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Device Fabrication and Photosensitizing Role of ZnO Nanostructures in Photodynamic Therapy of Cancer
Linköping University, Department of Science and Technology. Linköping University, The Institute of Technology.
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In nanoscience and nanotechnology, zinc oxide (ZnO) is gaining much research attention due to direct wide band gap (3.3 eV), large exciton binding energy (60 meV), and deep level defects emissions that cover the whole visible range. ZnO nanorods (NRs) in comparison to normal bio molecules and large surface area to volume ratio, allow them to interact within the cell thus are used as convincing intracellular carriers of photosensitizers. Vertical NRs are wave guiding cavities enhancing the light extraction efficiency from devices and are stable photosensitizing agents with their biophotonic, and biodegradation properties, therefore are appealing candidates for the photodynamic therapy of cancer.

The heterojunction LEDs of ZnO NRs/p-GaN are best choice to take the advantage of GaN ideal blue-light emission and fabricated LEDs explore the potential of white LEDs with superior performance. The main objective of this thesis is not only to fabricate ZnO NRs/p-GaN, or ZnO nanotubes (ZNTs)/p-GaN heterostructures, but also to investigate their optical properties for photodynamic therapy. These LEDs have showed enhanced EL intensity covering the visible band (425–750 nm).

ZnO nanorods are grown on the borosilicate glass capillaries (0.7 μm diameter) and then conjugated with photosensitizer. Such glass capillaries having ZnO nanorods complex with photosensitizer on them are used as pointer for intracellular mediated photochemistry in cells to achieve their necrosis. Mitochondrial staining of melanoma and foreskin fibroblast cells was done by Mitotracker Red with the aim of targeting the specific organelle with the prepared ZnO nanowires (NWs) Femtotip to see ROS production. Cytotoxic effects of nanometallic oxides e.g. ZnO-NRs, MnO2 NRs, and Fe2O3 NPs individually and their ligands with photosensitizers in osteosarcoma (U2OS) cells are also explored. Thus bare and ligands of nanometallic oxides, with particular focus of ZnO nanowires are having significant and convincing cytotoxic effects via the liberation of reactive oxygen species as well as Zn+2 ions in labeled cells, thus can be assigned as anticancer agents for breast cancer, melanoma cancer and osteosarcoma cells.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press , 2011. , 56 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1392
Keyword [en]
Zinc oxide nanostructures, light emitting diodes, reactive oxygen species, photosensitizer, cancer cell, photodynamic therapy
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-71319ISBN: 978-91-7393-083-3 (print)OAI: oai:DiVA.org:liu-71319DiVA: diva2:447267
Public defence
2011-10-21, K2, Kåkenhus, Campus Norrköping, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2011-10-11 Created: 2011-10-11 Last updated: 2014-01-15Bibliographically approved
List of papers
1. Electro-optical and Cathodoluminescence properties of low temperature grown ZnO nanorods/p-GaN white light emitting diodes
Open this publication in new window or tab >>Electro-optical and Cathodoluminescence properties of low temperature grown ZnO nanorods/p-GaN white light emitting diodes
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2010 (English)In: PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE, ISSN 1862-6300, Vol. 207, no 1, 67-72 p.Article in journal (Refereed) Published
Abstract [en]

Vertically aligned ZnO nanorods (NRs) with a diameter in the range of 160-200 nm were grown on p-GaN/sapphire substrates by aqueous chemical growth technique and white light emitting I diodes (LEDs) are fabricated. The properties of this LED were investigated by parameter analyzer, cathodoluminescence (CL), electroluminescence (EL), and photoluminescence (PL). The I-V characteristics of the fabricated ZnO/GaN heterojunction revealed rectifying behavior and the LED emits visible EL when bias is applied. From the CL it was confirmed that both the ZnO NRs and the p-GaN are contributing to the observed peaks. The observed EL measurements showed two emission hands centered at 450 nm and a second broad deep level defect related emission centered at 630 nm and extending from 500 rim and up to over 700 rim. Moreover, the room temperature PL spectrum of the ZnO NRs/p-GaN reveals an extra peak at the green color wavelength centered at 550 nm. Comparison of the PL, CL, and EL data suggest that the blue and near red emissions in the EL spectra are originating from Mg acceptor levels in the p-GaN and from the deep levels defects present in the ZnO NRs, respectively. The mixture of high and low energy colors, i.e., blue, green, and red, has led to the white observed luminescence.

