Inferring the Interfacial Reactivity of Gold Nanoparticles by Surface Plasmon Resonance Measurements.

Gold nanoparticles (GNPs) require a functionalization step in most cases to be suitable for applications. Optimizing this step in order to maintain both the stability and the plasmonic properties of the GNPs is a demanding process. Indeed, multiple analyses are required to get sufficient information on the grafting rate and the stability of the obtained suspension, leading to material and time waste. In this study, we propose to investigate ligand reactivity on a gold surface with surface plasmon resonance (SPR) measurements as a way to simulate the reactivity in GNP suspensions. We consider two thiolated ligands in this work: thioglycolic acid (TA) and 6-mercaptohexanoic acid (MHA). These thiols are grafted using different conditions on GNPs (monitored by optical absorption) and on a gold surface (monitored by SPR) and the grafting efficiency and stability are compared. The same conclusions are reached in both cases regarding the best protocol to implement, namely, the thiol molecules should be introduced in a water solution at a low concentration. This demonstrates the suitability of SPR to predict the reactivity on a GNP surface.

Versatile and robust synthesis process for the fine control of the chemical composition and core-crystallinity of spherical core-shell Au@Ag nanoparticles.

Au nanoparticles (NPs) characterized by distinct surface chemistry (including dodecanethiol or oleylamine as capping agent), different sizes (∼5 and ∼10 nm) and crystallinities (polycrystalline or single crystalline), were chosen as seeds to demonstrate the versatility and robustness of our two-step core-shell Au@Ag NP synthesis process. The central component of this strategy is to solubilize the shell precursor (AgNO3) in oleylamine and to induce the growth of the shell on selected seeds under heating. The shell thickness is thus controlled by the temperature, the annealing time, the (shell precursor)/(seed) concentration ratio, seed size and crystallinity. The shell thickness is thus shown to increase with the reactant concentration and to grow faster on polycrystalline seeds. The crystalline structure and chemical composition were characterized by HRTEM, STEM-HAADF, EELS and Raman spectroscopy. The plasmonic response of Au@Ag core-shell NPs as a function of core size and shell thickness was assessed by spectrophotometry and simulated by calculations based on the discrete dipole approximation (DDA) method. Finally, the nearly monodisperse core-shell Au@Ag NPs were shown to form micrometer-scale facetted 3D fcc-ordered superlattices (SLs) after solvent evaporation and deposition on a solid substrate. These SLs are promising candidates for applications as a tunable surface-enhanced Raman scattering platform.

Cu-Doped ZnO Nanoparticles for Non-Enzymatic Glucose Sensing.

Copper-doped zinc oxide nanoparticles (NPs) CuxZn1-xO (x = 0, 0.01, 0.02, 0.03, and 0.04) were synthesized via a sol-gel process and used as an active electrode material to fabricate a non-enzymatic electrochemical sensor for the detection of glucose. Their structure, composition, and chemical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) and Raman spectroscopies, and zeta potential measurements. The electrochemical characterization of the sensors was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). Cu doping was shown to improve the electrocatalytic activity for the oxidation of glucose, which resulted from the accelerated electron transfer and greatly improved electrochemical conductivity. The experimental conditions for the detection of glucose were optimized: a linear dependence between the glucose concentration and current intensity was established in the range from 1 nM to 100 µM with a limit of detection of 0.7 nM. The proposed sensor exhibited high selectivity for glucose in the presence of various interfering species. The developed sensor was also successfully tested for the detection of glucose in human serum samples.

Loading of Cisplatin into Mesoporous Silica Nanoparticles: Effect of Surface Functionalization.

