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Summary The synthetic potential of carbon dioxide as an abundant and renewable C1 chemical feedstock has attracted considerable attention in the past decade with a particular focus on devising novel catalytic transformations to access carboxylic acid building blocks in a direct and selective manner. Yet, beyond addressing limitations in substrate generality, little effort has been made toward improving the robustness and applicability of established carboxylation methodologies, resulting in a serious lack of uptake within the industrial sector. Herein, we provide a critical view of the catalytic carboxylation arena, discuss the current limitations, and explore how the most recent advances offer tantalizing hints of how these challenges may be addressed. We speculate that carboxylation reactions are in the midst of a transition to a much broader role in the synthetic community and may represent an important contribution toward a circular carbon economy if they become viable for industrialization.

In this work, we present an approach to cross-link cellulose nanofibrils (CNFs) with various metallic cations (Fe3+, Al3+, Ca2+, and Mg2+) to produce inks suitable for three-dimensional (3D) printing application. The printability of each hydrogel ink was evaluated, and several parameters such as the optimal ratio of Mn+:TOCNF:H2O were discussed. CNF suspensions were produced by mechanical disintegration of cellulose pulp with a microfluidizer and then oxidized with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). Finally, metal cations were introduced to the deprotonated TEMPO-oxidized CNF (TOCNF) suspension to cross-link the nanofibrils and form the corresponding hydrogels. The performances of each gel-ink were evaluated by rheological measurements and 3D printing. Only the gels incorporated with divalent cations Ca2+ and Mg2+ were suitable for 3D printing. The 3D printed structures were freeze-dried and characterized with Fourier transform infrared spectroscopy (FT-IR) and Scanning Electron Microscopy (SEM). The better interaction of the TOCNFs with the divalent metallic cations in terms of printability, the viscoelastic properties of the inks, and the variation trends owing to various metal cations and ratios are discussed.

The removal of unwanted entities or soiling material from surfaces is an essential operation in many personal, industrial, societal, and environmental applications. The use of liquid cleansers for cleaning and decontamination is ubiquitous, and this review seeks to identify commonality in the fluid flow phenomena involved, particularly in those that determine the effectiveness of such operations. The state of quantitative understanding and modeling is reviewed in relation to the topics of ( a) the cleanser contacting the soiled area, ( b) processes by which the cleanser effects soil removal, and ( c) transport of the soil or its derivatives away from the surface. This review focuses on rigid substrates and does not consider processes based on gas flows or bubbles.

This paper investigates a strategy to convert hydrophilic cellulose nanofibrils (CNF) into a hydrophobic highly cross-linked network made of cellulose nanofibrils and inorganic nanoparticles. First, the cellulose nanofibrils were chemically modified through an esterification reaction to produce a nanocellulose-based macroinitiator. Barium titanate (BaTiO3, BTO) nanoparticles were surface-modified by introducing a specific monomer on their outer-shell surface. Finally, we studied the ability of the nanocellulose-based macroinitiator to initiate a single electron transfer living radical polymerization of stearyl acrylate (SA) in the presence of the surface-modified nanoparticles. The BTO nanoparticles will transfer new properties to the nanocellulose network and act as a cross-linking agent between the nanocellulose fibrils, while the monomer (SA) directly influences the hydrophilic-lipophilic balance. The pristine CNF and the nanoparticle cross-linked CNF are characterized by FTIR, SEM, and solid-state 13C NMR. Rheological and dynamic mechanical analyses revealed a high dregee of cross-linking.

We study the steady laminar advective transport of a diffusive passive scalar released at the base of narrow three-dimensional longitudinal open channels with non-absorbing side walls and rectangular or truncated-wedge-shaped cross-sections. The scalar field in the advective--diffusive boundary layer at the base of the channels is fundamentally three-dimensional in the general case, owing to a three-dimensional velocity field and differing boundary conditions at the side walls. We utilise three-dimensional numerical simulations and asymptotic analysis to understand how this inherent three-dimensionality influences the advective-diffusive transport as described by the normalised average flux, the Sherwood $Sh$ or Nusselt numbers for mass or heat transfer, respectively. We show that $Sh$ is well approximated by an appropriately formulated two-dimensional calculation, even when the boundary layer structure is itself far from two-dimensional. This important result can significantly simplify the modelling of many laminar advection--diffusion scalar transfer problems: the cleaning or decontamination of confined channels, or transport processes in chemical or biological microfluidic devices., Comment: Accepted for International Journal of Heat and Mass Transfer (13/02/20)

