Adsorption of mercaptosilanes on nanocrystalline and single crystal zinc oxide surfaces

Singh, Jagdeep; Im, Jisun; Whitten, James E.; Soares, Jason W.; Meehan, Alexa M.; Steeves, Diane M.

doi:10.1117/12.794805

Cited by 18 publications

(12 citation statements)

References 15 publications

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“…This could be in part due to a 'dilution effect' caused by the high percentage of non-emitting thiol species, or due to a specific chemical interaction with the nano-ZnO. We also recently demonstrated the ability to modify nano-ZnO with a so-called 'mixed modifier' possessing both silane and thiol functionalities, such as 3-mercaptopropyltrimethoxysilane 14 . The inherent PL emission of the nano-ZnO was affected in a combinatorial manner, reflecting the influence of both the silane and thiol modifiers independently; that is the UV emission band was increased while the visible was partially quenched.…”

Section: Introductionmentioning

confidence: 96%

Effect of surface modification on the optical properties of nanocrystalline zinc oxide materials

Soares

Steeves

Singh

et al. 2010

Oxide-Based Materials and Devices

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The wide band gap and unique photoluminescence (PL) spectrum of nanocrystalline zinc oxide (nano-ZnO) make it useful for a variety of photonics and sensor applications. Toward the goal of modifying the electronic structure and optical properties of nano-ZnO, nanorods were functionalized with electron withdrawing organosilanes, 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDS) and pentafluorophenyltriethoxysilane (PFS), and a partially conjugated heterobifunctional molecule, p-maleimidophenyl isothiocyanate (PMPI). Fourier transform infrared (FTIR) spectroscopy and x-ray photoelectron spectroscopy (XPS) confirmed the presence of the modifiers on the nano-ZnO surface and verified covalent attachment. PL spectroscopy was performed to evaluate the influence of the modifiers on the nano-ZnO inherent optical behavior. An increase in the nano-ZnO near-band edge emission (UV) was evident for the organosilane modifiers, despite their differing electronic structures, while the defect emission (visible) remained unchanged. However, surface modification with the non-silane modifier PMPI resulted in unaltered UV and visible emission intensity. The varying influence of the modifiers may be due to the absence of a silane group in the PMPI, allowing for more efficient electron transport to the modifier. The influence of size/shape of the nanocrystalline ZnO was also examined by reacting spherical nanoparticles with PFDS. Preliminary results indicate that PFDS modification of the nanospheres resulted in similar PL behavior as the nanorods; although, the inherent PL of the spheres differs from the nanorods. These studies will elucidate the role of modifier structure on surface-modified nano-ZnO optical behavior, so that optical tailoring of the nano-ZnO inherent PL can be realized.

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Section: Introductionmentioning

confidence: 96%

Effect of surface modification on the optical properties of nanocrystalline zinc oxide materials

Soares

Steeves

Singh

et al. 2010

Oxide-Based Materials and Devices

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“…Various experiments, including ones in our laboratories, have demonstrated that underivatized alkanethiols chemisorb onto zinc oxide [13][14][15][16][17][18][19][20][21], and quantum mechanical modeling confirms chemisorption [22]. In contrast, however, FTIR measurements on ZnO nanotips indicate an absence of hexanethiol adsorption [23].…”

Section: Introductionmentioning

confidence: 96%

Chemisorption of a thiol-functionalized ruthenium dye on zinc oxide nanoparticles: Implications for dye-sensitized solar cells

Singh¹,

Im²,

Whitten³

et al. 2010

Chemical Physics Letters

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Soares, Jason W.; and Steeves, Diane M., "Chemisorption of a thiol-functionalized ruthenium dye on zinc oxide nanoparticles: Implications for dye-sensitized solar cells" (2010 [4-thiopyridine] onto ZnO nanorods has been studied using X-ray and ultraviolet photoelectron spectroscopies (XPS and UPS). XPS indicates chemisorption with a surface density of ca. 1 Â 10 15 molecules/cm 2 , confirming the possibility of using thiol-terminated dyes for ZnO-based DSSC devices. The energy level diagram, based on UPS and absorbance spectroscopy, indicates that the LUMO of this dye is lower in energy than the ZnO conduction band edge, providing minimal enthalpic driving force for photovoltaic electron injection. However, optimization of thiol-functionalized Ru dyes could result in competitive ZnO-based DSSCs.

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“…Even more, the pHdependence of the Zeta potential of any sample is rarely determined over the full pH range, yet only its full assessment (Shang et al 2012;Garvas et al 2015) would allow predicting the surface charge of the nanoparticles in various cellular compartments with varying pH-for instance, in the phagolysosome (Cho et al 2012); such information can predictably impact the interpretation of experimental results. Besides Zeta potential, many other experimental methods can also test the success of the nanoparticle' surface functionalization: Fourier transform infrared spectroscopy (FTIR) (Soares et al 2006;Singh et al 2008;Chen and Yakovlev 2010;Zhao et al 2012;Killian 2013;Garvas et al 2015), high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) (Garvas et al 2015;Jiang et al 2020), secondary ion mass spectrometry (SIMS) (Killian 2013), energy dispersive Xray spectroscopy (EDX) (Killian 2013), and/or X-ray photoelectron spectroscopy (XPS) (Soares et al 2006;Singh et al 2008). Although crucial, such a step is often omitted.…”

Section: Introductionmentioning

confidence: 99%

How to control fluorescent labeling of metal oxide nanoparticles for artefact-free live cell microscopy

Kokot

Umek

et al. 2021

Nanotoxicology

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Nanotechnologies hold great promise for various applications. To predict and guarantee the safety of novel nanomaterials, it is essential to understand their mechanism of action in an organism, causally connecting adverse outcomes with early molecular events. This is best investigated using noninvasive advanced optical methods, such as high-resolution live-cell fluorescence microscopy, which require stable labeling of nanoparticles with fluorescent dyes. However, as shown here, when the labeling is performed inadequately, unbound fluorescent dyes and inadvertently altered chemical and physical properties of the nanoparticles can result in experimental artefacts and erroneous conclusions. To prevent such unintentional errors, we introduce a tested minimal combination of experimental methods to enable artefact-free fluorescent labeling of metal-oxide nanoparticles-the largest subpopulation of nanoparticles by industrial production and applications-and demonstrate its application in the case of TiO 2 nanotubes. We (1) characterize potential changes of the nanoparticles' surface charge and morphology that might occur during labeling by using zeta potential measurements and transmission electron microscopy, respectively, and (2) assess stable binding of the fluorescent dye to the nanoparticles with either fluorescence intensity measurements or fluorescence correlation spectroscopy, which ensures correct nanoparticle localization. Together, these steps warrant the reliability and reproducibility of advanced optical tracking, which is necessary to explore nanomaterials' mechanism of action and will foster widespread and safe use of new nanomaterials.

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Adsorption of mercaptosilanes on nanocrystalline and single crystal zinc oxide surfaces

Cited by 18 publications

References 15 publications

Effect of surface modification on the optical properties of nanocrystalline zinc oxide materials

Effect of surface modification on the optical properties of nanocrystalline zinc oxide materials

Chemisorption of a thiol-functionalized ruthenium dye on zinc oxide nanoparticles: Implications for dye-sensitized solar cells

How to control fluorescent labeling of metal oxide nanoparticles for artefact-free live cell microscopy

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