Isolating and enhancing single-photon emitters for 1550 nm quantum light sources using double nanohole optical tweezers.

Single-photon sources are required for quantum technologies and can be created from individual atoms and atom-like defects. Erbium ions produce single photons at low-loss fiber optic wavelengths, but they have low emission rates, making them challenging to isolate reliably. Here, we tune the size of gold double nanoholes (DNHs) to enhance the emission of single erbium emitters, achieving 50× enhancement over rectangular apertures previously demonstrated. This produces enough enhancement to show emission from single nanocrystals at wavelengths not seen in our previous work, i.e., 400 and 1550 nm. We observe discrete levels of emission for nanocrystals with low numbers of emitters and demonstrate isolating single emitters. We describe how the trapping time is proportional to the enhancement factor for a given DNH structure, giving us an independent way to measure the enhancement. This shows a promising path to achieving single emitter sources at 1550 nm.

Isolating Nanocrystals with an Individual Erbium Emitter: A Route to a Stable Single-Photon Source at 1550 nm Wavelength.

Single-photon emitters based on individual atoms or individual atomic-like defects are highly sought-after components for future quantum technologies. A key challenge in this field is how to isolate just one such emitter; the best approaches still have an active emitter yield of only 50% so that deterministic integration of single active emitters is not yet possible. Here, we demonstrate the ability to isolate individual erbium emitters embedded in 20 nm nanocrystals of NaYF4 using plasmonic aperture optical tweezers. The optical tweezers capture the nanocrystal, whereas the plasmonic aperture enhances the emission of the Er and allows the measurement of discrete emission rate values corresponding to different numbers of erbium ions. Three separate synthesis runs show near-Poissonian distribution in the discrete levels of emission yield that correspond to the expected ion concentrations, indicating that the yield of active emitters is approximately 80%. Fortunately, the trap allows for selecting the nanocrystals with only a single emitter, and so this gives a route to isolating and integrating single emitters in a deterministic way. This demonstration is a promising step toward single-photon quantum information technologies that utilize single ions in a solid-state medium, particularly because Er emits in the low-loss fiber-optic 1550 nm telecom band.

Site-specific conjugation of the quencher on peptide's N-terminal for the synthesis of a targeted non-spreading activatable optical probe.

Optical imaging offers high sensitivity and portability at low cost. The design of 'smart' or 'activatable' probes can decrease the background noise and increase the specificity of the signal. By conjugating a fluorescent dye and a compatible quencher on each side of an enzyme's substrate, the signal remains in its 'off ' state until it reaches the area where a specific enzyme is expressed. However, the signal can leak from that area unless the dye is attached to a molecule able to bind to a specific target also presented in that area. The aim of this study was to (i) specifically conjugate the quencher on the α-amino group of the peptide's N-terminus, (ii) conjugate the dye on the ε-amino group of a lysine in C-terminus, and (iii) conjugate the carboxyl group of the peptide's C-terminus to an amino group present on an antibody, using carbodiimide chemistry. The use of protecting groups, such as Boc or Fmoc, to allow site-specific conjugation, presents several drawbacks including 'on beads labeling', additional steps required for deprotection and removal from the resin, decreased yield, and dye degradation. A method of preferential labeling of α-amino N-terminal group in slightly acidic solution, proposed by Selo et al. (1996) has partially solved the problem. The present study reports improvements of the method allowing to (i) avoid the homo-bilabeling, (ii) increase the yield of the N-terminal labeling by two folds, and (iii) decrease the cost by 44-fold. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd.

Neodymium-doped LaF(3) nanoparticles for fluorescence bioimaging in the second biological window.

The future perspective of fluorescence imaging for real in vivo application are based on novel efficient nanoparticles which is able to emit in the second biological window (1000-1400 nm). In this work, the potential application of Nd(3+) -doped LaF(3) (Nd(3+) :LaF(3) ) nanoparticles is reported for fluorescence bioimaging in both the first and second biological windows based on their three main emission channels of Nd(3+) ions: (4) F(3/2) →(4) I(9/2) , (4) F(3/2) →(4) I(11/2) and (4) F(3/2) →(4) I(13/2) that lead to emissions at around 910, 1050, and 1330 nm, respectively. By systematically comparing the relative emission intensities, penetration depths and subtissue optical dispersion of each transition we propose that optimum subtissue images based on Nd(3+) :LaF(3) nanoparticles are obtained by using the (4) F3/2 →(4) I11/2 (1050 nm) emission band (lying in the second biological window) instead of the traditionally used (4) F(3/2) →(4) I(9/2) (910 nm, in the first biological window). After determining the optimum emission channel, it is used to obtain both in vitro and in vivo images by the controlled incorporation of Nd(3+) :LaF(3) nanoparticles in cancer cells and mice. Nd(3+) :LaF(3)nanoparticles thus emerge as very promising fluorescent nanoprobes for bioimaging in the second biological window.

