Optical characteristics and photothermal conversion of natural iron oxide colloid
© Kang et al.; licensee Springer. 2013
Received: 4 September 2013
Accepted: 17 October 2013
Published: 15 November 2013
Chemical compositions and spectroscopic characteristics of the natural floating colloids in brine mineral water were investigated in this study.
The natural colloidal materials were investigated using electron microscopy, X-ray crystallography, elemental analysis, and absorption and emission spectroscopies.
The natural colloidal particles have a spherical shape, with average diameter of 200 nm, and amorphous crystalline structure. The colloids are mostly composed of iron and oxygen atoms; they also contained small amounts of trace elements and rare earth minerals. In particular, the colloids show remarkable absorption and emission characteristics in the wide spectral region from ultraviolet (UV) to near infrared (NIR), which could make it useful in photoconversion and hyperthermal applications.
From the photothermal conversion efficiency measurement using an infrared thermography under irradiation of visible and NIR light, interestingly, it was found that the natural colloids have higher photothermal conversion efficiency, as compared with those of several different-typed minerals.
Brine mineral water (BMW) is defined as any spring water that is gushed out from the bedrock located within about 1 km from the coast generally. BMW is known to include more abundant mineral ingredients, such as calcium (Ca), magnesium (Mg), strontium (Sr), manganese (Mn), zinc (Zn), nickel (Ni), and iron (Fe) in comparison with other ocean deep water. Moreover, BMW has an excellent mineral balance similar to that of human body fluids (Kim et al. 2008; Moon et al. 2004). Recently, BMW drawn from 1,100 m below the coast terrace of Geumjin (GJ) area (Gangneung City, Republic of Korea) has attracted special attention because it contains several functional minerals such as selenium (Se) and vanadium (V). Moreover, it is confirmed that this BMW has the most suitable mineral balance for Ca and Mg particularly because it is helpful for absorbing Ca to the human body. Using this unique BMW from the GJ area (GJ BMW), many studies have been recently performed in the various fields of industry, like functional food, cosmetics, and medicine. Kim et al. (2010) reported for the effect of the GJ BMW on atopic dermatitis in vivo with atopic dermatitis model. They have shown that the GJ BMW can not only suppress the ear swelling induced by trimellitic anhydride (TMA) but also attenuate hyperactivated lymph nodes stimulated by TMA. Moreover, they reported that the growth of several kinds of cancer cells was inhibited by GJ BMW through a dose-dependent manner (Kim et al. 2009). Contrary to the various studies and the practical uses of the GJ BMW, however, the floating colloidal particles, which are observed in the GJ BMW, are still not well known. These colloidal particles are suspended in high concentration in the GJ BMW, and they cause the GJ BMW to have a unique opaque color like red wine. However, after several hours, the floating colloids are mostly deposited on the bottom by self-aggregation. By now, there has been no systematic study on these sediments. In this work, we report on the chemical compositions and spectroscopic properties of the natural colloidal particles in the GJ BMW. The optical properties of the colloidal particles were investigated by ultraviolet–visible (UV–vis) absorption and near-infrared photoluminescence (NIR-PL) spectroscopies and then their photothermal conversion characteristics were compared with those of the other mineral materials by infrared (IR) thermography. Here, we first report the unique optical characteristics of broad vis-NIR absorption and intense NIR emissions from the natural colloidal material. Interestingly, the colloidal material shows notable photothermal conversion property.
Morphology and composition characterization
To study the particle formation kinetics, dynamic light scattering (DLS) measurement values were examined using an electrophoretic light scattering spectrophotometer (ELS-8000, Otsuka Electronics Co., Ltd., Osaka, Japan). The shape and size of the GJ colloidal particles were analyzed using a field emission scanning electron microscope (FESEM, SU-70, Hitachi Ltd. Tokyo, Japan) operating at 15-kV accelerating voltage. Powder X-ray diffraction crystallography (XRD) patterns were obtained with an X-ray diffractometer (X'Pert Pro, PANalytical, Almelo, The Netherlands). Elemental composition was determined using an energy dispersive X-ray spectrometer (EDS) which is attached to the FESEM. More quantitative analysis of trace elements in the GJ colloidal particles was performed by inductive coupled plasma mass spectrophotometry (ICP-MS) (Elan DRCII, Perkin Elmer, Santa Clara, CA, USA) and inductively coupled plasma atomic emission spectrometry (ICP-AES) (JY Ultima2C, Jobin Yvon, Paris, France).
UV–vis absorption spectrum of the GJ colloidal particles which are dispersed in ethylene glycol was recorded immediately using an UV–vis spectrophotometer (S-3100, Scinco Co., Ltd., Seoul, South Korea) at room temperature. A conventional quartz cuvette of 1-cm optical path was used for the measurements.
NIR photoluminescence (PL) spectrum of the GJ colloidal particles was also measured on a spectrophotometer (iHRA-330 PL, Jobin Yvon, Horiba) equipped with a liquid nitrogen-cooled InGaAs photodetector in a wavelength range of 800 to 1500 nm with a monochromatic 580-nm light (Xe lamp) as an excitation source.
Photothermal conversion measurements
Halogen illuminator (FHL-101, 100 W, Asahi-Spectra Co., Ltd., Tokyo, Japan) was used as a visible-NIR light source. The illuminating light from FHL-101 was delivered to the surface of the sample by fiber optic ring light guide (MRG53-1000S, Moritex Corp., Saitama, Japan). The distance between the sample surface and the fiber optic ring was about 8 cm. The illumination power was fixed at 200 mW/cm2 at the sample surface. After light illumination, the temperature change of the samples was recorded using an infrared thermal camera (SC7600, FLIR Systems, Croissy-Beaubourg, France), every 10 s for 30 min. All the dispersed samples (10 mg/10 ml DI water) were placed in Teflon bath (10-mm diameter, 500 μl).