Motivated by potential effects of the Earth's rotation on the Deepwater Horizon oil plume, we conducted laboratory experiments on salt-water point plumes in a homogeneous rotating environment across a wide range of Rossby numbers 0.02 < Ro < 1.3. We report a striking physical instability in the plume dynamics near the source: after approximately one rotation period, the plume tilts laterally and starts to precess anticyclonically. The mean precession frequency ω scales linearly with the rotation rate Ω as ω≈0.4Ω. We find no evidence of a critical Rossby number above which precession ceases. We infer that a conventionally defined Rossby number is not an appropriate parameter when the plume is maintained over a long time: provided Ω ≠ 0, rotation is always important to the dynamics. This indicates that precession may occur in persistent oceanic or atmospheric plumes even at low latitudes.

Superhydrophobic surfaces (SHSs) have the potential to reduce drag at solid boundaries. However, multiple independent studies have recently shown that small amounts of surfactant, naturally present in the environment, can induce Marangoni forces that increase drag, at least in the laminar regime. To obtain accurate drag predictions, one must solve the mass, momentum, bulk surfactant and interfacial surfactant conservation equations. This requires expensive simulations, thus preventing surfactant from being widely considered in SHS studies. To address this issue, we propose a theory for steady, pressure-driven, laminar, two-dimensional flow in a periodic SHS channel with soluble surfactant. We linearise the coupling between flow and surfactant, under the assumption of small concentration, finding a scaling prediction for the local slip length. To obtain the drag reduction and interfacial shear, we find a series solution for the velocity field by assuming Stokes flow in the bulk and uniform interfacial shear. We find how the slip and drag depend on the nine dimensionless groups that together characterize the surfactant transport near SHSs, the gas fraction and the normalized interface length. Our model agrees with numerical simulations spanning orders of magnitude in each dimensionless group. The simulations also provide the constants in the scaling theory. Our model significantly improves predictions relative to a surfactant-free one, which can otherwise overestimate slip and underestimate drag by several orders of magnitude. Our slip length model can provide the boundary condition in other simulations, thereby accounting for surfactant effects without having to solve the full problem.

Gold nanoparticles have been the center of interest for scientists since many decades. Within the last 20 years, the research in that field has soared with the possibility to design and study nanoparticles with controlled shapes. From spheres to more complex shapes such as stars, or anisotropic architectures like rods or bipyramids, these new systems feature plasmonic properties making them the tools of choice for studies on light-matter interactions. In that context, fluorescence quenching and enhancement by gold nanostructures is a growing field of research. In this review, we report a non-exhaustive summary of the synthetic modes for various shapes and sizes of isotropic and anisotropic nanoparticles. We then focus on fluorescent studies of these gold nano-objects, either considering “bare” particles (without modifications) or hybrid particles (surface interaction with a chromophore). In the latter case, the well-known metal-enhanced fluorescence (MEF) is more particularly developed; the mechanisms of MEF are discussed in terms of the additional radiative and non-radiative decay rates caused by several parameters such as the vicinity of the chromophore to the metal or the size and shape of the nanostructures.

Blue phases (BPs), a distinct class of liquid crystals (LCs) with 3D periodic ordering of double twist cylinders involving orthogonal helical director twists, have been theoretically studied as potential templates for tunable colloidal crystals. Here, we report the spontaneous formation of thermally reversible, cubic crystal nanoparticle (NP) assemblies in BPs. Gold NPs, functionalized to be highly miscible in cyanobiphenyl-based LCs, were dispersed in BP mixtures and characterized by polarized optical microscopy and synchrotron small-angle X-ray scattering (SAXS). The NPs assemble by selectively migrating to periodic strong trapping sites in the BP disclination lines. The NP lattice, remarkably robust given the small particle size (4.5 nm diameter), is commensurate with that of the BP matrix. At the BP I to BP II phase transition, the NP lattice reversibly switches between two different cubic structures. The simultaneous presence of two different symmetries in a single material presents an interesting opportunity to develop novel dynamic optical materials.

