CdS:Mn nanocrystals passivated by ZnS: synthesis and luminescent properties

Synthesis and characterization of highly luminescent ZnS-passivated CdS:Mn (CdS:Mn/ZnS) core/shell structured nanocrystals are reported. Mn-doped CdS core nanocrystals are produced ranging from 1.5 to 2.3 nm in diameter with epitaxial ZnS shell of wider band gap via a reverse micelle process. UV irradiation-stimulated photo-oxidation of the ZnS shell results in formation of sulfate (ZnSO(4)) as determined by x-ray photoelectron spectroscopy, which increases the photoluminescence emission intensity and subsequent photostability. Luminescent relaxation lifetime data present two different decay components, consisting of slow decay emission from the Mn center and a fast decay emission from a defect-related center. The impact of the density of surface defect states upon the emission spectra is discussed.     

Intrachain triplet energy transfer in platinum-acetylide copolymers

A series of platinum-acetylide homo- and copolymers was prepared and characterized by using photophysical methods. The polymers feature repeat units of the type [trans-Pt(PBu3)2(-CC-Ar-CC-)], where Ar = 1,4-phenylene (P) or 2,5-thienylene (T). The properties of homopolymers that contain only the 1,4-phenylene or 2,5-thienylene repeat units were compared with those of random copolymers having the structure -[-(Pt(PBu3)2(-CC-T-CC-))x-(Pt(PBu3)2(-CC-P-CC-))(1-x)-)] where x = 0.05, 0.15, and 0.25. Absorption and photoluminescence spectroscopy demonstrates that the singlet and triplet excitations localized on 1,4-phenylene units are higher in energy relative to those localized on the 2,5-thienylene units. The mechanism and dynamics of intrachain triplet energy transfer from 1,4-phenylene to the 2,5-thienylene repeats were explored in the copolymers. Photoluminescence and nanosecond transient absorption spectroscopy indicate that at room temperature P --> T energy transfer is efficient and rapid (k > 10(8) s(-1)), even in the copolymer that contains only 5% 2,5-thienylene repeat units. At 77 K, steady-state and time-resolved photoluminescence spectroscopy reveals that triplet energy transfer is much less efficient and a fraction of the triplet excitations is "trapped" on the high-energy 1,4-phenylene units. Intrachain energy transfer is believed to occur by two mechanisms, one involving P --> T singlet energy transfer followed by intersystem crossing, whereas the other involves intersystem crossing prior to P --> T triplet energy transfer. The relationship between the observed energy transfer efficiencies and mechanisms in the copolymers is discussed.     

Photooxidation of Diimine Dithiolate Platinium(II) Complexes Induced by Charge Transfer to Diimine Excitation

A photochemical and photophysical investigation was carried out on (tbubpy)Pt(II)(dpdt) and (tbubpy)Pt(II)(edt) (1 and 2, respectively, where tbubpy = 4,4'-di-tert-butyl-2,2'-bipyridine, dpdt = meso-1,2-diphenyl-1,2-ethanedithiolate and edt = 1,2-ethanedithiolate). Luminescence and transient absorption studies reveal that these complexes feature a lowest excited state with Pt(S)(2) --> tbubpy charge transfer to diimine character. Both complexes are photostable in deoxygenated solution; however, photolysis into the visible charge transfer band in air-saturated solution induces moderately efficient photooxidation. Photooxidation of 1 produces the dehydrogenation product (tbubpy)Pt(II)(1,2-diphenyl-1,2-ethenedithiolate) (4). By contrast, photooxidation of 2 produces S-oxygenated complexes in which one or both thiolate ligands are converted to sulfinate (-SO(2)R) ligands. Mechanistic photochemical studies and transient absorption spectroscopy reveal that photooxidation occurs by (1) energy transfer from the charge transfer to diimine excited state of 1 to (3)O(2) to produce (1)O(2) and (2) reaction between (1)O(2) and the ground state 1. Kinetic data indicates that excited state 1 produces (1)O(2) efficiently and that reaction between ground state 1 and (1)O(2) occurs with k approximately 3 x 10(8) M(-)(1) s(-)(1).     

