Near-Infrared Dual-Band LSPR Coupling in Oriented Assembly of Doped Metal Oxide Nanocrystal Platelets.

Coupling effects of localized surface plasmon resonance (LSPR) represent an efficient means to tune the plasmonic modes and to enhance the near-field. While LSPR coupling in metal nanoparticles has been extensively explored, limited attention has been given to heavily doped semiconductor nanocrystals. Here, we investigate the LSPR coupling behavior of Cs-doped tungsten oxide (CsxWO3-δ) nanocrystal platelets as they undergo an oriented assembly into parallel stacks. The oriented assembly was achieved by lowering the dispersion stability of the colloidal nanoplatelets, of which the basal surface was selectively ligand-functionalized. This assembly induces simultaneous blue-shifts and red-shifts of dual-mode LSPR peaks without compromising the intensity and quality factor. This stands in contrast to the significant damping, broadening, and overall red-shift of the LSPR observed in random assemblies. Computational simulations successfully replicate the experimental observations, affirming the potential of this coupling phenomenon of near-infrared dual-mode LSPR in diverse applications including solar energy, bio-optics, imaging, and telecommunications.

Multititration: The New Method for Implementing Ultrasensitive and Quantitative Multiplexed In-Field Immunoassays Despite Cross-Reactivity?

The accurate in-field titration of multiple pathogens is essential to efficiently describe and monitor environmental or biological contamination, isolate, act, and treat adequately. This underscores the requirement of portable, fast, quantitative, and multiplexed detection technologies, which, however, have not been properly developed so far, notably because it has been hindered by the phenomenon of cross-reactivity. In this work, we proposed a new analytical method based on the imaging through a portable device of lanthanide-based nanoparticles (YVO4:Eu) for spatially multiplexed detection, relying on a multiparameter analysis, i.e., a simultaneous analysis of all of the luminescence signals through the comparison to a calibration surface built in the presence of multiple analytes of interest. We then demonstrated the possibility to simultaneously quantify by multiplexed lateral flow assay (xLFA) the three enterotoxins SEG, SEH, and SEI in unknown mixtures, over two concentration decades (from a dozen of pg·mL-1 to few ng·mL-1). Assays were performed in less than an hour (25 min of strip migration followed by 30 min of drying at room temperature), the time during which the presence of the operator was not required for more than 5 min, in order to dip the strip and have it imaged by the reader. The concepts of nominal concentration recovery, coefficient of variation (CV), limit of blank (LOB), and limit of detection (LOD) were discussed in detail in the context of multiplexed assays. With our new definitions, quantitative results demonstrated a high recovery of the nominal concentrations (115%), reliability (CV = 20%), and sensitivity (LOBs of 3, 27, and 6 pg·mL-1 for SEG, SEH, and SEI respectively, and LODs of 6, 48, and 11 pg·mL-1 for SEG, SEH, and SEI, respectively). Based on this method, we observed an increase in sensitivity of 100 compared to the other multiplexed LFA labeled with gold particles and we approached the sensitivity of the simplex enzyme-linked immunosorbent assay (ELISA) performed with the same capture and detection antibodies. To conclude, our results, which are applicable to virtually any kind of multiplexed test, pave the way to the next generation of in-field analytical immunoassays by providing fast, quantitative, and highly sensitive multiplexed detection of biomarkers or pathogens.

Charge-driven liquid-crystalline behavior of ligand-functionalized nanorods in apolar solvent.

