The effect of photoinduced processes on CdSe/ZnS quantum dots surface on the functionality of TiO2 nanoparticles/quantum dots hybrid structures was investigated. It is shown that preliminary irradiation of quantum dots makes it possible to achieve a threefold increase in the efficiency of electron transfer from quantum dot to TiO2 nanoparticle in these structures. It has been demonstrated that photoinduced processes affect both the quantum yield of quantum dots luminescence and the reactive oxygen species generation by structures under visible light.
Here we report our investigations of the formation conditions and photophysical properties of complexes between luminescent semiconducting nanoparticles (quantum dots, QDs) and the photosensitizer chlorin e6, which is widely used for the photodynamic therapy. In our complexes, bovine serum albumin (BSA), the most abundant protein in blood serum, was used as a linker between QDs and chlorin e6 molecules. The influence of BSA on the optical properties of Ce6 and QDs in complexes was properly examined using spectral-luminescent methods. It was found that BSA passivated QD surface and substantially QD quantum yield of luminescence was increased. In addition, BSA prevented the aggregation of chlorin e6 molecules in complexes with QDs. We demonstrated that the use of BSA as a linker allows to create functional QD-chlorin e6 complexes with effective photoexcitation energy transfer from QDs to the molecules.
A morphology and photoinduced changes of luminescence properties of two types of hybrid structures based
on TiO2 nanoparticles and CdSe/ZnS QDs were examined. A spin-coating method and a modified Langmuir-
Blodgett technique have been applied to form the multilayer hybrid structures on glass slides. It was
demonstrated that uniformity of QD surface concentration in hybrid structures depends on the method of
structure formation. A photodegradation of luminescence properties of the structures is associated with the
formation of QD aggregates. The QD aggregate concentration and their size depend on the method of the
structure formation and the concentration of TiO2 nanoparticles. A decay of luminescence of QD aggregates
in hybrid structures contains a microsecond components. An exposure of the hybrid structures with uniform
QD surface concentration by visible light resulted in a photopassivation of their surface, which is
accompanied by significant increase of luminescence quantum yield of QDs.
Plasmon-enhanced nonradiative energy transfer is demonstrated in two inorganic semiconductor systems. The first is
comprised of colloidal nanocrystal CdTe donor and acceptor quantum dots, while the second is a hybrid InGaN quantum
well-CdSe/ZnS quantum dot donor-acceptor system. Both structures are in a planar geometry. In the first case a
monolayer of Au nanospheres is sandwiched between donor and acceptor quantum dot monolayers. The largest energy
transfer efficiency is seen when the donor is ~3 nm from the Au nanopshere. A plasmon-enhanced energy transfer
efficiency of ~ 40% has been achieved for a separation of 3 nm between the Au nanopshere monolayer and the acceptor
monolayer. Despite the increased energy transfer efficiency these conditions result in strong quenching of the acceptor
QD emission. By tuning the Au nanosphere concentration and Au nanosphere-acceptor QD separation the acceptor QD
emission can be increased by a factor of ~2.8. The plasmon-enhanced nonradiative energy transfer is observed to extend
over larger distances than conventional Forster resonance energy transfer. Under the experimental conditions reported
herein, it can be described by the same d-4 dependence but with a larger characteristic distance. Using a Ag nanobox
array plasmonic component plasmon-enhanced nonradiative energy transfer has also demonstrated from an InGaN
quantum well to a ~80 nm thick layer of CdSe/ZnS colloidal quantum dots. An efficiency of ~27% is achieved, with an
overall increase in the QD emission by ~70%.
The main goal of our research is to develop new types of technologically important optically active quantum dot (QD) based materials, study their properties and explore their biological applications. For the first time chiral II-VI QDs have been prepared by us using microwave induced heating with the racemic (Rac), D- and L-enantiomeric forms of penicillamine as stabilisers. Circular dichroism (CD) studies of these QDs have shown that D- and L-penicillamine stabilised particles produced mirror image CD spectra, while the particles prepared with a Rac mixture showed only a weak signal. It was also demonstrated that these QDs show very broad emission bands between 400 and 700 nm due to defects or trap states on the surfaces of the nanocrystals. These QDs have demonstrated highly specific chiral recognition of various biological species including aminoacids. The utilisation of chiral stabilisers also allowed the preparation of new water soluble white emitting CdS nano-tetrapods, which demonstrated circular dichroism in the band-edge region of the spectrum. Biological testing of chiral CdS nanotetrapods displayed a chiral bias for an uptake of the D- penicillamine stabilised nano-tetrapods by cancer cells. It is expected that this research will open new horizons in the chemistry of chiral nanomaterials and their application in nanobiotechnology, medicine and optical chemo- and bio-sensing.