Cisplatin ( cis-diaminedichloroplatinum(II), CDDP) plays a crucial role in the treatment of various malignant tumors. However, its clinical efficacy and applicability are restricted by issues of toxicity and resistance. Here, for drug delivery purposes, the outer surface of MCM-41 mesoporous silica nanoparticles (MSNs) was functionalized with poly(ethylene glycol) ( Mw = 10 000 g/mol) or low-molecular-weight ( Mw = 1800 g/mol) branched polyethyleneimine (PEI). Given the strong affinity of sulfur for platinum, thiol-functionalized MSNs were synthesized for comparison by co-condensation with (3-mercaptopropyl)triethoxysilane. CDDP loading was performed either by adsorption or impregnation in aqueous media without the use of dimethyl sulfoxide as a solubilizer. CDDP loading capacities obtained by impregnation were higher than those obtained by adsorption and varied from 3.9 to 16.1 wt %, depending on the functional group. Loaded nanomaterials were characterized by scanning electron microscopy, scanning transmission electron microscopy-high-angle annular dark-field, and Raman spectroscopy. Depending on the functional groups, platinum-based species were either dispersed in the nanomaterials as nanocrystals or uniformly distributed as molecular species. The spectral signature of CDDP was strongly modified when platinum species were homogeneously distributed within the nanomaterials. Preliminary drug release studies performed at 37 °C showed that the behavior of CDDP-loaded MSNs strongly depends on the nature of the present functional groups. Among the functionalization routes investigated in this paper, PEI-based functionalization showed the most promising results for further applications in controlled drug release with the absence of burst release and a sustained release over 72 h.

Nanovectorization of TRAIL with single wall carbon nanotubes enhances tumor cell killing.

Tumor necrosis factor-related apoptosis-inducing ligand (TRAIL or Apo2L) is a member of the tumor necrosis factor (TNF) superfamily. This type II transmembrane protein is able to bound specifically to cancer cell receptors (i.e., TRAIL-R1 (or DR4) and TRAIL-R2 (or DR5)) and to induce apoptosis without being toxic for healthy cells. Because membrane-bound TRAIL induces stronger receptor aggregation and apoptosis than soluble TRAIL, we proposed here to vectorize TRAIL using single-walled carbon nanotubes (SWCNTs) to mimic membrane TRAIL. Owing to their exceptional and revolutional properties, carbon nanotubes, especially SWCNTs, are used in a wide range of physical or, now, medical applications. Indeed due to their high mechanical resistance, their high flexibility and their hydrophobicity, SWCNTs are known to rapidly diffuse in an aqueous medium such as blood, opening the way of development of new drug nanovectors (or nanocarriers). Our TRAIL-based SWCNTs nanovectors proved to be more efficient than TRAIL alone death receptors in triggering cancer cell killing. These NPTs increased TRAIL pro-apoptotic potential by nearly 20-fold in different Human tumor cell lines including colorectal, nonsmall cell lung cancer, or hepatocarcinomas. We provide thus a proof-of-concept that TRAIL nanovector derivatives based on SWCNT may be useful to future nanomedicine therapies.

Poisson ratio and excess low-frequency vibrational states in glasses.

In glass, starting from a dependence of the Angell's fragility on the Poisson ratio [V. N. Novikov and A. P. Sokolov, Nature 431, 961 (2004)], and a dependence of the Poisson ratio on the atomic packing density [G. N. Greaves, A. L. Greer, R. S. Lakes, and T. Rouxel, Nature Mater. 10, 823 (2011)], we propose that the heterogeneities are predominantly density fluctuations in strong glasses (lower Poisson ratio) and shear elasticity fluctuations in fragile glasses (higher Poisson ratio). Because the excess of low-frequency vibration modes in comparison with the Debye regime (boson peak) is strongly connected to these fluctuations, we propose that they are breathing-like (with change of volume) in strong glasses and shear-like (without change of volume) in fragile glasses. As a verification, it is confirmed that the excess modes in the strong silica glass are predominantly breathing-like. Moreover, it is shown that the excess breathing-like modes in a strong polymeric glass are replaced by shear-like modes under hydrostatic pressure as the glass becomes more compact.

Comment on Manna et al. SARS-CoV-2 Inactivation in Aerosol by Means of Radiated Microwaves. Viruses 2023, 15, 1443.

In a recent article published in Viruses by Manna et al. [...].

