Upconverting and NIR emitting rare earth based nanostructures for NIR-bioimaging Eva Hemmer, Nallusamy Venkatachalam, Hiroshi Hyodo, Akito Hattori, Yoshie Ebina, Hidehiro Kishimoto, Kohei Soga Nanoscale, 2013 In recent years, significant progress was achieved in the field of nanomedicine and bioimaging, but the development of new biomarkers for reliable detection of diseases at an early stage, molecular imaging, targeting and therapy remains crucial. The disadvantages of commonly used organic dyes include photobleaching, autofluorescence, phototoxicity and scattering when UV (ultraviolet) or visible light is used for excitation. The limited penetration depth of the excitation light and the visible emission into and from the biological tissue is a further drawback with regard to in vivo bioimaging. Lanthanide containing inorganic nanostructures emitting in the near-infrared (NIR) range under NIR excitation may overcome those problems. Due to the outstanding optical and magnetic properties of lanthanide ions (Ln(3+)), nanoscopic host materials doped with Ln(3+), e.g. Y2O3:Er(3+),Yb(3+), are promising candidates for NIR-NIR bioimaging. Ln(3+)-doped gadolinium-based inorganic nanostructures, such as Gd2O3:Er(3+),Yb(3+), have a high potential as opto-magnetic markers allowing the combination of time-resolved optical imaging and magnetic resonance imaging (MRI) of high spatial resolution. Recent progress in our research on over-1000 nm NIR fluorescent nanoprobes for in vivo NIR-NIR bioimaging will be discussed in this review.
Er 3+-doped y 2 O 3 nanophosphors for near-infrared fluorescence bioimaging applications Nallusamy Venkatachalam, Tomoyoshi Yamano, Eva Hemmer, Hiroshi Hyodo, Hidehiro Kishimoto, Kohei Soga Journal of the American Ceramic Society, 2013 Rare‐earth‐doped ceramic nanophosphor ( RED ‐ CNP ) materials are promising near‐infrared ( NIR ) fluorescence bioimaging ( FBI ) agents that can overcome problems of currently used organic dyes including photobleaching, phototoxicity, and light scattering. Here, we report a NIR – NIR bioimaging system by using NIR emission at 1550 nm under 980 nm excitation which can allow a deeper penetration depth into biological tissues than ultraviolet or visible light excitation. In this study, erbium‐doped yttrium oxide nanoparticles ( Er 3+ : Y 2 O 3 ) with an average particle size of 100 and 500 nm were synthesized by surfactant‐assisted homogeneous precipitation method. NIR emission properties of Er 3+ : Y 2 O 3 were investigated under 980 nm excitation. The surface of Er 3+ : Y 2 O 3 was electrostatically PEG ylated using poly (ethylene glycol)‐ b ‐poly(acrylic acid) ( PEG ‐ b ‐ PAAc ) block copolymer to improve the chemical durability and dispersion stability of Er 3+ : Y 2 O 3 under physiological conditions. In vitro cytotoxic effects of bare and PEG ‐ b ‐ PAAc ‐modified Er 3+ : Y 2 O 3 were investigated by incubation with mouse macrophage cells (J774). Microscopic and macroscopic FBI were demonstrated in vivo by injection of bare or PEG ‐ b ‐ PAAc ‐modified Er 3+ : Y 2 O 3 into C57BL/6 mice. The NIR fluorescence images showed that PEG ‐ b ‐ PAAc modification significantly reduced the agglomeration of Er 3+ : Y 2 O 3 in mice and enhanced the distribution of Er 3+ :Y 2 O 3 .
