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Title: Upconverting Nanoparticles as Optical Sensors of Nano- to Micro-Newton Forces

Abstract

Mechanical forces affect a myriad of processes, from bone growth to material fracture to touch-responsive robotics. While nano- to micro-Newton forces are prevalent at the microscopic scale, few methods have the nanoscopic size and signal stability to measure them in vivo or in situ. Here, we develop an optical force-sensing platform based on sub-25 nm NaYF 4 nanoparticles (NPs) doped with Yb 3+, Er 3+, and Mn 2+. The lanthanides Yb 3+ and Er 3+ enable both photoluminescence and upconversion, while the energetically coupled d-metal Mn 2+ adds force tunability through its crystal field sensitivity. IN using a diamond anvil cell to exert up to 3.5 GPa pressure or ~10 μN force per particle, we track stress-induced spectral responses. The red (660 nm) to green (520, 540 nm) emission ratio varies linearly with pressure, yielding an observed color change from orange to red for α-NaYF 4 and from yellow–green to green for d-metal optimized β-NaYF 4 when illuminated in the near infrared. We record consistent readouts over multiple pressure cycles and hours of illumination. With the nanoscopic size, a dynamic range of 100 nN to 10 μN, and photostability, these nanoparticles lay the foundation for visualizing dynamic mechanical processes, suchmore » as stress propagation in materials and force signaling in organisms.« less

Authors:
ORCiD logo [1];  [2];  [2];  [2]; ORCiD logo [3];  [4];  [5];  [2]
  1. Stanford Univ., CA (United States). Dept. of Applied Physics
  2. Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
  3. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
  4. Stanford Univ., CA (United States). Dept. of Molecular and Cellular Physiology
  5. Stanford Univ., CA (United States). Dept. of Geological Sciences
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
OSTI Identifier:
1390327
Grant/Contract Number:
FG02-99ER45775; SC0001293; 2013156180; AC02-06CH11357; AC02-76SF00515; NA0001974
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 7; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; crystal field theory; d-metal; diamond anvil cell; force sensor; lanthanides; upconversion

Citation Formats

Lay, Alice, Wang, Derek S., Wisser, Michael D., Mehlenbacher, Randy D., Lin, Yu, Goodman, Miriam B., Mao, Wendy L., and Dionne, Jennifer A. Upconverting Nanoparticles as Optical Sensors of Nano- to Micro-Newton Forces. United States: N. p., 2017. Web. doi:10.1021/acs.nanolett.7b00963.
Lay, Alice, Wang, Derek S., Wisser, Michael D., Mehlenbacher, Randy D., Lin, Yu, Goodman, Miriam B., Mao, Wendy L., & Dionne, Jennifer A. Upconverting Nanoparticles as Optical Sensors of Nano- to Micro-Newton Forces. United States. doi:10.1021/acs.nanolett.7b00963.
Lay, Alice, Wang, Derek S., Wisser, Michael D., Mehlenbacher, Randy D., Lin, Yu, Goodman, Miriam B., Mao, Wendy L., and Dionne, Jennifer A. Tue . "Upconverting Nanoparticles as Optical Sensors of Nano- to Micro-Newton Forces". United States. doi:10.1021/acs.nanolett.7b00963.
@article{osti_1390327,
title = {Upconverting Nanoparticles as Optical Sensors of Nano- to Micro-Newton Forces},
author = {Lay, Alice and Wang, Derek S. and Wisser, Michael D. and Mehlenbacher, Randy D. and Lin, Yu and Goodman, Miriam B. and Mao, Wendy L. and Dionne, Jennifer A.},
abstractNote = {Mechanical forces affect a myriad of processes, from bone growth to material fracture to touch-responsive robotics. While nano- to micro-Newton forces are prevalent at the microscopic scale, few methods have the nanoscopic size and signal stability to measure them in vivo or in situ. Here, we develop an optical force-sensing platform based on sub-25 nm NaYF4 nanoparticles (NPs) doped with Yb3+, Er3+, and Mn2+. The lanthanides Yb3+ and Er3+ enable both photoluminescence and upconversion, while the energetically coupled d-metal Mn2+ adds force tunability through its crystal field sensitivity. IN using a diamond anvil cell to exert up to 3.5 GPa pressure or ~10 μN force per particle, we track stress-induced spectral responses. The red (660 nm) to green (520, 540 nm) emission ratio varies linearly with pressure, yielding an observed color change from orange to red for α-NaYF4 and from yellow–green to green for d-metal optimized β-NaYF4 when illuminated in the near infrared. We record consistent readouts over multiple pressure cycles and hours of illumination. With the nanoscopic size, a dynamic range of 100 nN to 10 μN, and photostability, these nanoparticles lay the foundation for visualizing dynamic mechanical processes, such as stress propagation in materials and force signaling in organisms.},
doi = {10.1021/acs.nanolett.7b00963},
journal = {Nano Letters},
number = 7,
volume = 17,
place = {United States},
year = {Tue Jun 13 00:00:00 EDT 2017},
month = {Tue Jun 13 00:00:00 EDT 2017}
}