Recently, the use of stereospecific chiral stabilising molecules has also opened another avenue of interest in the area of
quantum dot (QD) research. The main goal of our research is to develop new types of technologically important quantum
dot materials containing chiral defects, study their properties and explore their applications. The utilisation of chiral
penicillamine stabilisers allowed the preparation of new water soluble white emitting CdS quantum nanostructures
which demonstrated circular dichroism in the band-edge region of the spectrum. It was also demonstrated that all three
types of QDs (D-, L-, and Rac penicillamine stabilised) show very broad emission bands between 400 and 700 nm due to
defects or trap states on the surfaces of the nanocrystals. In this work the chiral CdS based quantum nanostructures have
also been doped by copper metal ions and new chiral penicilamine stabilized CuS nanoparticles have been prepared and
investigated. It was found that copper doping had a strong effect at low levels in the synthesis of chiral CdS
nanostructures. We expect that this research will open new horizons in the chemistry of chiral nanomaterials and their
application in biotechnology, sensing and asymmetric synthesis.
We develop a theory of time-resolved pump–probe optical spectroscopy for modelling interband absorption by an anisotropic semiconductor nanodumbbell. By considering three transition schemes where the pump and probe pulses are nearly resonant to a dipole-allowed interband transition of different elements of the nanodumbbell, and assuming that the populations of the exited states are coupled through the nonradiative relaxation processes, we analytically calculate the absorption efficiency of the probe as a function of its delay from the pump for relatively short pulses. The obtained functional dependency, being the sum of exponentials with exponents proportional to the energy relaxation rates of the excited electronic states, is useful for the analysis of experimental absorption spectra aiming at retrieving the relaxation parameters of the nanodumbbell’s electronic subsystem.
Quantum dots (QDs) are fluorescent semiconductor (e.g. II-VI) nanocrystals, which have a strong characteristic
spectral emission. This emission is tunable to a desired energy by selecting variable particle size, size distribution and
composition of the nanocrystals. QDs have recently attracted enormous interest due to their unique photophysical
properties and range of potential applications in photonics and biochemistry. The main aim of our work is develop new
chiral quantum dots (QDs) and establish fundamental principles influencing their structure, properties and biosensing
behaviour. Here we present the synthesis and characterisation of chiral CdSe semiconductor nanoparticles and their
utilisation as new chiral biosensors. Penicillamine stabilised CdSe nanoparticles have shown both very strong and very
broad luminescence spectra. Circular dichroism (CD) spectroscopy studies have revealed that the D- and Lpenicillamine
stabilised CdSe QDs demonstrate circular dichroism and possess almost identical mirror images of CD
signals. Studies of photoluminescence and CD spectra have shown that there is a clear relationship between defect
emission and CD activity. We have also demonstrated that these new QDs can serve as fluorescent nanosensors for
various chiral biomolecules including nucleic acids. These novel nanosensors can be potentially utilized for detection of
various chiral biological and chemical species with the broad range of potential applications.
In recent years the application of nano-porous templates, such as anodic alumina and PTFE, in the production of cylindrical nanostructures has been vast. In our work we used porous alumina membranes to produce luminescent nanowires from polystyrene and silica. The silica wires were fabricated by infiltration of a TEOS derived sol-gel into 200 nm diameter porous alumina membranes with vacuum assistance followed by annealing at 400 °C. Polystyrene luminescent, magnetic nanowires have been fabricated using a similar technique. The wires were studied by optical, confocal and transmission electron microscopy. Silica nanowires demonstrated a broad luminescence spectrum due to interstitial carbon defect emission. Polystyrene nanowires have demonstrated strong emission and interesting magnetic behaviour. Both polystyrene and silica maghemite loaded nanowires show alignment to an external magnetic field. We believe that these silica and polystyrene nanowires might find potential applications in photonics, bio-sensing and biological imaging.