The role of pH in PEG-b-PAAc modification of gadolinium oxide nanostructures for biomedical applications Eva Hemmer, Nallusamy Venkatachalam, Hiroshi Hyodo, Kohei Soga Advances in Materials Science and Engineering, 2012 Upconversion and near-infrared emitting Gd2O3:Er3+,Yb3+nanostructured phosphors (nanoparticles and nanorods) for applications in bioimaging have been synthesized by precipitation methods and hydrothermal treatment. Variation of the material synthesis conditions (additives and pH) allows controlling particle size (40 nm to μm range) and rod aspect ratio (5 to 18). It was shown that PEG-b-PAAc (poly(ethylene glycol) poly(acrylic acid) block polymer) is suitable to provide the required chemical durability, dispersion stability, and noncytotoxic behaviour for biomedical applications, where the coating of Gd2O3with a protecting and biocompatible layer is essential in order to prevent the release of toxic Gd3+ions. Physicochemical properties of the Gd2O3:Er3+,Yb3+nanostructures modified with PEG-b-PAAc have been investigated by TG-DTA, FT-IR, and DLS revealing a strong influence of modification conditions, namely, pH of the reaction media, on the nature of the PEG-b-PAAc layer.
Application of ceramic phosphors for near infrared biomedical imaging technologies Kohei Soga, Kimikazu Tokuzen, Kosuke Tsuji, Tomoyoshi Yamano, Nallusamy Venkatachalam, Hiroshi Hyodo, Hidehiro Kishimoto Proceedings of SPIE the International Society for Optical Engineering, 2010 Near infrared wavelength region between 0.8 and 2 μm is an attractive region for biomedical imaging due to the low loss in biomedical objects in the region. Rare-earth doped ceramic phosphors are known to emit efficient fluorescence in the same wavelength region. The authors have developed micro fluorescence bioimaging system for cellular or tissue imaging and macro one for in vivo imaging. This paper will review the materials synthesis for the near infrared fluorescence probes as well as the system development and demonstrative works. Er-doped or Yb/Er-doped ceramic phosphors were synthesized with required particle size. The phosphors were partly modified with polyethylene glycol to give dispersion and controlled interaction with the biological objects. By using the micro imaging system, nematodes, mouse tissue and M1 cells were observed by detecting 1.5 μm emission from Er doped in the ceramic phosphor. in vivo imaging with the same fluorescence scheme was also performed for the digestive organs of live mouse.
Synthesis of Er3+ doped Y2O3 nanophosphors Nallusamy Venkatachalam, Yu Saito, Kohei Soga Journal of the American Ceramic Society, 2009 The synthesis and characterization of yttrium hydroxyl carbonate (Y(OH)CO 3 2− ) and yttrium nitrate hydroxide hydrate (Y(OH)NO 3 H 2 O) precursor materials as well as Y 2 O 3 nanoparticles are reported. The resultant precursor particle size is about 10–12 nm with a narrow size distribution by the enzymatic decomposition method, whereas the particle size was smaller than those acquired by the homogeneous and alkali precipitation methods. The formation of Y(OH)CO 3 2− and Y(OH)NO 3 H 2 O species was also evident from the fourier‐transform infrared spectrometry (FT‐IR) analysis. Precipitated Y(OH)CO 3 2− precursors have an amorphous nature whereas Y(OH)NO 3 H 2 O precursors have a crystalline nature, which was manifested from the XRD analysis. Moreover, precipitated Y(OH)NO 3 H 2 O precursors were found in the agglomerated form and Y(OH)CO 3 2− was established in the monodispersed form, as determined from the FE‐SEM, TEM and DLS measurements. It was demonstrated that calcination of precursor materials at 900°C eventually removed the inorganic anions from the precursors and consequently produced crystalline Y 2 O 3 nanoparticles, which was evident from the XRD and FT‐IR analysis. The EDS analysis confirms Er 3+ doping in the Y 2 O 3 nanoparticles. The morphology and the size of the Y 2 O 3 nanoparticles are almost unchanged before and after the calcination.
Effect of K3PO4 addition as sintering inhibitor during calcination of Y2O3 nanoparticles K Soga, Y Okumura, K Tsuji, N Venkatachalam Journal of Physics Conference Series, 2009 Erbium-doped yttrium oxide nanoparticle is one of the most important for fluorescence bioimaging under near infrared excitation. Particle size of it below 100 nm is an important requirement for a cellular bioimaging. However, the synthesis with such small particles is difficult at the calcination temperature above 1200 °C due to the sintering and crystal growth of the particles. In this study, yttrium oxide nanoparticles with average size of 30 nm were successfully synthesized by using K3PO4 as a sintering inhibitor during the calcination. A single phase of cubic Y2O3 as the resultant material was confirmed by XRD, which was also confirmed to emit a bright upconversion emission under 980-nm excitation. Improvement of chemical durability due to the introduction of phosphate group on the surface of the Y2O3 particles is also reported.