Concentrated colloidal suspensions of nanorods often exhibit liquid-crystalline (LC) behavior. The transition to a nematic LC phase, with long-range orientational order of the particles, is usually well-captured by Onsager's theory for hard rods, at least qualitatively. The theory shows how the volume fraction at the transition decreases with increasing aspect ratio of the rods. It also explains that the long-range electrostatic repulsive interaction occurring between rods stabilized by their surface charge can significantly increase their effective diameter, resulting in a decrease in the volume fraction at the transition, as compared to sterically stabilized rods. Here, we report on a system of ligand-stabilized LaPO4 nanorods, of aspect ratio ≈ 11, dispersed in apolar medium exhibiting the counter-intuitive observation that the onset of nematic self-assembly occurs at an extremely low volume fraction of ≈ 0.25%, which is lower than observed (≈ 3%) with the same particles when charged-stabilized in polar solvent. Furthermore, the nanorod volume fraction at the transition increases with increasing concentration of ligands, in a similar way as in polar media where increasing the ionic strength leads to surface charge screening. This peculiar system was investigated by dynamic light scattering, Fourier-transform infrared spectroscopy, zetametry, electron microscopy, polarized light microscopy, photoluminescence measurements, and X-ray scattering. Based on these experimental data, we formulate several tentative scenarios that might explain this unexpected phase behavior. However, at this stage, its full understanding remains a pending theoretical challenge. Nevertheless, this study shows that dispersing anisotropic nanoparticles in an apolar solvent may sometimes lead to spontaneous ordering events that defy our intuitive ideas about colloidal systems.

Crystallization within Intermediate Amorphous Phases Determines the Polycrystallinity of Nanoparticles from Coprecipitation.

Intense research on nanocrystals synthesized in solution is motivated by their original physical properties, which are determined by their sizes and shapes on various scales. However, morphology control on the nanoscale is limited by our understanding of crystallization, which is challenged by the now well-established prevalence of noncrystalline intermediates. In particular, the impact of such intermediates on the final sizes and crystal quality remains unclear because the characterization of their evolution on the nanometer and millisecond scales with nonperturbative analyses has remained a challenge. Here we use in situ X-ray scattering to show that the nucleation and growth of YVO4:Eu nanocrystals is spatially restrained within amorphous, nanometer-scaled intermediates. The reactivity and size of these amorphous intermediates determine (i) the mono versus polycrystalline character of final crystals and (ii) the size of final crystals. This implies that designing amorphous intermediates themselves that form in <6 ms is one of the keys to controlled bottom-up syntheses of optimized nanoparticles.

Zwitterionic Polymers toward the Development of Orientation-Sensitive Bioprobes.

Dynamics with an orientational degree of freedom are fundamental in biological events. Probes with polarized luminescence enable a determination of the orientation. Lanthanide-doped nanocrystals can provide more precise analysis than quantum dots due to the nonphotoblinking/bleaching nature and the multiple line-shaped emission. However, the intrinsic polarization property of the original nanocrystals often deteriorates in complex physiological environments because the colloidal stability easily breaks and the probes aggregate in the media with abundant salts and macromolecules. Engineering the surface chemistry of the probes is thus essential to be compatible with biosystems, which has remained a challenging task that should be exclusively addressed for each specific probe. Here, we demonstrate a facile and efficient surface functionalization of lanthanide-doped nanorods by zwitterionic block copolymers. Due to the steric interaction and the intrinsic zwitterionic nature of the polymers, high colloidal stability of the zwitterionic nanorod suspension is achieved over wide ranges of pH and concentration of salts, even giving rise to the lyotropic liquid crystalline behavior of the nanorods in physiological media. The shear-aligned ability is shown to be unaltered by the coated polymers, and thus, the strongly polarized emission of Eu3+ is preserved. Besides, biological experiments reveal good biocompatibility of the zwitterionic nanorods with negligible nonspecific binding. This study is a stepping stone for the use of the nanorods as orientation probes in biofluids and validates the strategy of coupling zwitterions to lanthanide-doped nanocrystals for various bioapplications.

Vectorial probing of electric and magnetic transitions in variable optical environments and vice-versa.

We use europium doped single crystalline NaYF4nanorods for probing the electric and magnetic contributions to the local density of optical states (LDOS). Reciprocically, we determine intrinsic properties of the emitters (oscillator strength, quantum yield) by comparing their measured and simulated optical responses in front of a mirror. We first experimentally determine the specifications of the nanoprobe (orientation and oscillator strength of the electric and magnetic dipoles moments) and show significant orientation sensitivity of the branching ratios associated with electric and magnetic transitions. In a second part, we measure the modification of the LDOS in front of a gold mirror in a Drexhage's experiment. We discuss the role of the electric and magnetic LDOS on the basis of numerical simulations, taking into account the orientation of the dipolar emitters. We demonstrate that they behave like degenerated dipoles sensitive to polarized partial LDOS.