In this paper we describe a novel technique for the fabrication of aluminosilicate microfibres and microtubes which are
shown to act as optical cylindrical microresonators. The alumosilicate microfibres and microtubes were fabricated by
using vacuum-assisted wetting and filtration of silica gel through a microchannel glass matrix. The microfibres and
microtubes were studied using Scanning Electron Microscopy (SEM), micro-photoluminescence spectroscopy and
fluorescence lifetime imaging confocal microscopy. In the emission spectra of the micro-resonators we find very narrow
periodic peaks corresponding to the whispering gallery modes of two orthogonal polarizations with quality factors up to
3200. A strong enhancement in photoluminescence decay rates at high excitation power demonstrates the occurrence of
amplified spontaneous emission from a single microtube. These microtubes show a large evanescent field extending
many microns beyond the tube radius. Potential applications for these novel microresonators will be in the area of optical
microsensors for a single molecule detection of biological and chemical species, including anti-terrorism and defense
sectors.
KEYWORDS: Gold, Fluorescence resonance energy transfer, Surface plasmons, Quartz, Absorption, Resonance energy transfer, Nanoparticles, Luminescence, Quantum dots, Energy transfer
F&diaero;rster resonant energy transfer (FRET) between the CdTe quantum dot (QD) acting as donors and acceptors is
investigated at nanoscale proximity to gold nanoparticles (Au NPs). Photoluminescence (PL) studies of the acceptor QD
emission from a mixed monolayer showed a distance dependent enhancement of the acceptor emission compared with
that achieved for a donor-acceptor mixed monolayer in the absence of the Au NP layer. Time-resolved photoluminescence measurements showing a reduction in the donor lifetime, accompanied by an increase in the acceptor PL lifetime, provide further evidence for surface plasmon enhanced FRET.
We present a detailed study of the photonic modes in microtube cavity of ~ 7-8 μm outer diameter that can act as micron-scale optical cylindrical resonator. We demonstrate a new route to the fabrication of individual microtubes with the maximum length of 200 &mgr;m, using a vacuum assisted wetting and filtration through a microchannel glass matrix. The microtubes were studied using micro-photoluminescence spectroscopy and luminescence lifetime imaging confocal microscopy. In the emission spectra of the microresonators we find periodic very narrow peaks corresponding to the whispering gallery modes of two orthogonal polarizations with quality factors upto 3200 at room temperature. In order to identify the peaks in the observed mode structure, we have adopted the boundary-value solution to the problem of scattering of electromagnetic waves by a dielectric micro-cylinder. A strong enhancement in photoluminescence decay rates at high excitation power suggest the occurrence of amplified spontaneous emission from a single microtube. The evanescent field in these photonic structures extends a couple of micrometers into the surroundings providing the possibility for efficient coupling to an external photonic device.
We present the results of studies on small photonic microtube structures of less than 10 microns diameter. A new
technique based on vacuum assisted filtration is used to produce the microtube resonantors. Whispering gallery modes
are probed through the photoluminescence emission from the glass material forming the cavity. We observe resonances
with polarized emission having quality factors up to 3000. These microresonator structures exhibit a large evanescent
field which makes them interesting for potential photonic applications.
This work reports synthesis and photochemical studies of 3,6-Bis(3,5-dimethylpyrazol-1-yl)-tetrazine ligand (dmptz) and its Cu(I) complex. Dmptz was found to be an excellent bridging ligand for Cu(I) complexes. The Cu(I) complex has been shown to have a dinuclear structure where a single dmptz ligand links two metal centers. It is apparent that the methyl groups of dmptz have a large steric effect on the structure of the complexes preventing the formation of larger tetra- or penta- nuclear complexes reported in the literature for similar ligands (bptz). We have shown that Cu(I) dmptz complexes possess interesting luminescent properties, that might be potentially used to prepare new luminescent materials for sensing and energy conversion applications.