Er 3+ ‐Doped Y 2 O 3 Nanophosphors for Near‐Infrared Fluorescence Bioimaging Applications N Venkatachalam, T Yamano, E Hemmer, H Hyodo, H Kishimoto, K Soga Journal of the American Ceramic Society 96 (9), 2759-2765 , 2013 2013 Citations: 61
Upconverting and NIR emitting rare earth based nanostructures for NIR-bioimaging E Hemmer, N Venkatachalam, H Hyodo, A Hattori, Y Ebina, H Kishimoto, ... Nanoscale 5 (23), 11339-11361 , 2013 2013 Citations: 390
Cytotoxic aspects of gadolinium oxide nanostructures for up-conversion and NIR bioimaging E Hemmer, T Yamano, H Kishimoto, N Venkatachalam, H Hyodo, K Soga Acta Biomaterialia 9 (1), 4734-4743 , 2013 2013 Citations: 91
In vitro and in vivo investigations of upconversion and NIR emitting Gd sub (2) O sub (3): Er super ( 3+), Yb super (3+) nanostructures for biomedical applications E Hemmer, H Takeshita, T Yamano, T Fujiki, Y Kohl, K Low, ... Journal of Materials Science: Materials in Medicine 23 (10), 2399-2412 , 2012 2012
In vitro and in vivo investigations of upconversion and NIR emitting Gd 2 O 3 :Er 3+ ,Yb 3+ nanostructures for biomedical applications E Hemmer, H Takeshita, T Yamano, T Fujiki, Y Kohl, K Löw, ... Journal of Materials Science: Materials in Medicine 23 (10), 2399-2412 , 2012 2012 Citations: 51
Synthesis and toxicity assay of ceramic nanophosphors for bioimaging with near-infrared excitation N Venkatachalam, E Hemmer, T Yamano, H Hyodo, H Kishimoto, K Soga Progress in crystal growth and characterization of materials 58 (2-3), 121-134 , 2012 2012 Citations: 25
The Role of pH in PEG‐ b ‐PAAc Modification of Gadolinium Oxide Nanostructures for Biomedical Applications E Hemmer, N Venkatachalam, H Hyodo, K Soga Advances in Materials Science and Engineering 2012 (1), 748098 , 2012 2012 Citations: 16
Application of ceramic phosphors for near infrared biomedical imaging technologies K Soga, K Tokuzen, K Tsuji, T Yamano, N Venkatachalam, H Hyodo, ... Optical Components and Materials VII 7598, 64-72 , 2010 2010 Citations: 35
Effect of K {sub 3} PO {sub 4} addition as sintering inhibitor during calcination of Y {sub 2} O {sub 3} nanoparticles K Soga, Y Okumura, K Tsuji, N Venkatachalam Journal of Physics. Conference Series (Online) 191 , 2009 2009
Bioimaging of M1 cells using ceramic nanophosphors: Synthesis and toxicity assay of Y 2 O 3 nanoparticles N Venkatachalam, Y Okumura, K Soga, R Fukuda, T Tsuji Journal of Physics: Conference Series 191 (1), 012002 , 2009 2009 Citations: 15
Effect of K 3 PO 4 addition as sintering inhibitor during calcination of Y 2 O 3 nanoparticles K Soga, Y Okumura, K Tsuji, N Venkatachalam Journal of Physics: Conference Series 191 (1), 012003 , 2009 2009 Citations: 9
Synthesis of Er 3+ Doped Y 2 O 3 Nanophosphors N Venkatachalam, Y Saito, K Soga Journal of the American Ceramic Society 92 (5), 1006-1010 , 2009 2009 Citations: 72
Synthesis of Ceramic Nanophosphors for Upconversion Bioimaging V Nallusamy, Y Okumura, K Soga Preprints of Annual Meeting of The Ceramic Society of Japan Preprints of … , 2009 2009
Sol–gel preparation and characterization of nanosize TiO2: Its photocatalytic performance N Venkatachalam, M Palanichamy, V Murugesan Materials Chemistry and Physics 104 (2-3), 454-459 , 2007 2007 Citations: 337