Visualization of gas–liquid mass transfer and wake structure of rising bubbles using pH-sensitive PLIF

A planar laser-induced fluorescence (PLIF) technique for visualizing gas–liquid mass transfer and wake structure of rising gas bubbles is described. The method uses an aqueous solution of the pH-sensitive dye Naphthofluorescein and CO₂ as a tracer gas. It features a high spatial resolution and frame rates of up to 500 Hz, providing the ability to capture cinematographic image sequences. By steering the laser beam with a set of two programmable scanning mirrors, sequences of three-dimensional LIF images can be recorded. The technique is applied to freely rising bubbles with diameters between 0.5 and 5 mm, which perform rectilinear, oscillatory or irregular motions. The resulting PLIF image sequences reveal the evolution of characteristic patterns in the near and far wake of the bubbles and prove the potential of the technique to provide new and detailed insights into the spatio-temporal dynamics of mass transfer of rising gas bubbles. The image sequences further allow the estimation of bubble size and rise velocity. The analysis of bubble rise velocities in the Naphthofluorescein solution indicates that surfactant-contaminated conditions are encountered.     

Interfacial morphology and photoelectrochemistry of conjugated polyelectrolytes adsorbed on single crystal TiO2

The nanoscale morphology and photoactivity of conjugated polyelectrolytes (CPEs) deposited from different solvents onto single crystal TiO(2) were investigated with atomic force microscopy (AFM) and photocurrent spectroscopy. CPE surface coverages on TiO(2) could be incremenentally increased by adsorbing the CPEs from static solutions. The solvents used for polymer adsorption influenced the surface morpohology of the CPEs on the TiO(2) surface. Photocurrent spectroscopy measurements in aqueous electrolytes, using iodide as a hole scavenger, revealed that the magnitude of the sensitized photocurrents was related to the surface coverages and the degree of aggregation of the CPEs as determined by AFM imaging. Absorbed photon-to-current efficiencies approaching 50% were measured for CPE layers as thick as 4 nm on TiO(2). These results suggest that precise control of CPE morphology at the TiO(2) interface can be achieved through optimization of the deposition conditions to improve the power conversion efficiencies of polymer-sensitized solar cells.     

Effect of polymer chain length on membrane perturbation activity of cationic phenylene ethynylene oligomers and polymers

The interactions of poly(phenylene ethynylene)- (PPE-) based cationic conjugated polyelectrolytes (CPEs) and oligo(phenylene ethynylene)s (OPEs) with different model lipid membrane systems were investigated to gain insight into the relationship between molecular structure and membrane perturbation ability. The CPE and OPE compounds exhibit broad-spectrum antimicrobial activity, and cell walls and membranes are believed to be their main targets. To better understand how the size, in terms of the number of repeat units, of the CPEs and OPEs affects their membrane disruption activities, a series of PPE-based CPEs and OPEs were synthesized and studied. A number of photophysical techniques were used to investigate the interactions of CPEs and OPEs with model membranes, including unilamellar vesicles and lipid monolayers at the air/water interface. CPE- or OPE-induced dye leakage from vesicles reveals that the CPEs and OPEs selectively perturb model bacterial membranes and that their membrane perturbation abilities are highly dependent on molecular size. Consistent with dye-leakage assay results, the CPEs and OPEs also exhibit chain-length-dependent ability to insert into 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (DPPG) monolayers. Our results suggest that, for PPE-based CPE and OPE antimicrobials, chain length can be tuned to optimize their membrane perturbation ability.     

Light-induced antibacterial activity of symmetrical and asymmetrical oligophenylene ethynylenes

The light-induced antibacterial activity of symmetric and asymmetric oligophenylene ethynylenes (OPEs) was investigated against Gram-positive (Staphylococcus aureus and Staphylococcus epidermidis) and Gram-negative (Escherichia coli) bacteria. To understand the light-induced biocidal effect better, the transient absorption and triplet lifetime of OPEs were studied in methanol and water. A higher triplet lifetime was observed for OPE samples in water than in methanol. The magnitudes of the changes in optical density (ΔOD) of the S-OPE-n(H) series of symmetric oligomers are much higher than that of the asymmetric OPE-n series in water and are generally correlated with the singlet oxygen yield. It was found that the antibacterial activity against both Gram-positive and Gram-negative bacteria is size-, concentration-, and time-dependent. The light-induced antibacterial activity may result from the coordinated interactions of membrane disruption and interfacial or intracellular singlet oxygen generation, and the dominant factor is most likely the latter. The results obtained in this study will aid in the design of more efficient biocides in the future.