Thermometric Analysis of Nanoaperture-Trapped Erbium-Containing Nanocrystals.

Temperature changes in plasmonic traps can affect biomolecules and quantum emitters; therefore, several works have sought out the capability of measuring the local temperature. Those works used ionic nanopore currents, fluorescence emission variations, and fluorescence-based diffusion tracking to measure the temperature dependence of shaped nanoapertures in metal films. Here, we make use of a stable erbium-containing NaYF4 nanocrystal that gives local temperature dependence while trapped in the nanoaperture hot spot. Ratiometric analysis of the emission at different wavelengths gives local temperature variation. Since the gold film dominates the thermal characteristic, we find that films of thickness 70, 100, and 130 nm give 0.64, 0.37, and 0.25 K/mW temperature change with laser power. Therefore, using thicker films can be effective in reducing the heating when it is not desired.

X-ray-Sensitive Doped CaF2-Based MRI Contrast Agents for Local Radiation Dose Measurement.

Ionizing radiation has become widely used in medicine, with application in diagnostic techniques, such as computed tomography (CT) and radiation therapy (RT), where X-rays are used to diagnose and treat tumors. The X-rays used in CT and, in particular, in RT can have harmful side effects; hence, an accurate determination of the delivered radiation dose is of utmost importance to minimize any damage to healthy tissues. For this, medical specialists mostly rely on theoretical predictions of the delivered dose or external measurements of the dose. To extend the practical use of ionizing radiation-based medical techniques, such as magnetic resonance imaging (MRI)-guided RT, a more precise measurement of the internal radiation dose internally is required. In this work, a novel approach is presented to measure dose in liquids for potential future in vivo applications. The strategy relies on MRI contrast agents (CAs) that provide a dose-sensitive signal. The demonstrated materials are (citrate-capped) CaF2 nanoparticles (NPs) doped with Eu3+ or Fe2+/Fe3+ ions. Free electrons generated by ionizing radiation allow the reduction of Eu3+, which produces a very small contrast in MRI, to Eu2+, which induces a strong contrast. Oxidative species generated by high-energy X-rays can be measured indirectly using Fe2+ because it oxidizes to Fe3+, increasing the contrast in MRI. Notably, in the results, a strong increase in the proton relaxation rates is observed for the Eu3+-doped NPs at 40 kV. At 6 MV, a significant increase in proton relaxation rates is observed using CaF2 NPs doped with Fe2+/Fe3+ after irradiation. The presented concept shows great promise for use in the clinic to measure in vivo local ionizing radiation dose, as these CAs can be intravenously injected in a saline solution.

Optimal dye-quencher pairs for the design of an "activatable" nanoprobe for optical imaging.

Optical imaging offers high sensitivity and portability at low cost. The design of an optimal "activatable" imaging agent could greatly decrease the background noise and increase specificity of the signal. Five different molecules have been used to quench basal fluorescence of an enzyme substrate labeled with Cy5, Cy5.5 or IR800 at a distance of 8 amino acids (32 Å): a 6 nm gold nanoparticle (NP), a 20 nm and a 30 nm iron oxide (FeO) NP, the black hole quencher BHQ-3 and the IRdye quencher QC-1. The quenching efficiencies were 99% for QC1-IR800, 98% for QC1-Cy5.5, 96% for 30 nm FeO NP-Cy5.5, 89% for BHQ3-Cy5, 84% for BHQ3-Cy5.5, 77-90% for 6 nm gold NP-Cy5.5, depending on the number of dyes around the NP, 79% for 20 nm FeO NP-Cy5.5 and 77% for Cy5.5-Cy5. Signal activation upon cleavage by the matrix metalloproteinase MMP9 was proportional to the quenching efficiencies, ranging from 3-fold with Cy5.5-Cy5 to 67-fold with QC1-IR800. This independent work reports on the properties of the dyes and quenchers explaining the superior performance of QC-1 and 30 nm FeO NPs.

Contrast Enhancement in MRI Using Combined Double Action Contrast Agents and Image Post-Processing in the Breast Cancer Model.