Sensitivity of Localized Surface Plasmon Resonance and Acoustic Vibrations to Edge Rounding in Silver Nanocubes.

Precise knowledge of the dependence of nano-object properties on their structural characteristics such as their size, shape, composition, or crystallinity, in turn, enables them to be finely characterized using appropriate techniques. Spectrophotometry and inelastic light scattering spectroscopy are noninvasive techniques that are proving highly robust and efficient for characterizing the optical response and vibrational properties of metal nano-objects. Here, we investigate the optical and vibrational properties of monodomain silver nanocubes synthesized by the chemical route, with edge length ranging from around 20 to 58 nm. The synthesized nanocrystals are not perfectly cubic and exhibit rounded edges and corners. This rounding was quantitatively taken into account by assimilating the shape of the nanocubes to superellipsoids. The effect of rounding on their optical response was clearly evidenced by localized surface plasmon resonance spectroscopy and supported by calculations based on the discrete dipole approximation method. The study of their acoustic vibrations by high-resolution low-frequency Raman scattering revealed a substructure of the T2g band, which was analyzed as a function of rounding. The measured frequencies are consistent with the existence of an anticrossing pattern of the two T2g branches. Such an avoided crossing in the T2g modes is clearly evidenced by calculating the vibrational frequencies of silver nanocubes using the Rayleigh-Ritz variational method that accounts for both their real size, shape, and cubic elasticity. These results show that it is possible to assess the rounding of nanocubes, including by means of ensemble spectroscopic measurements on well-calibrated particles.

Sub-THz Vibrational Dynamics in Ordered Mesoporous Silica Nanoparticles.

The vibrational dynamics in the sub-THz range of mesoporous silica nanoparticles (MSNs) having ordered cylindrical mesopores was investigated. MCM-41 and SBA-15 particles were synthesized, and their structure was determined using scanning electron microscopy (SEM), low-angle X-ray diffraction (XRD), N2 physisorption analyses, and Raman scattering. Brillouin scattering measurements are reported and enabled determining the stiffness of the silica walls (speed of sound) using finite element calculations for the ordered mesoporous structure. The relevance of this approach is discussed based on the comparison between the numerical and experimental results and previous works reported in the literature.

Identification of the Proteins Determining the Blood Circulation Time of Nanoparticles.

The therapeutic efficacy and adverse impacts of nanoparticles (NPs) are strongly dependent on their systemic circulation time. The corona proteins adsorbed on the NPs determine their plasma half-lives, and hence, it is crucial to identify the proteins shortening or extending their circulation time. In this work, the in vivo circulation time and corona composition of superparamagnetic iron oxide nanoparticles (SPIONs) with different surface charges/chemistries were analyzed over time. SPIONs with neutral and positive charges showed the longest and shortest circulation times, respectively. The most striking observation was that corona-coated NPs with similar opsonin/dysopsonin content showed different circulation times, implying these biomolecules are not the only contributing factors. Long-circulating NPs adsorb higher concentrations of osteopontin, lipoprotein lipase, coagulation factor VII, matrix Gla protein, secreted phosphoprotein 24, alpha-2-HS-glycoprotein, and apolipoprotein C-I, while short-circulating NPs adsorb higher amounts of hemoglobin. Therefore, these proteins may be considered to be determining factors governing the NP systemic circulation time.

Acousto-plasmonic and surface-enhanced Raman scattering properties of coupled gold nanospheres/nanodisk trimers.