Results and discussion
Analysis of the GJ colloid powder by ICP-AES
Analysis of the GJ colloid powder by ICP-MS
We have investigated for the composition, structure, and optical characteristics, and photothermal conversion efficiency of the floating colloidal particles in brine mineral water at the Geumjin area. In this study, we first observed unique optical characteristics of broad vis-NIR absorption and intense NIR emissions from the natural colloidal material including additional co-doped elements. The colloidal material shows notable photothermal conversion efficiency compared to the other natural products. The obtained results show that the GJ colloidal particles would have distinctive promise for use in various fields, such as therapeutic and biomedical diagnosis applications in addition to conventional photothermal therapy.
This work was supported by a grant (no. PGB066) from the Catholic University of Korea (Seoul St. Mary's Hospital), a grant (no. K3208F) from the Korea Basic Science Institute (KBSI), and partly by a KRF grant (no. 2011–0008671). We thank the Korea Basic Science Institute, Seoul Center (Seoul, Korea) for the help with the ICP-AES and ICP-MS measurements.
- Carleer M, Jenouvrier A, Vandaele AC, Bernath PF, Me´rienne MF, Colin R, Zobov NF, Polyansky OL, Tennyson J, Savin VA: The near infrared, visible, and near ultraviolet overtone spectrum of water. J Chem Phys 1999, 111: 2444–2450. 10.1063/1.479859View ArticleGoogle Scholar
- Jackson WB, Amer NM, Boccara AC, Fournier D: Photothermal deflection spectroscopy and detection. Appl Optics 1981, 20: 1333–1344. 10.1364/AO.20.001333View ArticleGoogle Scholar
- Kim YJ, Jung IS, Song HJ, Choi EY, Choi IS, Choi YJ: Study of deep ground sea-like water on antioxidant activity and the immune response in RAW264.7 macrophages. J Life Sci 2008, 18: 329–335. 10.5352/JLS.2008.18.3.329View ArticleGoogle Scholar
- Kim WJ, Li H, Yoon TJ, Sim JM, Choi SK, Lee KH: Inhibitory activity of brine mineral water on counter cell growth, materials and angiogenesis. Korean J Food Nut 2009, 22: 542–547.Google Scholar
- Kim JJ, Kim WJ, Sim JM, Choi SK, Kwon SS, Kim JD, Lee KH: Effect of brine mineral water on TMA-induced contact hypersensitivity reaction in the mouse model. Korean J Food Nut 2010, 23: 440–445.Google Scholar
- Kwon SK, Kimijima K, Kanie K, Muramatsu A, Suzuki S, Matsubara E, Waseda Y: Inhibition of conversion process from Fe(OH) 3 to β-FeOOH and α-Fe 2 O 3 by the addition of silicate ions. ISIJ Int 2005, 45: 77–81. 10.2355/isijinternational.45.77View ArticleGoogle Scholar
- Lee SM, Park H, Yoo KH: Synergistic cancer therapeutic effects of locally delivered drug and heat using multifunctional nanoparticles. Adv Mater 2010, 22: 4049–4053. 10.1002/adma.201001040View ArticleGoogle Scholar
- Moon DS, Jung HJ, Kim HJ, Shin PK: Comparative analysis on resources characteristics of deep ocean water and brine groundwater. J Kor Soc Mar Environ Engi 2004, 7: 42–46.Google Scholar
- Ogawa M, Kosaka N, Choyke PL, Kobayashi H: In vivo molecular imaging of cancer with a quenching near-infrared fluorescent probe using conjugates of monoclonal antibodies and indocyanine green. Cancer Res 2009, 69: 1268–1272. 10.1158/0008-5472.CAN-08-3116View ArticleGoogle Scholar
- Park H, Yang J, Seo S, Kim K, Suh J, Kim D, Haam S, Yoo KH: Multifunctional nanoparticles for photothermally controlled drug delivery and magnetic resonance imaging enhancement. Small 2008, 4: 192–196. 10.1002/smll.200700807View ArticleGoogle Scholar
- Park H, Yang J, Lee J, Haam S, Choi IH, Yoo KH: Multifunctional nanoparticles for combined doxorubicin and photothermal treatments. ACS Nano 2009, 3: 2919–2926. 10.1021/nn900215kView ArticleGoogle Scholar
- Park JH, Von Maltzahn G, Xu MJ, Fogal V, Kotamraju VR, Ruoslahti E, Bhatia SN, Sailor MJ: Cooperative nanomaterial system to sensitize, target, and treat tumors. Proc Natl Acad Sci USA 2010, 107: 981–986. 10.1073/pnas.0909565107View ArticleGoogle Scholar
- Ronda C: Luminescence: from theory to applications. New York: Wiley; 2007.View ArticleGoogle Scholar
- Sharma R, Wendt JA, Rasmussen JC, Adams KE, Marshall MV, Sevick-Muraca EM: New horizons for imaging lymphatic function. Ann N Y Acad Sci 2008, 1131: 13–36. 10.1196/annals.1413.002View ArticleGoogle Scholar
- Sherlock SP, Tabakman SM, Xie L, Dai H: Photothermally enhanced drug delivery by ultrasmall multifunctional FeCo/graphitic shell nanocrystals. ACS Nano 2011, 5: 1505–1512. 10.1021/nn103415xView ArticleGoogle Scholar
- Weissleder R: A clearer vision for in vivo imaging. Nat Biotechnol 2001, 19: 316–317. 10.1038/86684View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.