National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-54058 (URN)10.1002/pssa.200925393 (DOI)000274280900010 ()
Available from: 2010-02-22 Created: 2010-02-22 Last updated: 2014-01-15
2. A comparative study of the electrodeposition and the aqueous chemical growth techniques for the utilization of ZnO nanorods on p-GaN for white light emitting diodes
Open this publication in new window or tab >>A comparative study of the electrodeposition and the aqueous chemical growth techniques for the utilization of ZnO nanorods on p-GaN for white light emitting diodes
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2011 (English)In: Superlattices and Microstructures, ISSN 0749-6036, E-ISSN 1096-3677, Vol. 49, no 1, 32-42 p.Article in journal (Refereed) Published
Abstract [en]

Vertically well aligned zinc oxide nanorods (ZnO NRs) were grown on p-GaN by electrodeposition (ED) and aqueous chemical growth (ACG) techniques and the structures were employed to fabricate white light emitting diodes (LEDs). Room temperature current voltage (IV), photoluminescence (PL), and electroluminescence (EL) measurements were performed to investigate and compare both LEDs. In general, the IV characteristics and the PL spectra of both LEDs were rather similar. Nevertheless, the EL of the ED samples showed an extra emission peak shoulder at 730 nm. Moreover, at the same injection current, the EL spectrum of the ED light emitting diode showed a small UV shift of 12 nm and its white peak was found to be broader when compared to the ACG grown LED. The broadening of the EL spectrum of the LED grown by ED is due to the introduction of more radiative deep level defects. The presented LEDs have shown excellent color rendering indexes reaching a value as high as 95. These results indicate that the ZnO nanorods grown by both techniques possess very interesting electrical and optical properties but the ED is found to be faster and more suitable for the fabrication of white LEDs.

Place, publisher, year, edition, pages
Elsevier, 2011
Keyword
ZnO nanorods; GaN; Chemical growth; White light emitting diodes
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-71312 (URN)10.1016/j.spmi.2010.10.004 (DOI)
Available from: 2011-10-11 Created: 2011-10-11 Last updated: 2017-12-08Bibliographically approved
3. White Electroluminescence Using ZnO Nanotubes/GaN Heterostructure Light-Emitting Diode
Open this publication in new window or tab >>White Electroluminescence Using ZnO Nanotubes/GaN Heterostructure Light-Emitting Diode
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2010 (English)In: NANOSCALE RESEARCH LETTERS, ISSN 1931-7573, Vol. 5, no 6, 957-960 p.Article in journal (Refereed) Published
Abstract [en]

We report the fabrication of heterostructure white light-emitting diode (LED) comprised of n-ZnO nanotubes (NTs) aqueous chemically synthesized on p-GaN substrate. Room temperature electroluminescence (EL) of the LED demonstrates strong broadband white emission spectrum consisting of predominating peak centred at 560 nm and relatively weak violet-blue emission peak at 450 nm under forward bias. The broadband EL emission covering the whole visible spectrum has been attributed to the large surface area and high surface states of ZnO NTs produced during the etching process. In addition, comparison of the EL emission colour quality shows that ZnO nanotubes have much better quality than that of the ZnO nanorods. The colour-rendering index of the white light obtained from the nanotubes was 87, while the nanorods-based LED emit yellowish colour.

Place, publisher, year, edition, pages
Springer Science Business Media, 2010
Keyword
ZnO nanotubes, Light-emitting diodes, Electroluminescence, Lightning, White light sources
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-57167 (URN)10.1007/s11671-010-9588-z (DOI)000278096000008 ()
Available from: 2010-06-11 Created: 2010-06-11 Last updated: 2014-09-25
4. Intracellular ZnO Nanorods Conjugated with Protoporphyrin for Local Mediated Photochemistry and Efficient Treatment of Single Cancer Cell
Open this publication in new window or tab >>Intracellular ZnO Nanorods Conjugated with Protoporphyrin for Local Mediated Photochemistry and Efficient Treatment of Single Cancer Cell
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2010 (English)In: NANOSCALE RESEARCH LETTERS, ISSN 1931-7573, Vol. 5, no 10, 1669-1674 p.Article in journal (Refereed) Published
Abstract [en]

