005 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-16833623

RESUMEN

UV-vis absorption and resonance Raman spectra of the complexes fac-[Re(Cl)(CO)3(stpy)2] and fac-[Re(stpy)(CO)3(bpy)]+ (stpy = t-4-styrylpyridine, bpy = 2,2'-bipyridine) show that their lowest absorption bands are dominated by stpy-localized intraligand (IL) pi pi* transitions. For the latter complex a Re --> bpy transition contributes to the low-energy part of the absorption band. Optical population of the 1IL excited state of fac-[Re(Cl)(CO)3(stpy)2] is followed by an intersystem crossing (< or =0.9 ps) to an 3IL state with the original planar trans geometry of the stpy ligand. This state undergoes a approximately 90 degrees rotation around the stpy C=C bond with a 11 ps time constant. An electronically excited species with an approximately perpendicular orientation of the phenyl and pyridine rings of the stpy ligand is formed. Conversion to the ground state and isomerization occurs in the nanosecond range. Intraligand excited states of fac-[Re(stpy)(CO)3(bpy)]+ show the same behavior. Moreover, it was found that the planar reactive 3IL excited state is rapidly and efficiently populated after optical excitation into the Re --> bpy 1MLCT excited state. A 1MLCT --> 3MLCT intersystem crossing takes place first with a time constant of 0.23 ps followed by an intramolecular energy transfer from the ReI(CO)3(bpy) chromophore to a stpy-localized 3IL state with a 3.5 ps time constant. The fast rate ensures complete conversion. Coordination of the stpy ligand to the ReI center thus switches the ligand trans-cis isomerization mechanism from singlet to triplet (intramolecular sensitization) and, in the case of fac-[Re(stpy)(CO)3(bpy)]+, opens an indirect pathway for population of the reactive 3IL excited state via MLCT states.


Asunto(s)
Compuestos Organometálicos/química , Piridinas/química , Estirenos/química , Isomerismo , Cinética , Ligandos , Estructura Molecular , Análisis Espectral , Factores de Tiempo
18.
Inorg Chem ; 43(5): 1723-34, 2004 Mar 08.
Artículo en Inglés | MEDLINE | ID: mdl-14989665

RESUMEN

The characters, dynamics, and relaxation pathways of low-lying excited states of the complexes [W(CO)(5)L] [L = 4-cyanopyridine (pyCN) and piperidine (pip)] were investigated using theoretical and spectroscopic methods. DFT calculations revealed the delocalized character of chemically and spectroscopicaly relevant molecular orbitals and the presence of a low-lying manifold of CO pi-based unoccupied molecular orbitals. Traditional ligand-field arguments are not applicable. The lowest excited states of [W(CO)(5)(pyCN)] are W --> pyCN MLCT in character. They are closely followed in energy by W --> CO MLCT states. Excitation at 400 or 500 nm populates the (3)MLCT(pyCN) excited state, which was characterized by picosecond time-resolved IR and resonance Raman spectroscopy. Excited-state vibrations were assigned using DFT calculations. The (3)MLCT(pyCN) excited state is initially formed highly excited in low-frequency vibrations which cool with time constants between 1 and 20 ps, depending on the excitation wavelength, solvent, and particular high-frequency nu(CO) or nu(CN) mode. The lowest excited states of [W(CO)(5)(pip)] are W --> CO MLCT, as revealed by TD-DFT interpretation of a nanosecond time-resolved IR spectrum that was measured earlier in a low-temperature glass (Johnson, F. P. A.; George, M. W.; Morrison, S. L.; Turner, J. J. J. Chem. Soc., Chem. Commun. 1995, 391-393). MLCT(CO) excitation involves transfer of electron density from the W atom and, to a lesser extent, the trans CO to the pi orbitals of the four cis CO ligands. Optical excitation into MLCT(CO) transition of either complex in fluid solution triggers femtosecond dissociation of a W-N bond, producing [W(CO)(5)(solvent)]. It is initially vibrationally excited both in nu(CO) and anharmonicaly coupled low-frequency modes. Vibrational cooling occurs with time constants of 16-22 ps while the intramolecular vibrational energy redistribution from the v = 1 nu(CO) modes is much slower, 160-220 ps. No LF excited states have been found for the complexes studied in a spectroscopically relevant range up to 6-7 eV. It follows that spectroscopy, photophysics, and photochemistry of [W(CO)(5)L] and related complexes are well described by an interplay of close-lying MLCT(L) and MLCT(CO) excited states. The high-lying LF states play only an indirect photochemical role by modifying potential energy curves of MLCT(CO) states, making them dissociative.