A strategy is devised for the conversion of cellulose nanofibrils (CNF) into fluorescently labeled probes involving the synthesis of CNF-based macroinitiators that initiate radical polymerization of methyl acrylate and acrylic acid N-hydroxysuccinimide ester producing a graft block copolymer modified CNF. Finally, a luminescent probe (Lucifer yellow derivative) was labeled onto the modified CNF through an amidation reaction. The surface modification steps were verified with solid-state (13)C nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy. Fluorescence correlation spectroscopy (FCS) confirmed the successful labeling of the CNF; the CNF have a hydrodynamic radius of about 700 nm with an average number of dye molecules per fibril of at least 6600. The modified CNF was also imaged with confocal laser scanning microscopy. Luminescent CNF proved to be viable biomarkers and allow for fluorescence-based optical detection of CNF uptake and distribution in organisms such as crustaceans. The luminescent CNF were exposed to live juvenile daphnids and microscopy analysis revealed the presence of the luminescent CNF all over D. magna's alimentary canal tissues without any toxicity effect leading to the death of the specimen.

Cellulose nanofibril (CNF)-based materials are increasingly used in industrial and commercial applications. However, the impacts of CNF on aquatic life are poorly understood, and there are concerns regarding their potential toxicity. Using a combination of standard ecotoxicological tests and feeding experiments, we assessed the effects of CNF exposure (0.206-20.6 mg/L) on the feeding (food uptake and gut residence time) and life-history traits (growth and reproduction) in the cladoceran Daphnia magna. No mortality was observed in a 48 h acute exposure at 2060 mg/L. Moreover, a 21-day exposure at low food and moderate CNF levels induced a stimulatory effect on growth, likely driven by increased filtration efficiency, and, possibly, partial assimilation of the CNF by the animals. However, at low food levels and the highest CNF concentrations, growth and reproduction were negatively affected. These responses were linked to caloric restriction caused by dilution of the food source, but not an obstruction of the alimentary canal. Finally, no apparent translocation of CNF past the alimentary canal was detected. We conclude that CNF displays a low toxic potential to filter-feeding organisms and the expected environmental risks are low.

This paper is associated with a video winner of a 2017 APS/DFD Gallery of Fluid Motion Award. The original video is available from the Gallery of Fluid Motion, https://doi.org/10.1103/APS.DFD.2017.GFM.V0098, Physical Review Fluids, 3 (10), ISSN:2469-990X

Highly functionalized 5-bromo-2-amino-1,3-thiazoles bearing various substituents could be easily prepared by a rapid and efficient one-pot method, using simple starting materials and mild conditions while avoiding the use of metal catalysts or inconvenient reagents such as elemental halogens. These useful products can serve as starting materials for other reactions or as pharmacologically interesting compounds. In our work we have shown that the resulting 5-bromothiazole compounds could lead to monoacylglycerol lipase (MAGL) inhibition in the μM range.

Superhydrophobic surfaces (SHSs) have the potential to achieve large drag reduction for internal and external flow applications. However, experiments have shown inconsistent results, with many studies reporting significantly reduced performance. Recently, it has been proposed that surfactants, ubiquitous in flow applications, could be responsible, by creating adverse Marangoni stresses. Yet, testing this hypothesis is challenging. Careful experiments with purified water show large interfacial stresses and, paradoxically, adding surfactants yields barely measurable drag increases. This suggests that other physical processes, such as thermal Marangoni stresses or interface deflection, could explain the lower performance. To test the surfactant hypothesis, we perform the first numerical simulations of flows over a SHS inclusive of surfactant kinetics. These simulations reveal that surfactant-induced stresses are significant at extremely low concentrations, potentially yielding a no-slip boundary condition on the air--water interface (the "plastron") for surfactant amounts below typical environmental values. These stresses decrease as the streamwise distance between plastron stagnation points increases. We perform microchannel experiments with thermally-controlled SHSs consisting of streamwise parallel gratings, which confirm this numerical prediction. We introduce a new, unsteady test of surfactant effects. When we rapidly remove the driving pressure following a loading phase, a backflow develops at the plastron, which can only be explained by surfactant gradients formed in the loading phase. This demonstrates the significance of surfactants in deteriorating drag reduction, and thus the importance of including surfactant stresses in SHS models. Our time-dependent protocol can assess the impact of surfactants in SHS testing and guide future mitigating designs., Comment: 25 pages including supplemental information, 7 figures; videos available on request