Toward a Chemical Control of Colloidal YVO4 Nanoparticles Microstructure.

Rare-earth-doped oxides are a class of compounds that have been largely studied in the context of the development of luminescent nanocrystals for various applications including fluorescent labels for bioimaging, MRI contrast agents, luminescent nanocomposite coatings, etc. Elaboration of colloidal suspensions is usually achieved through coprecipitation. Particles exhibit emission properties that are similar to the bulk counterparts, although altered by crystalline defects or surface quenching species. Focusing on YVO4:Eu, one of the first reported systems, the aim of this work is to revisit the elaboration of nanoparticles obtained through a simple aqueous coprecipitation route. The objective is more precisely to get a better understanding of the parameters affecting the particles' internal microstructure, a feature that is poorly controlled and characterized. We show that the hydroxyl concentration in the precursor solution has a drastic effect on the particles' microstructure. Moreover, discrepancies in the reported particle structure are shown to possibly arise from the carbonation of the strongly basic orthovanadate precursor. For this study, SAXS/WAXS is shown to be a powerful tool to characterize the multiscale structure of the particles. It could be shown that playing on the precursor composition, it may be varied between almost monocrystalline nanocrystals to particles exhibiting a hierarchical microstructure well described by a surface fractal model. This work provides a new methodology for the characterization of nanoparticles microstructure and opens new directions for its optimization in view of applications.

Enhancing Magnetic Light Emission with All-Dielectric Optical Nanoantennas.

Electric and magnetic optical fields carry the same amount of energy. Nevertheless, the efficiency with which matter interacts with electric optical fields is commonly accepted to be at least 4 orders of magnitude higher than with magnetic optical fields. Here, we experimentally demonstrate that properly designed photonic nanoantennas can selectively manipulate the magnetic versus electric emission of luminescent nanocrystals. In particular, we show selective enhancement of magnetic emission from trivalent europium-doped nanoparticles in the vicinity of a nanoantenna tailored to exhibit a magnetic resonance. Specifically, by controlling the spatial coupling between emitters and an individual nanoresonator located at the edge of a near-field optical scanning tip, we record with nanoscale precision local distributions of both magnetic and electric radiative local densities of states (LDOS). The map of the radiative LDOS reveals the modification of both the magnetic and electric quantum environments induced by the presence of the nanoantenna. This manipulation and enhancement of magnetic light-matter interaction by means of nanoantennas opens up new possibilities for the research fields of optoelectronics, chiral optics, nonlinear and nano-optics, spintronics, and metamaterials, among others.

Polarized Luminescence of Anisotropic LaPO4:Eu Nanocrystal Polymorphs.

Lanthanide elements exhibit highly appealing spectroscopic properties that are extensively used for phosphor applications. Their luminescence contains precise information on the internal structure of the host materials. Especially, the polarization behavior of the transition sublevel peaks is a fingerprint of the crystal phase, symmetry, and defects. However, this unique feature is poorly explored in current research on lanthanide nanophosphors. We here report on a detailed investigation of the evolution of Eu3+ luminescence during the thermally induced phase transition of LaPO4 nanocrystal hosts. By means of c-axis-aligned nanocrystal assemblies, we demonstrate a dramatic change of the emission polarization feature corresponding to the distinct Eu3+ site symmetries in different LaPO4 polymorphs. We also show that changes of the nanocrystal structure can be identified by this spectroscopic method, with a much higher sensitivity than the X-ray diffraction analysis. This new insight into the nanostructure-luminescence relationship, associated with the unprecedented polarization characterizations, provides a new methodology to investigate phase transitions in nanomaterials. It also suggests a novel function of lanthanide emitters as orientation-sensing nanoprobes for innovative applications such as in bioimaging or microfluidics.