19.
J Clin Monit Comput ; 17(3-4): 241-7, 2002.
Artículo en Inglés | MEDLINE | ID: mdl-12455743

RESUMEN

OBJECTIVE: A repetitive graphic display of the single breath pulmonary function can indicate changes in cardiac and pulmonary physiology brought on by clinical events. Parallel advances in computer technology and monitoring make real-time, single breath pulmonary function clinically practicable. We describe a system built from a commercially available airway gas monitor and off the shelf computer and data-acquisition hardware. METHODS: Analog data for gas flow rate, O2, and CO2 concentrations are introduced into a computer through an analog-to-digital conversion board. Oxygen uptake (VO2) and carbon dioxide output (VCO2) are calculated for each breath. Inspired minus expired concentrations for O2 and CO2 are displayed simultaneously with the expired gas flow rate curve for each breath. Dead-space and alveolar ventilation are calculated for each breath and readily appreciated from the display. RESULTS: Graphs illustrating the function of the system are presented for the following clinical scenarios; upper airway obstruction, bronchospasm, bronchopleural fistula, pulmonary perfusion changes and inadequate oxygen delivery. CONCLUSIONS: This paper describes a real-time, single breath pulmonary monitoring system that displays three parameters graphed against time: expired flow rate, oxygen uptake and carbon dioxide production. This system allows for early and rapid recognition of treatable conditions that may lead to adverse events without any additional patient measurements or invasive procedures. Monitoring systems similar to the one described in this paper may lead to a higher level of patient safety without any additional patient risk.


Asunto(s)
Monitoreo Fisiológico , Intercambio Gaseoso Pulmonar , Humanos , Pruebas de Función Respiratoria
20.
Inorg Chem ; 43(16): 4994-5002, 2004 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-15285676

RESUMEN

The nature and dynamics of the lowest excited states of fac-[Re(I)(L)(CO)(3)(phen)](+) and fac-[Re(I)(L)(CO)(3)(5-NO(2)-phen)](+) [L = Cl(-), 4-ethyl-pyridine (4-Etpy), imidazole (imH); phen = 1,10-phenanthroline] have been investigated by picosecond visible and IR transient absorption spectroscopy in aqueous (L = imH), acetonitrile (L = 4-Etpy, imH), and MeOH (L = imH) solutions. The phen complexes have long-lived Re(I) --> phen (3)MLCT excited states, characterized by CO stretching frequencies that are upshifted relative to their ground-state values and by widely split IR bands due to the out-of-phase A'(2) and A"nu(CO) vibrations. The lowest excited states of the 5-NO(2)-phen complexes also have (3)MLCT character; the larger upward nu(CO) shifts accord with much more extensive charge transfer from the Re(I)(CO)(3) unit to 5-NO(2)-phen in these states. Transient visible absorption spectra indicate that the excited electron is delocalized over the 5-NO(2)-phen ligand, which acquires radical anionic character. Similarly, involvement of the -NO(2) group in the Franck-Condon MLCT transition is manifested by the presence of an enhanced nu(NO(2)) band in the preresonance Raman spectrum of [Re(I)(4-Etpy)(CO)(3)(5-NO(2)-phen)](+). The Re(I) --> 5-NO(2)-phen (3)MLCT excited states are very short-lived: 7.6, 170, and 43 ps for L = Cl(-), 4-Etpy, and imH, respectively, in CH(3)CN solutions. The (3)MLCT excited state of [Re(I)(imH)(CO)(3)(5-NO(2)-phen)](+) is even shorter-lived in MeOH (15 ps) and H(2)O (1.3 ps). In addition to (3)MLCT, excitation of [Re(I)(imH)(CO)(3)(5-NO(2)-phen)](+) populates a (3)LLCT (imH --> 5-NO(2)-phen) excited state. Most of the (3)LLCT population decays to the ground state (time constants of 19 (H(2)O), 50 (MeOH), and 72 ps (CH(3)CN)); in a small fraction, however, deprotonation of the imH.+ ligand occurs, producing a long-lived species, [Re(I)(im.)(CO)(3)(5-NO(2)-phen).-]+.


Asunto(s)
Compuestos Organometálicos/química , Renio/química , Imidazoles/química , Fenantrolinas/química , Piridinas/química , Espectrofotometría Infrarroja , Espectrometría Raman , Termodinámica , Factores de Tiempo
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