ZnO nanorods (NRs) with high surface area to volume ratio and biocompatibility is used as an efficient photosensitizer carrier system and at the same time providing intrinsic white light needed to achieve cancer cell necrosis. In this letter, ZnO nanorods used for the treatment of breast cancer cell (T47D) are presented. To adjust the sample for intracellular experiments, we have grown the ZnO nanorods on the tip of borosilicate glass capillaries (0.5 mu m diameter) by aqueous chemical growth technique. The grown ZnO nanorods were conjugated using protoporphyrin dimethyl ester (PPDME), which absorbs the light emitted by the ZnO nanorods. Mechanism of cytotoxicity appears to involve the generation of singlet oxygen inside the cell. The novel findings of cell-localized toxicity indicate a potential application of PPDME-conjugated ZnO NRs in the necrosis of breast cancer cell within few minutes.

Place, publisher, year, edition, pages
Springer Science Business Media, 2010
Keyword
ZnO nanorods, Cancer cell necrosis, Photodynamic therapy, Protoporphyrin dimethyl ester
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-61180 (URN)10.1007/s11671-010-9693-z (DOI)000283124800022 ()21076704 (PubMedID)
Available from: 2010-11-05 Created: 2010-11-05 Last updated: 2014-09-25
5. Investigation of the phototoxic effect of ZnO nanorods on fibroblasts and melanoma human cells
Open this publication in new window or tab >>Investigation of the phototoxic effect of ZnO nanorods on fibroblasts and melanoma human cells
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2014 (English)In: Laser Physics Letters, ISSN 1612-2011, E-ISSN 1612-202X, Vol. 11, no 11, 115606Article in journal (Refereed) Published
Abstract [en]

Photo-cytotoxicity of zinc oxide (ZnO) nanowires (NWs) either bare or conjugated with photosensitizers was studied in dark and after ultraviolet light exposure, in human melanoma and foreskin fibroblast cells. ZnO NWs were grown on the capillary tip and then coated with photosensitizer. This coated tip was used as pointer for intracellular insertion of ZnO NWs and photosensitizer. ZnO NWs pointer was inserted into a specific cell and then irradiated with ultraviolet (UVA), which led to loss of mitochondrial membrane potential, as estimated by loss of the Mitotracker Red staining. Dissolved ZnO NWs showed cytotoxicity as detected by MTT viability assay and morphological evaluation. UVA-irradiation enhanced the toxicity and caused the production of reactive oxygen species (ROS) resulting in cell necrosis. ZnO NWs were photo-toxic for both normal and cancer cells, questioning their bio-safety.

Place, publisher, year, edition, pages
Institute of Physics (IOP), 2014
Keyword
ZnO nanowires, photodynamic therapy, reactive oxygen species, δ- Aminolevulinic acid, protoporphyrin 1X
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-71316 (URN)10.1088/1612-2011/11/11/115606 (DOI)
Note

The previous status of this article was Manuscript and the working title was Photo toxicity of Zinc Oxide Nanowires in Human Melanoma and Fibroblast Cells.

Available from: 2011-10-11 Created: 2011-10-11 Last updated: 2017-08-30Bibliographically approved
6. Biotoxicity of nanometallic oxides and their ligands with photosensitizers in osteosarcom a cells
Open this publication in new window or tab >>Biotoxicity of nanometallic oxides and their ligands with photosensitizers in osteosarcom a cells
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

The cytotoxic effects in osteosarcoma (U2OS) cells to different nanosized metallic oxides e.g. zinc oxide nanowires (ZnO-NWs), manganese di-oxide nanowires (MnO2 NWs), ferric oxide nanoparticles (Fe2O3 NPs) individually and their complex forms with photosensitizers photofrin®, 5-Aminolevulinic acid (5-ALA), and protoporphyrin IX (Pp IX) were studied. The cellular effects were assayed by analyzing the cellular morphology. The reactive oxygen species (ROS) were detected using 2', 7'-Dichlorofluorescein diacetate, and cell viability were assessed using MTT assay under ultraviolet (UV), visible light and laser exposed conditions. Prominent cell death with above cited nanomaterials in their complex forms with photosensitizer was observed in labeled U2OS cells. This cell death might be due to their synergetic effect via the release of singlet oxygen species in osteosarcoma cells showing their anticancer-cell effects.

Keyword
Osteosarcoma cell, reactive oxygen species (ROS), MTT assay, photodynamic therapy (PDT)
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-71317 (URN)
Available from: 2011-10-11 Created: 2011-10-11 Last updated: 2014-01-15Bibliographically approved

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