Gd- and Fe-based contrast agents reduce T1 and T2 relaxation times, respectively, are frequently used in MRI, providing improved cancer detection. Recently, contrast agents changing both T1/T2 times, based on core/shell nanoparticles, have been introduced. Although advantages of the T1/T2 agents were shown, MR image contrast of cancerous versus normal adjacent tissue induced by these agents has not yet been analyzed in detail as authors considered changes in cancer MR signal or signal-to-noise ratio after contrast injection rather than changes in signal differences between cancer and normal adjacent tissue. Furthermore, the potential advantages of T1/T2 contrast agents using image manipulation such as subtraction or addition have not been yet discussed in detail. Therefore, we performed theoretical calculations of MR signal in a tumor model using T1-weighted, T2-weighted, and combined images for T1-, T2-, and T1/T2-targeted contrast agents. The results from the tumor model are followed by in vivo experiments using core/shell NaDyF4/NaGdF4 nanoparticles as T1/T2 non-targeted contrast agent in the animal model of triple negative breast cancer. The results show that subtraction of T2-weighted from T1-weighted MR images provides additional increase in the tumor contrast: over two-fold in the tumor model and 12% in the in vivo experiment.

Self-focusing by Ostwald ripening: a strategy for layer-by-layer epitaxial growth on upconverting nanocrystals.

We demonstrate a novel epitaxial layer-by-layer growth on upconverting NaYF(4) nanocrystals (NCs) utilizing Ostwald ripening dynamics tunable both in thickness and composition. Injection of small sacrificial NCs (SNCs) as shell precursors into larger core NCs results in the rapid dissolution of the SNCs and their deposition onto the larger core NCs to yield core-shell structured NCs. Exploiting this NC size dependent dissolution/growth, the shell thickness can be controlled either by manipulating the number of SNCs injected or by successive injection of SNCs. In either of these approaches, the NCs self-focus from an initial bimodal distribution to a unimodal distribution (σ <5%) of core-shell NCs. The successive injection approach facilitates layer-by-layer epitaxial growth without the need for tedious multiple reactions for generating tunable shell thickness, and does not require any control over the injection rate of the SNCs, as is the case for shell growth by precursor injection.

Saturation behaviour of colloidal PbSe quantum dot exciton emission coupled into silicon photonic circuits.

We report coupling of the excitonic photon emission from photoexcited PbSe colloidal quantum dots (QDs) into an optical circuit that was fabricated in a silicon-on-insulator wafer using a CMOS-compatible process. The coupling between excitons and sub-µm sized silicon channel waveguides was mediated by a photonic crystal microcavity. The intensity of the coupled light saturates rapidly with the optical excitation power. The saturation behaviour was quantitatively studied using an isolated photonic crystal cavity with PbSe QDs site-selectively located at the cavity mode antinode position. Saturation occurs when a few µW of continuous wave HeNe pump power excites the QDs with a Gaussian spot size of 2 µm. By comparing the results with a master equation analysis that rigorously accounts for the complex dielectric environment of the QD excitons, the saturation is attributed to ground state depletion due to a non-radiative exciton decay channel with a trap state lifetime ~ 3 µs.

An effective polymer cross-linking strategy to obtain stable dispersions of upconverting NaYF4 nanoparticles in buffers and biological growth media for biolabeling applications.

Ligands on the nanoparticle surface provide steric stabilization, resulting in good dispersion stability. However, because of their highly dynamic nature, they can be replaced irreversibly in buffers and biological medium, leading to poor colloidal stability. To overcome this, we report a simple and effective cross-linking methodology to transfer oleate-stabilized upconverting NaYF(4) core/shell nanoparticles (UCNPs) from hydrophobic to aqueous phase, with long-term dispersion stability in buffers and biological medium. Amphiphilic poly(maleic anhydride-alt-1-octadecene) (PMAO) modified with and without poly(ethylene glycol) (PEG) was used to intercalate with the surface oleates, enabling the transfer of the UCNPs to water. The PMAO units on the phase transferred UCNPs were then successfully cross-linked using bis(hexamethylene)triamine (BHMT). The primary advantage of cross-linking of PMAO by BHMT is that it improves the stability of the UCNPs in water, physiological saline buffers, and biological growth media and in a wide range of pH values when compared to un-cross-linked PMAO. The cross-linked PMAO-BHMT coated UCNPs were found to be stable in water for more than 2 months and in physiological saline buffers for weeks, substantiating the effectiveness of cross-linking in providing high dispersion stability. The PMAO-BHMT cross-linked UCNPs were extensively characterized using various techniques providing supporting evidence for the cross-linking process. These UCNPs were found to be stable in serum supplemented growth medium (37 °C) for more than 2 days. Utilizing this, we demonstrate the uptake of cross-linked UCNPs by LNCaP cells (human prostate cancer cell line), showing their utility as biolabels.