Luminescence Vapochromism of a Dynamic Copper Iodide Mesocate.

A copper iodide complex coordinated by three phosphine ligands with the formula [Cu2 I2 (Ph2 PC2 (C6 H4 )C2 PPh2 )3 ] exhibits solvatochromic and vapochromic luminescence properties. A mechanism based on solvent-dependent molecular motion appears to occur. The highly contrasted response observed upon THF solvent exposure makes this complex an appealing candidate for chemical sensor applications.

Evaluation of Ligands Effect on the Photophysical Properties of Copper Iodide Clusters.

Luminescent materials based on copper complexes are currently receiving increasing attention because of their rich photophysical properties, opening a wide field of applications. The copper iodide clusters formulated [Cu4I4L4] (L = ligand), are particularly relevant for the development of multifunctional materials based on their luminescence stimuli-responsive properties. In this context, controlling and modulating their photophysical properties is crucial and this can only be achieved by thorough understanding of the origin of the optical properties. We thus report here, the comparative study of a series of cubane copper iodide clusters coordinated by different phosphine ligands, with the goal of analyzing the effect of the ligands nature on the photoluminescence properties. The synthesis, structural, and photophysical characterizations along with theoretical investigations of copper iodide clusters with ligands presenting different electronic properties, are described. A method to simplify the analysis of the 31P solid-state NMR spectra is also reported. While clusters with electron-donating groups present classical luminescence properties, the cluster bearing strong electron-withdrawing substituents exhibits original behavior demonstrating a clear influence of the ligands properties. In particular, the electron-withdrawing character induces a decrease in energy of the unoccupied molecular orbitals, that consequently impacts the emission properties. The modification of the luminescence thermochromic properties of the clusters are supported by density functional theory (DFT) calculations. This study demonstrates that the control of the luminescence properties of these compounds can be achieved through modification of the coordinated ligands, nevertheless the role of the crystal packing should not be underestimated.

Tin dioxide nanoparticles as catalyst precursors for plasma-assisted vapor-liquid-solid growth of silicon nanowires with well-controlled density.

The fabrication of arrays of silicon nanowires (Si NWs) with well-defined surface coverage using the vapor-liquid-solid process requires a good control of the density and size distribution for the metal catalyst. We report on a cost-effective bottom-up approach to produce Si NWs by a low-temperature deposition technology using plasma-enhanced chemical vapor deposition and tin dioxide (SnO2) nanoparticles as the source of tin catalyst. This strategy offers a straightforward method to select specific particle sizes by conventional colloidal techniques, and to tune the surface coverage using a polyelectrolyte layer to efficiently immobilize the particles on the substrate by electrostatic grafting. After a further step of reduction into tin metal droplets using hydrogen plasma treatment, the catalyst particles are used for the growth of Si NWs. This approach allows the prodcution of controlled Si NWs arrays which can be used as a template for radial junction thin film solar cells.

Metrology of Multiphoton Microscopes Using Second Harmonic Generation Nanoprobes.

In multiphoton microscopy, the ongoing trend toward the use of excitation wavelengths spanning the entire near-infrared range calls for new standards in order to quantify and compare the performances of microscopes. This article describes a new method for characterizing the imaging properties of multiphoton microscopes over a broad range of excitation wavelengths in a straightforward and efficient manner. It demonstrates how second harmonic generation (SHG) nanoprobes can be used to map the spatial resolution, field curvature, and chromatic aberrations across the microscope field of view with a precision below the diffraction limit and with unique advantages over methods based on fluorescence. KTiOPO4 nanocrystals are used as SHG nanoprobes to measure and compare the performances over the 850-1100 nm wavelength range of several microscope objectives designed for multiphoton microscopy. Finally, this approach is extended to the post-acquisition correction of chromatic aberrations in multicolor multiphoton imaging. Overall, the use of SHG nanoprobes appears as a uniquely suited method to standardize the metrology of multiphoton microscopes.