This work is devoted to the fundamental understanding of the interaction between acoustic vibrations and surface plasmons in metallic nano-objects. The acoustoplasmonic properties of coupled spherical gold nanoparticles and nanodisk trimers are investigated experimentally by optical transmission measurements and resonant Raman scattering experiments. For excitation close to resonance with the localized surface plasmons of the nanodisk trimers, we are able to detect several intense Raman bands generated by the spherical gold nanoparticles. On the basis of both vibrational dynamics calculations and Raman selection rules, the measured Raman bands are assigned to fundamental and overtones of the quadrupolar and breathing vibration modes of the spherical gold nanoparticles. Simulations of the electric near-field intensity maps performed at the Raman probe wavelengths showed strong localization of the optical energy in the vicinity of the nanodisk trimers, thus corroborating the role of the interaction between the acoustic vibrations of the spherical nanoparticles and the surface plasmons of the nanodisk trimers. Acoustic phonons surface enhanced Raman scattering is here demonstrated for the first time for such coupled plasmonic systems. This work paves the way to surface plasmon engineering for sensing the vibrational properties of nanoparticles.

Free Vibrations of Anisotropic Nano-Objects with Rounded or Sharp Corners.

An extension of the Rayleigh-Ritz variational method to objects with superquadric and superellipsoid shapes and cylinders with cross-sections delimited by a superellipse is presented. It enables the quick calculation of the frequencies and displacements for shapes commonly observed in nano-objects. Original smooth shape variations between objects with plane, convex, and concave faces are presented. The validity of frequently used isotropic approximations for experimentally relevant vibrations is discussed. This extension is expected to facilitate the assignment of features observed with vibrational spectroscopies, in particular in the case of single-nanoparticle measurements.

In vivo protein corona on nanoparticles: does the control of all material parameters orient the biological behavior?

Nanomaterials have a huge potential in research fields from nanomedicine to medical devices. However, surface modifications of nanoparticles (NPs) and thus of their physicochemical properties failed to predict their biological behavior. This requires investigating the "missing link" at the nano-bio interface. The protein corona (PC), the set of proteins binding to the NPs surface, plays a critical role in particle recognition by the innate immune system. Still, in vitro incubation offers a limited understanding of biological interactions and fails to explain the in vivo fate. To date, several reports explained the impact of PC in vitro but its applications in the clinical field have been very limited. Furthermore, PC is often considered as a biological barrier reducing the targeting efficiency of nano vehicles. But the protein binding can actually be controlled by altering PC both in vitro and in vivo. Analyzing PC in vivo could accordingly provide a deep understanding of its biological effect and speed up the transfer to clinical applications. This review demonstrates the need for clarifications on the effect of PC in vivo and the control of its behavior by changing its physicochemical properties. It unfolds the recent in vivo developments to understand mechanisms and challenges at the nano-bio interface. Finally, it reports recent advances in the in vivo PC to overcome and control the limitations of the in vitro PC by employing PC as a boosting resource to prolong the NPs half-life, to improve their formulations and thereby to increase its use for biomedical applications.

Ligand-dependent nano-mechanical properties of CdSe nanoplatelets: calibrating nanobalances for ligand affinity monitoring.

The influence of ligands on the low frequency vibration of cadmium selenide colloidal nanoplatelets of different thicknesses is investigated using resonant low frequency Raman scattering. The strong vibration frequency shifts induced by ligand modifications as well as sharp spectral linewidths make low frequency Raman scattering a tool of choice to follow ligand exchange as well as the nano-mechanical properties of the NPLs, as evidenced by a carboxylate to thiolate exchange study. Apart from their molecular weight, the nature of the ligands, such as the sulfur to metal bond of thiols, induces a modification of the NPLs as a whole, increasing the thickness by one monolayer. Moreover, as the weight of the ligands increases, the discrepancy between the mass-load model and the experimental measurements increase. These effects are all the more important when the number of layers is small and can only be explained by a modification of the longitudinal sound velocity. This modification takes its origin in a change of the lattice structure of the NPLs, that reflects on their elastic properties. These nanobalances are finally used to characterize ligand affinity with the surface using binary thiol mixtures, illustrating the potential of low frequency Raman scattering to finely characterize nanocrystal surfaces.

Acousto-plasmonic hot spots in metallic nano-objects.