Sol–gel preparation and characterization of alkaline earth metal doped nano TiO2: Efficient photocatalytic degradation of 4-chlorophenol N Venkatachalam, M Palanichamy, V Murugesan Journal of Molecular Catalysis A: Chemical 273 (1-2), 177-185 , 2007 2007 Citations: 305
Alkaline earth metal doped nanoporous TiO2 for enhanced photocatalytic mineralisation of bisphenol-A N Venkatachalam, M Palanichamy, B Arabindoo, V Murugesan Catalysis Communications 8 (7), 1088-1093 , 2007 2007 Citations: 93
characterization of Zr"*^, La^^ and Ce^^ doped mesoporous TiOi: Evaluation of their photocatalytic activityMol N Venkatachalam, M Palanichamy, BM Arabindoo, S VJ Catal. A 266, 158 , 2007 2007 Citations: 29
Photocatalytic activity of ZnO impregnated Hβ and mechanical mix of ZnO/Hβ in the degradation of monocrotophos in aqueous solution S Anandan, A Vinu, N Venkatachalam, B Arabindoo, V Murugesan Journal of Molecular Catalysis A: Chemical 256 (1-2), 312-320 , 2006 2006 Citations: 158
Visible light active photocatalytic degradation of bisphenol-A using nitrogen doped TiO2 N Venkatachalam, A Vinu, S Anandan, B Arabindoo, V Murugesan Journal of nanoscience and nanotechnology 6 (8), 2499-2507 , 2006 2006 Citations: 53
Fine route for an efficient removal of 2, 4-dichlorophenoxyacetic acid (2, 4-D) by zeolite-supported TiO2 MV Shankar, S Anandan, N Venkatachalam, B Arabindoo, V Murugesan Chemosphere 63 (6), 1014-1021 , 2006 2006 Citations: 209
MOST CITED SCHOLAR PUBLICATIONS
Upconverting and NIR emitting rare earth based nanostructures for NIR-bioimaging E Hemmer, N Venkatachalam, H Hyodo, A Hattori, Y Ebina, H Kishimoto, ... Nanoscale 5 (23), 11339-11361 , 2013 2013 Citations: 390
Sol–gel preparation and characterization of nanosize TiO2: Its photocatalytic performance N Venkatachalam, M Palanichamy, V Murugesan Materials Chemistry and Physics 104 (2-3), 454-459 , 2007 2007 Citations: 337
Sol–gel preparation and characterization of alkaline earth metal doped nano TiO2: Efficient photocatalytic degradation of 4-chlorophenol N Venkatachalam, M Palanichamy, V Murugesan Journal of Molecular Catalysis A: Chemical 273 (1-2), 177-185 , 2007 2007 Citations: 305
Fine route for an efficient removal of 2, 4-dichlorophenoxyacetic acid (2, 4-D) by zeolite-supported TiO2 MV Shankar, S Anandan, N Venkatachalam, B Arabindoo, V Murugesan Chemosphere 63 (6), 1014-1021 , 2006 2006 Citations: 209
Photocatalytic activity of ZnO impregnated Hβ and mechanical mix of ZnO/Hβ in the degradation of monocrotophos in aqueous solution S Anandan, A Vinu, N Venkatachalam, B Arabindoo, V Murugesan Journal of Molecular Catalysis A: Chemical 256 (1-2), 312-320 , 2006 2006 Citations: 158
Novel thin‐film reactor for photocatalytic degradation of pesticides in an aqueous solution MV Shankar, S Anandan, N Venkatachalam, B Arabindoo, V Murugesan Journal of Chemical Technology & Biotechnology: International Research in … , 2004 2004 Citations: 100
Alkaline earth metal doped nanoporous TiO2 for enhanced photocatalytic mineralisation of bisphenol-A N Venkatachalam, M Palanichamy, B Arabindoo, V Murugesan Catalysis Communications 8 (7), 1088-1093 , 2007 2007 Citations: 93