Target-Specific Magnetic Resonance Imaging of Human Prostate Adenocarcinoma Using NaDyF4-NaGdF4 Core-Shell Nanoparticles.

We illustrate the development of NaDyF4-NaGdF4 core-shell nanoparticles (NPs) for targeting prostate cancer cells using a preclinical 9.4 T magnetic resonance imaging (MRI) of live animals. The NPs composed of paramagnetic Dy3+ and Gd3+ (T2- and T1-contrast agents, respectively) demonstrate proton relaxivities of r1 = 20.2 mM-1 s-1 and r2 = 32.3 mM-1 s-1 at clinical 3 T and r1 = 9.4 mM-1 s-1 and r2 = 144.7 mM-1 s-1 at preclinical 9.4 T. The corresponding relaxivity values per NP are r1 = 19.4 × 105 mMNP-1 s-1 and r2 = 33.0 × 105 mMNP-1 s-1 at 3 T and r1 = 9.0 × 105 mMNP-1 s-1 and r2 = 147.0 × 105 mMNP-1 s-1 at 9.4 T. In vivo active targeting of human prostate tumors grown in nude mice revealed docking of anti-prostate-specific membrane antigen (PSMA) antibody-tagged NPs at tumor sites post-24 h of their intravenous injection. On the other hand, in vivo passive targeting showed preferential accumulation of NPs at tumor sites only within 2 h of their injection, ascribed to the enhanced permeation and retention effect of the tumor. A biodistribution study employing the harvested organs of mice, post-24 h injection of NPs, quantified active targeting as nearly twice as efficient as passive targeting. These outcomes provide potential opportunities for noninvasive diagnosis using NaDyF4-NaGdF4 core-shell NPs for target-specific MRI.

Directional study of the optical properties of Tb3+- and Eu3+-doped nanoparticles embedded in silica photonic crystals.

The effects of the stop band (SB) in colloidal photonic crystals composed of silica spheres containing Eu(3+)- and Tb(3+)-doped yttria nanoparticles are analysed. Reflection and transmission spectra indicate movement of the stop band, due to the 111 series of planes, towards shorter wavelengths with increasing angle of observation. The profile of the emission spectra is modified by the presence of the SB depending on the angle of measurement. Such a modification is more effective for a narrow emission band and it is thus more evident in the case of Tb(3+) than Eu(3+). An angular effect is also observed in the lifetime, which presents two maxima and one minimum. In the case of Tb(3+) the maxima are at observation angles of 35 and 50 degrees, and the minimum at 45 degrees. We attribute this behaviour to penetration of the excitation beam at 475 nm modulated by the stop band. The ions excited in this way emit from different depths in the crystal, and therefore their lifetime will be affected differently by the same stop band, depending on the thickness of the crystal that must be crossed. Eu(3+) shows a similar but less pronounced effect for two reasons: first, the main stop band (due to the 111 planes) is not effective at the excitation wavelength of 392 nm; second, the broadness of the Eu(3+) emission is comparable to the width of the SB, and a decrease in the transition rate at the wavelength of the SB maximum is compensated by an increase at the sides of the SB.

Surface modification of upconverting NaYF4 nanoparticles with PEG-phosphate ligands for NIR (800 nm) biolabeling within the biological window.

We present a technique for the replacement of oleate with a PEG-phosphate ligand [PEG = poly(ethylene glycol)] as an efficient method for the generation of water-dispersible NaYF(4) nanoparticles (NPs). The PEG-phosphate ligands are shown to exchange with the original oleate ligands on the surface of the NPs, resulting in water-dispersible NPs. The upconversion intensity of the NPs in aqueous environments was found to be severely quenched when compared to the original NPs in organic solvents. This is attributed to an increase in the multiphonon relaxations of the lanthanide excited state in aqueous environments due to high energy vibrational modes of water molecules. This problem could be overcome partially by the synthesis of core/shell NPs which demonstrated improved photophysical properties in water over the original core NPs. The PEG-phosphate coated upconverting NPs were then used to image a line of ovarian cancer cells (CaOV3) to demonstrate their promise in biological application.

Site-selective optical coupling of PbSe nanocrystals to Si-based photonic crystal microcavities.

A novel method for patterning optically active colloidal PbSe nanocrystals on Si surfaces is reported. Oleate-capped PbSe nanocrystals were found to adhere preferentially to H-terminated Si surfaces over oxide and alkyl-terminated Si surfaces. Scanning probe lithography was used to oxidize locally a dodecyl monolayer on the Si surface of a silicon-on-insulator wafer prepatterned with photonic crystal microcavities. Aqueous HF was then used to remove the oxide and expose H-terminated Si areas, yielding patterned PbSe nanocrystals on the Si surface after exposure to a nanocrystal solution. This patterning technique allows for the selective deposition of PbSe nanocrystals at the main antinode of the silicon-based microcavities. More than a 10-fold photoluminescence enhancement due to the cavity-nanocrystal coupling was observed.