We investigate the acousto-plasmonic dynamics of metallic nano-objects by means of resonant Raman scattering and time-resolved femtosecond transient absorption. We observe an unexpectedly strong acoustic vibration band in the Raman scattering of silver nanocolumns, usually not found in isolated nano-objects. The frequency and the polarization of this unexpected Raman band allow us to assign it to breathing-like acoustic vibration modes. On the basis of full electromagnetic near-field calculations coupled to the elasticity theory, we introduce a new concept of "acousto-plasmonic hot spots" which arise here because of the indented shape of the nanocolumns. These hot spots combine both highly localized surface plasmons and strong shape deformation by the acoustic vibrations at specific sites of the nano-objects. We show that the coupling between breathing-like acoustic vibrations and surface plasmons at the "acousto-plasmonic hot spots" is strongly enhanced, turning almost silent vibration modes into efficient Raman scatterers.

Inelastic Light Scattering by Long Narrow Gold Nanocrystals: When Size, Shape, Crystallinity, and Assembly Matter.

We report the synthesis of long narrow gold nanocrystals and the study of their vibrational dynamics using inelastic light-scattering measurements. Rich experimental spectra are obtained for monodomain gold nanorods and pentagonal twinned bipyramids. Their assignment involves diameter-dependent nontotally symmetric vibrations which are modeled in the framework of continuum elasticity by taking into account simultaneously the size, shape, and crystallinity of the nanocrystals. Light scattering by vibrations with angular momenta larger than 2 is reported. It is shown to increase with the ratio of the nanocrystals diameter to the interparticle separation. It originates from the plasmonic coupling due to the self-assembly of the nanocrystals after deposition.

Iron oxide-based nanostructured ceramics with tailored magnetic and mechanical properties: development of mechanically robust, bulk superparamagnetic materials.

Nanostructured iron-oxide based materials with tailored mechanical and magnetic behavior are produced in bulk form. By applying ultra-fast heating routines via spark plasma sintering (SPS) to supercrystalline pellets, materials with an enhanced combination of elastic modulus, hardness and saturation magnetization are achieved. Supercrystallinity - namely the arrangement of the constituent nanoparticles into periodic structures - is achieved through self-assembly of the organically-functionalized iron oxide nanoparticles. The optimization of the following SPS regime allows the control of organics' removal, necking, iron oxide phase transformations and nano-grain size retention, and thus the fine-tuning of both mechanical properties and magnetic response, up until the production of bulk mm-size superparamagnetic materials.

Contact laws between nanoparticles: the elasticity of a nanopowder.

Studies of the mechanical contact between nanometer-scale particles provide fundamental insights into the mechanical properties of materials and the validity of contact laws at the nanoscale which are still under debate for contact surfaces approaching atomic dimensions. Using in situ Brillouin light scattering under high pressure, we show that effective medium theories successfully predict the macroscopic sound velocities in nanopowders if one takes into account the cementation of the contacts Our measurements suggest the relevance of the continuum approach and effective medium theories to describe the contact between nanoparticles of diameters as small as 4 nm, i.e. with radii of contact of a few angstroms. In particular, we demonstrate that the mechanical properties of nanopowders strongly depend on the surface state of the nanoparticles. The presence of molecular adsorbates modifies significantly the contact laws.

Damping by bulk and shear viscosity of confined acoustic phonons for nanostructures in aqueous solution.

A nanoparticle in aqueous solution is modeled as a homogeneous elastic isotropic continuum sphere in contact with an infinite viscous compressible Newtonian fluid. The frequencies and damping of the confined vibrational modes of the sphere are calculated for the material parameters of a CdSe nanoparticle in water and a poly(methyl methacrylate) nanosphere in water. Although the effects of viscosity are found to be negligible for macroscopic objects, for nanoscale objects, both the frequency and damping of the vibrational modes are significantly affected by the viscosity of the liquid. Furthermore, both shear viscosity and bulk viscosity play an important role. A model of the spherical satellite tobacco mosaic virus consisting of outer solid layers with a water core is also investigated, and the viscosity of the water core is found to significantly damp the free vibrational modes. The same approach can be applied for nonspherical geometries and also to viscoelastic nanoparticles.