Cytotoxic aspects of gadolinium oxide nanostructures for up-conversion and NIR bioimaging E Hemmer, T Yamano, H Kishimoto, N Venkatachalam, H Hyodo, K Soga Acta Biomaterialia 9 (1), 4734-4743 , 2013 2013 Citations: 91
Synthesis of Er 3+ Doped Y 2 O 3 Nanophosphors N Venkatachalam, Y Saito, K Soga Journal of the American Ceramic Society 92 (5), 1006-1010 , 2009 2009 Citations: 72
Er 3+ ‐Doped Y 2 O 3 Nanophosphors for Near‐Infrared Fluorescence Bioimaging Applications N Venkatachalam, T Yamano, E Hemmer, H Hyodo, H Kishimoto, K Soga Journal of the American Ceramic Society 96 (9), 2759-2765 , 2013 2013 Citations: 61
Visible light active photocatalytic degradation of bisphenol-A using nitrogen doped TiO2 N Venkatachalam, A Vinu, S Anandan, B Arabindoo, V Murugesan Journal of nanoscience and nanotechnology 6 (8), 2499-2507 , 2006 2006 Citations: 53
In vitro and in vivo investigations of upconversion and NIR emitting Gd 2 O 3 :Er 3+ ,Yb 3+ nanostructures for biomedical applications E Hemmer, H Takeshita, T Yamano, T Fujiki, Y Kohl, K Löw, ... Journal of Materials Science: Materials in Medicine 23 (10), 2399-2412 , 2012 2012 Citations: 51
Application of ceramic phosphors for near infrared biomedical imaging technologies K Soga, K Tokuzen, K Tsuji, T Yamano, N Venkatachalam, H Hyodo, ... Optical Components and Materials VII 7598, 64-72 , 2010 2010 Citations: 35
characterization of Zr"*^, La^^ and Ce^^ doped mesoporous TiOi: Evaluation of their photocatalytic activityMol N Venkatachalam, M Palanichamy, BM Arabindoo, S VJ Catal. A 266, 158 , 2007 2007 Citations: 29
Synthesis and toxicity assay of ceramic nanophosphors for bioimaging with near-infrared excitation N Venkatachalam, E Hemmer, T Yamano, H Hyodo, H Kishimoto, K Soga Progress in crystal growth and characterization of materials 58 (2-3), 121-134 , 2012 2012 Citations: 25
The Role of pH in PEG‐ b ‐PAAc Modification of Gadolinium Oxide Nanostructures for Biomedical Applications E Hemmer, N Venkatachalam, H Hyodo, K Soga Advances in Materials Science and Engineering 2012 (1), 748098 , 2012 2012 Citations: 16
Bioimaging of M1 cells using ceramic nanophosphors: Synthesis and toxicity assay of Y 2 O 3 nanoparticles N Venkatachalam, Y Okumura, K Soga, R Fukuda, T Tsuji Journal of Physics: Conference Series 191 (1), 012002 , 2009 2009 Citations: 15
Effect of K 3 PO 4 addition as sintering inhibitor during calcination of Y 2 O 3 nanoparticles K Soga, Y Okumura, K Tsuji, N Venkatachalam Journal of Physics: Conference Series 191 (1), 012003 , 2009 2009 Citations: 9
In vitro and in vivo investigations of upconversion and NIR emitting Gd sub (2) O sub (3): Er super ( 3+), Yb super (3+) nanostructures for biomedical applications E Hemmer, H Takeshita, T Yamano, T Fujiki, Y Kohl, K Low, ... Journal of Materials Science: Materials in Medicine 23 (10), 2399-2412 , 2012 2012
Effect of K {sub 3} PO {sub 4} addition as sintering inhibitor during calcination of Y {sub 2} O {sub 3} nanoparticles K Soga, Y Okumura, K Tsuji, N Venkatachalam Journal of Physics. Conference Series (Online) 191 , 2009 2009