Porous materials in general have received great attention from the last century. The development of new porous materials and the preparation of new composites based on porous materials is a subject of interest. The development of porous silicon based optical composite materials opened up new ways of incorporating optically active sol-gel materials into porous silicon. High purity silica optical fibres allow the most rapid and efficient data transmission. The objective of this work is to develop micro-channel glass / porous silicon-rare earth doped xerogel and glass composites, which would serve as compact optical amplifiers and delay line devices. Micro-channel glass / porous silicon-xerogel composites have been prepared by incorporation of sol-gel prepared from tetraethoxysilane, aluminium iso-propoxide and europium chloride into the porous matrix. Both xerogel and glass composites have been studied by various techniques such as FTIR, micro-Raman, photoluminescence spectroscopy, EDX and Scanning Electron Microscopy (SEM).
In this study CdTe quantum dots have been successfully prepared in aqueous medium using several different thiol stabilizers. The resulting nanocrystals were purified and the photoluminescence efficiency was subsequently enhanced through post preparative procedures such as photochemical etching and ageing. An optical study was carried out on the resulting CdTe nanocrystals as proof as their improvement. Preliminary tests of the thiol stabilised QDs as potential biolabels have been performed. It has been shown that L-cysteine stabilised QDs localising to the outer cell membrane in living cells. TGA stabilised CdTe QDs can potentially serve as live cell imaging tools as they exhibit strong luminescence and excellent photostability. In addition, the ability of TGA stabilised CdTe QDs to traverse the cell membrane of macrophages is a formidable quality that may potentially be harnessed for imaging and therapeutics. Modulating the delivery of QDs to subcellular locations in living cells opens a myriad of potential applications ranging from drug delivery to examination of intracellular processes.
Magnetite nanoparticles have been coated by a porphyrin derivative to produce new magnetic materials with fluorescent properties. The magnetic nanoparticles were prepared using two different methods, one based on sol-gel techniques and ultrasonic processing, and the other via a controlled chemical co-precipitation. Different types of porphyrin functionalised magnetic nanoparticles have been prepared and have been characterised by electron microscopy (TEM and SEM), XRD, FTIR, Raman, UV-vis, and fluorescence spectroscopy. Microscopy results showed the formation of core-shell nanostructures, with IR and photoluminescence spectroscopy results confirming the presence of porphyrin in the shell.
We report highly efficient Forster resonance energy transfer between CdTe nanocrystals and two different dyes, Rhodamine B and Oxazine, where the nanocrystals are mixed with the dyes on top of glass substrates. A faster NC decay curve is observed in the samples containing NCs mixed with dyes than in those containing NCs on their own. For the samples containing nanocrystals mixed with Rhodamine B, room temperature PL measurements are presented as a function of the ratio between the amount of acceptors and the amount of donors, CA/CD. This ratio is varied between 0.03 and 5. The strongest enhancement of the acceptor PL intensity relative to that of the donor PL intensity is reached for 0.2A/CD<5, suggesting that most efficient FRET is also achieved in this region.
The discovery of room temperature photoluminescence in porous silicon has opened up a range of applications for this material in new areas such as optical, photodetector, photovoltaic, micromachine and sensors. For this reason there have been significant efforts in recent years directed at modification of silicon surfaces via formation of Si-C and Si-O-E (E = H, C, N) bonds on the silicon surfaces. However, research on bonding of metallorganic fragments to the silicon surface is scant. The main objectives of our work are to develop and investigate new ways of specific chemical bonding of selected metallorganic compounds to the Si surface and to prepare new types of silicon-based materials. New metallorganic composites have been developed on macro- and micro- porous silicon surfaces. The silicon surfaces have been effectively modified using inorganic and organometallic chemistry approaches. The work includes: (i) preparation and investigation of Cl-, HO-, and Cp- modified porous Si-surfaces; (ii) preparation and characterisation of iron oxide layers
on porous silicon; (iii) characterization of metallorganic layers on porous silicon by FTIR, EDX and Scanning Electronic Microscopy (SEM). There are strong possibilities that those composite materials will have a wide range of applications in nano-technology and optoelectronics.
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