Luminescence Mechanochromism Induced by Cluster Isomerization.

Luminescent mechanochromic materials exhibiting reversible changes of their emissive properties in response to external mechanical forces are currently emerging as an important class of stimuli-responsive materials because of promising technological applications. Here, we report on the luminescence mechanochromic properties of a [Cu4I4(PPh3)4] copper iodide cluster presenting a chair geometry, being an isomer of the most common cubane form. This molecular cluster formulated [Cu4I4(PPh3)4]·2CHCl3 (1) exhibits a highly contrasted emission response to manual grinding, and, interestingly, the optical properties of the ground phase present striking similarities with those of the cubane isomer. In order to understand the underlying mechanism, a comparison with two related compounds has been conducted. The first one is a pseudopolymorph of 1 formulated as [Cu4I4(PPh3)4]·CH2Cl2 (2), which exhibits luminescent mechanochromic properties as well. The other one is also a chair compound but with a slightly different phosphine ligand, namely, [Cu4I4(PPh2C6H4CO2H)4] (3), lacking mechanochromic properties. Structural and optical characterizations of the clusters have been analyzed in light of previous electronic structure calculations. The results suggest an unpreceded mechanochromism phenomenon based on a solid-state chair → cubane isomer conversion. This study shows that polynuclear copper iodide compounds are particularly relevant for the development of luminescent mechanochromic materials.

Determination of paramagnetic concentrations inside a diamagnetic matrix using solid-state NMR.

The determination of very low doping levels in solid materials is an important issue for many applications. When considering paramagnetic dopants, the NMR relaxation technique appears to be much more accurate than classical techniques such as Vegard's law resulting from X-ray diffraction (XRD) measurements or chemical analysis that cannot provide information on appropriate dopant spatial distributions. In a recent report, the linear variation of 1/T1, i.e. the nuclear relaxation rate, as a function of Nd3+ content has been used to determine doping levels with a good dispersion homogeneity in the monazite LaPO4 matrix down to 0.1 mol%. We here extend this study to more complex compounds doped with Nd3+, such as YPO4, the solid solution Y0.8Sc0.2PO4, Ba5(PO4)3Cl and a phosphate glass. For all considered compounds except Ba5(PO4)3Cl:Nd, 1/T1 is found to be linearly proportional to the nominal Nd concentration, confirming the ability of the method to investigate the dopant concentration and spatial homogeneity. The results obtained for different compounds open up the discussion on the parameters, such as the orbital overlap and the average P-P distances, influencing the nuclear relaxation rate.

Mechanochromic luminescence of copper iodide clusters.

Luminescent mechanochromic materials are particularly appealing for the development of stimuli-responsive materials. Establishing the mechanism responsible for the mechanochromism is always an issue owing to the difficulty in characterizing the ground phase. Herein, the study of real crystalline polymorphs of a mechanochromic and thermochromic luminescent copper iodide cluster permits us to clearly establish the mechanism involved. The local disruption of the crystal packing induces changes in the cluster geometry and in particular the modification of the cuprophilic interactions, which consequently modify the emissive states. This study constitutes a step further toward the understanding of the mechanism involved in the mechanochromic luminescent properties of multimetallic coordination complexes.

Electric field induced birefringence in non-aqueous dispersions of mineral nanorods.

Lanthanum phosphate (LaPO4) nanorods dispersed in the non-aqueous solvent of ethylene glycol form a system exhibiting large intrinsic birefringence, high colloidal stability and the ability to self-organize into liquid crystalline phases. In order to probe the electro-optical response of these rod dispersions we study here the electric-field-induced birefringence, also called Kerr effect, for a concentrated isotropic liquid state with an in-plane a.c. sinusoidal electric field, in conditions of directly applied (electrodes in contact with the sample) or externally applied (electrodes outside the sample cell) fields. Performing an analysis of the electric polarizability of our rod-like particles in the framework of Maxwell-Wagner-O'Konski theory, we account quantitatively for the coupling between the induced steady-state birefringence and the electric field as a function of the voltage frequency for both sample geometries. The switching time of this non-aqueous transparent system has been measured, and combined with its high Kerr coefficients and its features of optically isotropic "off-state" and athermal phase behavior, this represents a promising proof-of-concept for the integration of anisotropic nanoparticle suspensions into a new generation of electro-optical devices.