Photon-counting computed tomography of lanthanide contrast agents with a high-flux 330-µm-pitch cadmium zinc telluride detector in a table-top system.

Purpose: We present photon-counting computed tomography (PCCT) imaging of contrast agent triplets similar in atomic number ( Z ) achieved with a high-flux cadmium zinc telluride (CZT) detector. Approach: The table-top PCCT imaging system included a 330 - µ m -pitch CZT detector of size 8 mm × 24 mm 2 capable of using six energy bins. Four 3D-printed 3-cm-diameter phantoms each contained seven 6-mm-diameter vials with water and low and high concentration solutions of various contrast agents. Lanthanum ( Z = 57 ), gadolinium (Gd) ( Z = 64 ), and lutetium ( Z = 71 ) were imaged together and so were iodine ( Z = 53 ), Gd, and holmium ( Z = 67 ). Each phantom was imaged with 1-mm aluminum-filtered 120-kVp cone beam x rays to produce six energy-binned computed tomography (CT) images. Results: K -edge images were reconstructed using a weighted sum of six CT images, which distinguished each contrast agent with a root-mean-square error (RMSE) of < 0.29 % and 0.51% for the 0.5% and 5% concentrations, respectively. Minimal cross-contamination in each K -edge image was seen, with RMSE values < 0.27 % in vials with no contrast. Conclusion: This is the first preliminary demonstration of simultaneously imaging three similar Z contrast agents with a difference in Z as low as 3.

Hard proof of the NaYF(4)/NaGdF(4) nanocrystal core/shell structure.

Hexagonal-phase NaYF(4)/NaGdF(4) core/shell nanocrystals were synthesized and investigated by X-ray photoelectron spectroscopy (XPS) using tunable synchrotron radiation. Based on the ratio of the Y(3+) 3d to Gd(3+) 4d core level intensities at varying photoelectron kinetic energies, we conclude that Gd(3+) resides predominantly at the surface of the nanocrystals, proving a core/shell structure. These nanocrystals show potential for use as contrast agents in magnetic resonance imaging (MRI) applications and optical imaging.

Determination of the Förster distance in polymer films by fluorescence decay for donor dyes with a nonexponential decay profile.

Fluorescence resonance energy transfer (FRET) experiments were carried out on three pairs of donor-acceptor dyes in polymer films in which the donor dyes had absorption maxima in the range of 350-450 nm. Two of the donors, a coumarin dye and a naphthalimide dye covalently bound to polystyrene, gave nonexponential decays in the absence of acceptors. The decay profiles could be fitted to a stretched exponential form with a beta value on the order of 0.9. We developed equations for analyzing donor fluorescence intensity decay profiles for donor-acceptor mixtures in rigid matrices for the case of donors showing relatively small deviations from exponentiality. To test these equations, we calculate values of the Förster radius (R0(FR)) from the decay profile data and compare these values to the Förster radius R0(SO) determined by the traditional spectral overlap method. Agreement between these values validates the methodology developed here for the use of such donor dyes in FRET studies of more complex polymer systems.

Resonant Plasmon-Enhanced Upconversion in Monolayers of Core-Shell Nanocrystals: Role of Shell Thickness.

The upconversion luminescence (UCL) of colloidal lanthanide-doped upconversion nanocrystals (UCNCs) can be improved either by precise encapsulation of the surface by optically inert shells around the core, by an alteration of the nearby environment via metal nanoparticles, or by a combination of both. Considering their potential importance in crystalline silicon photovoltaics, the present study investigates both effects for two-dimensional arrangements of UCNCs. Using excitation light of 1500 nm wavelength, we study the variation in the upconversion luminescence from an Er3+-doped NaYF4 core as a function of the thickness of a NaLuF4 shell in colloidal solutions as well as in spin-cast-assisted self-assembled monolayers of UCNCs. The observed UCL yields and decay times of Er3+ ions of the UCNCs increase with increasing shell thickness in both cases, and nearly no variation in decay times is observed in the transition of the UCNCs from solution to film configurations. The luminescence efficiency of the UCNC monolayers is further enhanced by electron-beam-lithographic-designed Au nanodiscs deposited either on top of or buried within the monolayer. It is observed that the improvement by the nanocrystal shells is greater than that of the Au nanodiscs.