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.2014 Feb 6;118(5):1319-26.
doi: 10.1021/jp409298f. Epub 2014 Jan 23.

The most effective gold nanorod size for plasmonic photothermal therapy: theory and in vitro experiments

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The most effective gold nanorod size for plasmonic photothermal therapy: theory and in vitro experiments

Megan A Mackey et al. J Phys Chem B..

Abstract

The development of new and improved photothermal contrast agents for the successful treatment of cancer (or other diseases) via plasmonic photothermal therapy (PPTT) is a crucial part of the application of nanotechnology in medicine. Gold nanorods (AuNRs) have been found to be the most effective photothermal contrast agents, both in vitro and in vivo. Therefore, determining the optimum AuNR size needed for applications in PPTT is of great interest. In the present work, we utilized theoretical calculations as well as experimental techniques in vitro to determine this optimum AuNR size by comparing plasmonic properties and the efficacy as photothermal contrast agents of three different sizes of AuNRs. Our theoretical calculations showed that the contribution of absorbance to the total extinction, the electric field, and the distance at which this field extends away from the nanoparticle surface all govern the effectiveness of the amount of heat these particles generate upon NIR laser irradiation. Comparing between three different AuNRs (38 × 11, 28 × 8, and 17 × 5 nm), we determined that the 28 × 8 nm AuNR is the most effective in plasmonic photothermal heat generation. These results encouraged us to carry out in vitro experiments to compare the PPTT efficacy of the different sized AuNRs. The 28 × 8 nm AuNR was found to be the most effective photothermal contrast agent for PPTT of human oral squamous cell carcinoma. This size AuNR has the best compromise between the total amount of light absorbed and the fraction of which is converted to heat. In addition, the distance at which the electric field extends from the particle surface is most ideal for this size AuNR, as it is sufficient to allow for coupling between the fields of adjacent particles in solution (i.e., particle aggregates), resulting in effective heating in solution.

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Figures

Figure 1
Figure 1
UV–vis spectra of AuNRs (black) as well as the NIR cw laserspectrum (red) (with corresponding TEM images, scale bar: 60 nm).(A) 38 × 11 nm AuNRs with longitudinal plasmon resonance at 740nm. (B) 28 × 8 nm AuNRs with longitudinal plasmon resonance at770 nm. (C) 17 × 5 nm AuNRs with longitudinal plasmon resonanceat 755 nm.
Figure 2
Figure 2
Photothermal heat conversion factor determined (per particle)forthe 17 × 5 nm AuNRs (17 nm, blue), 28 × 8 nm AuNRs (28 nm,yellow), and 38 × 11 nm AuNRs (38 nm, gray) at increasing NIRlaser irradiation time. All initial temperatures were 24 ± 1°C. Statistical significance (p < 0.05) indicatedby *.
Figure 3
Figure 3
Field contour plots for the longitudinal modeof the differentAuNRs, with particle dimensions indicated and the field decaying to1.25 at the extremities of each plot. (A) The field maximum of the38 × 10 nm AuNR (calculated at 804 nm) is 3500. (B) The fieldmaximum of the 25 × 7 nm AuNR (calculated at 761 nm) is 5220.(C) The field maximum of the 18 × 4 nm AuNR (calculated at 875nm) is 5480.
Figure 4
Figure 4
DDA extinction (black dots), absorption (red line), and scattering(green line, and shown in inset) spectra for the longitudinal modeof the different AuNRs in water. (A) The 38 × 10 nm AuNR hasan absorbance:scattering ratio of 63.8. (B) The 25 × 7 nm AuNRhas an absorbance:scattering ratio of 204. (C) The 18 × 4 nmAuNR has an absorbance:scattering ratio of 921.
Figure 5
Figure 5
Temperature change induced by plasmonic photothermal heatingofdifferent AuNRs (17, 28, and 38 nm in length) at different opticaldensities (0.5 and 1.5) and increasing NIR laser irradiation times.All initial temperatures were 24 ± 1 °C. Statistical significancebetween different sized AuNRs and optical densities at 2 min of laserirradiation (p < 0.5) is indicated by *.
Figure 6
Figure 6
Temperature change of the cell culture medium containing differentAuNRs. AuNRs 38 nm in length at OD 0.5 (light gray), AuNRs 28 nm inlength at OD 0.5 (yellow), AuNRs 17 nm in length at OD 0.5 (blue),and AuNRs 38 nm in length at OD 1.5 (dark gray) were all exposed toNIR laser irradiation at increasing lengths of time. All initial temperatureswere 32 ± 1 °C. Statistical significance between differentsized AuNRs and optical densities (p < 0.5) isindicated by * above bars.
Figure 7
Figure 7
Cell viability determined for HSC cells treated with differentAuNRs and subjected to PPTT via NIR laser irradiation. Cells treatedwith AuNRs 38 nm in length at OD 0.5 shown in light gray, AuNRs 28nm in length at OD 0.5 shown in yellow, AuNRs 17 nm in length at OD0.5 shown in blue, and AuNRs 38 nm in length at OD 1.5 shown in darkgray. Statistical significance (p < 0.05) indicatedby *. Statistical significance with respect to control (no AuNRs)indicated inside bars. Statistical significance between differenttreatments indicated above bars.
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