Pressure Control of Cuprophilic Interactions in a Luminescent Mechanochromic Copper Cluster.

For the development of applications based on mechanochromic luminescent materials, a comprehensive study of the mechanism responsible for the emission changes is required. We report the study of a mechanochromic copper iodide cluster under hydrostatic pressure, which allows control of crystal packing via modification of the intermolecular interactions. In situ single-crystal powder X-ray diffraction analysis and emission measurements under pressure permit one to establish a direct correlation between the molecular structure and luminescence properties and, in particular, to demonstrate that cuprophilic interactions are responsible for the stimuli-responsive luminescence properties of such multinuclear coordination compounds.

Geometry flexibility of copper iodide clusters: variability in luminescence thermochromism.

An original copper(I) iodide cluster of novel geometry obtained by using a diphosphine ligand is reported and is formulated [Cu6I6(PPh2(CH2)3PPh2)3] (1). Interestingly, this sort of "eared cubane" cluster based on the [Cu6I6] inorganic core can be viewed as a combination of the two known [Cu4I4] units, namely, the cubane and the open-chair isomeric geometries. The synthesis, structural and photophysical characterisations, as well as theoretical study of this copper iodide along with the derived cubane (3) and open-chair (2) [Cu4I4(PPh3)4] forms, were investigated. A new polymorph of the cubane [Cu4I4(PPh3)4] cluster is indeed presented (3). The structural differences of the clusters were analyzed by solid-state nuclear magnetic resonance spectroscopy. Luminescence properties of the three clusters were studied in detail as a function of the temperature showing reversible luminescence thermochromism for 1 with an intense orange emission at room temperature. This behavior presents different feature compared to the cubane cluster and completely contrasts with the open isomer, which is almost nonemissive at room temperature. Indeed, the thermochromism of 1 differs by a concomitant increase of the two emission bands by lowering the temperature, in contrast to an equilibrium phenomenon for 3. The luminescence properties of 2 are very different by exhibiting only one single band when cooled. To rationalize the different optical properties observed, density functional theory calculations were performed for the three clusters giving straightforward explanation for the different luminescence thermochromism observed, which is attributed to different contributions of the ligands to the molecular orbitals. Comparison of 3 with its [Cu4I4(PPh3)4] cubane polymorphs highlights the sensibility of the emission properties to the cuprophilic interactions.

Polymorphic copper iodide clusters: insights into the mechanochromic luminescence properties.

An in-depth study of mechanochromic and thermochromic luminescent copper iodide clusters exhibiting structural polymorphism is reported and gives new insights into the origin of the mechanochromic luminescence properties. The two different crystalline polymorphs exhibit distinct luminescence properties with one being green emissive and the other one being yellow emissive. Upon mechanical grinding, only one of the polymorphs exhibits great modification of its emission from green to yellow. Interestingly, the photophysical properties of the resulting partially amorphous crushed compound are closed to those of the other yellow polymorph. Comparative structural and optical analyses of the different phases including a solution of clusters permit us to establish a correlation between the Cu-Cu bond distances and the luminescence properties. In addition, the local structure of the [Cu4I4P4] cluster cores has been probed by (31)P and (65)Cu solid-state NMR analysis, which readily indicates that the grinding process modifies the phosphorus and copper atoms environments. The mechanochromic phenomenon is thus explained by the disruption of the crystal packing within intermolecular interactions inducing shortening of the Cu-Cu bond distances in the [Cu4I4] cluster core and eventually modification of the emissive state. These results definitely establish the role of cuprophilic interactions in the mechanochromism of copper iodide clusters. More generally, this study constitutes a step further into the understanding of the mechanism involved in the mechanochromic luminescent properties of metal-based compounds.