Journal Article:
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  • Mechanical forces affect a myriad of processes, from bone growth to material fracture to touch-responsive robotics. While nano- to micro-Newton forces are prevalent at the microscopic scale, few methods have the nanoscopic size and signal stability to measure them in vivo or in situ. Here, we develop an optical force-sensing platform based on sub-25 nm NaYF4 nanoparticles (NPs) doped with Yb3+, Er3+, and Mn2+. The lanthanides Yb3+ and Er3+ enable both photoluminescence and upconversion, while the energetically coupled d-metal Mn2+ adds force tunability through its crystal field sensitivity. Using a diamond anvil cell to exert up to 3.5 GPa pressuremore » or ~10 μN force per particle, we track stress-induced spectral responses. The red (660 nm) to green (520, 540 nm) emission ratio varies linearly with pressure, yielding an observed color change from orange to red for α-NaYF4 and from yellow–green to green for d-metal optimized β-NaYF4 when illuminated in the near infrared. Consistent readouts are recorded over multiple pressure cycles and hours of illumination. With the nanoscopic size, a dynamic range of 100 nN to 10 μN, and photostability, these nanoparticles lay the foundation for visualizing dynamic mechanical processes, such as stress propagation in materials and force signaling in organisms.« less
  • We report on improved image detectability for fluorescence diffuse optical tomography using upconverting nanoparticles doped with rare-earth elements. Core-shell NaYF{sub 4}:Yb{sup 3+}/Er{sup 3+}@NaYF{sub 4} upconverting nanoparticles were synthesized through a stoichiometric method. The Yb{sup 3+}/Er{sup 3+} sensitizer-activator pair yielded two anti-Stokes shifted fluorescence emission bands at 540 nm and 660 nm, here used to a priori estimate the fluorescence source depth with sub-millimeter precision. A spatially varying regularization incorporated the a priori fluorescence source depth estimation into the tomography reconstruction scheme. Tissue phantom experiments showed both an improved resolution and contrast in the reconstructed images as compared to not using any amore » priori information.« less
  • A class of biocompatible upconverting nanoparticles (UCNPs) with largely amplified red-emissions was developed. The optimal UCNP shows a high absolute upconversion quantum yield of 3.2% in red-emission, which is 15-fold stronger than the known optimal β-phase core/shell UCNPs. When conjugated to aminolevulinic acid, a clinically used photodynamic therapy (PDT) prodrug, significant PDT effect in tumor was demonstrated in a deep-tissue (>1.2 cm) setting in vivo at a biocompatible laser power density. Furthermore, we show that our UCNP–PDT system with NIR irradiation outperforms clinically used red light irradiation in a deep tumor setting in vivo. This study marks a major stepmore » forward in photodynamic therapy utilizing UCNPs to effectively access deep-set tumors.Lastly, it also provides an opportunity for the wide application of upconverting red radiation in photonics and biophotonics.« less
  • Highlights: {yields} In this article we have reported the formation of {gamma}-MnS nano/microcrystalline material by a novel proposed route. Na{sub 2}[Mn(HL){sub 2}(H{sub 2}O){sub 2}]; 1:2 (M:L) chelate complex was synthesized in the first step by our previously reported method. The chelate complex precursor was subsequently decomposed by alkaline solution of thiocarbamide, resulting formation of {gamma}-MnS crystals in situ. {yields} The effect of reaction time and surfactant have been observed and discussed. The materials were characterized for crystallanity and morphology by SEM, TEM, XRD, UV-Vis, PL spectra and the results are thoroughly discussed. {yields} {gamma}-MnS crystals were formed when metal complexmore » was used as metal source whereas Mn{sub 3}O{sub 4} was the dominant product when MnSO{sub 4}.H{sub 2}O was used as metal source. {yields} We have also proposed a plausible formation mechanism based on experimental evidence, analyses and previous reports. {yields} Optical property of the material has also been discussed in the present article. -- Abstract: {gamma}-MnS nanocrystalline materials have been prepared by reaction of Na{sub 2}[Mn(HL){sub 2}(H{sub 2}O){sub 2}]; 1:2 (M:L) chelate complex with alkaline solution of thiocarbamide in aqueous solution phase. Effect of metal chelate complex, reaction time and surfactant sodium dodecyl sulfate; SDS on phase, morphology and size of the products have been investigated. The metal chelate complex was synthesized by reacting Mn(II) ions with eriochrome black T (NaH{sub 2}L) in alkaline medium. {gamma}-MnS crystals were formed when metal complex was used as metal source whereas Mn{sub 3}O{sub 4} was the dominant product when MnSO{sub 4}.H{sub 2}O was used as metal source. Materials thus formed having various morphologies were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM) to determine the crystallinity, phase, structure and morphology. The optical properties of the thus prepared samples were determined by UV-vis absorption spectra and photoluminescence spectra. A possible formation mechanism of crystals has been discussed in this article.« less