A strategy is devised for the conversion of hydrophilic cellulose nanofibrils (CNFs) into hydrophobic CNF that form a stable nanocomposite dispersion for functional reinforcement of a polypropylene matrix. For that purpose, CNF was converted to a CNF-based microinitiator through an esterification reaction on the nanofibril surfaces, which efficiently initiated the controlled radical grafting polymerization of stearyl acrylate. The grafting-from modification was performed with and without a sacrificial initiator and verified with solid-state 13C nuclear magnetic resonance and Fourier transform infrared spectroscopy. CNF-based nanocomposites were prepared using the combination of a twin-screw mini extruder and melt pressing. Scanning electron microscopy reveals a homogeneous dispersion of the hydrophobic CNF in composite matrix with no signs of aggregation. Hydrophobic CNF showed a strong compatibility with the polypropylene matrix.

We present a small-angle coherent x-ray scattering technique used for measuring flow velocities in slow moving materials. The technique is an extension of X-ray Photon Correlation Spectroscopy (XPCS): It involves mixing the scattering from moving tracer particles with a static reference that heterodynes the signal. This acts to elongate temporal effects caused by flow in homodyne measurements, allowing for a more robust measurement of flow properties. Using coherent x-ray heterodyning, velocities ranging from 0.1 to 10 μm/s were measured for a viscous fluid pushed through a rectangular channel. We describe experimental protocols and theory for making these Poiseuille flow profile measurements and also develop the relevant theory for using heterodyne XPCS to measure velocities in uniform and Couette flows.

International audience; We describe the design of original nanocarriers that allows for ultrahigh chromophore loading while maintaining the photo-activity of each individual molecule. They consist in shells of charged biocompatible polymers grafted on gold nanospheres. The self-organization of extended polymer chains results from repulsive charges and steric interactions that are optimized by tuning the surface curvature of nanoparticles. This type of nano-scaffolds can be used as light-activated theranostic agents for fluorescence imaging and photodynamic therapy. We demonstrate that, labeled with a fluorescent photosensitizer, it can localize therapeutic molecules before triggering the cell death of B16-F10 melanoma with an efficiency that is similar to the efficiency of the polymer conjugate alone, and with the advantage of extremely high local loading of photosensitizers (object concentration in the picomolar range).

International audience; Light-matter interactions are of great interest for potential biological applications (bioimaging, biosensing, phototherapy). For such applications, sharp nanostructures exhibit interesting features since their extinction bands (surface plasmon resonance) cover a large bandwidth in the whole visible wavelength region due to the existence of ?hot spots? located at the end of the tips. In this context, gold nanostars appear to be interesting objects. However, their study remains difficult, mainly due to complicated synthetic methods and further functionalization. This paper reports the synthesis, functionalization, and photophysics of luminescent hybrid gold nanostars prepared using a layer-by-layer (LbL) deposition method for the tuning of chromophore-to-particle distances together with the impact of the spectral overlap between the plasmon and the emission/absorption of the dyes. Several luminescent dyes with different optical signatures were selectively adsorbed at the nanoparticle surface. The optimized systems, exhibiting the highest luminescence recovery, clearly showed that overlap must be as low as possible. Also, the fluorescence intensities were quenched in close vicinity of the metal surface and revealed a distance-dependence with almost full recovery of the dyes emission for 11 LbL layers, which corresponded to 15 nm distances evaluated on dried samples. The photophysics of the luminescent core?shell particles were carried out in suspension and correlated with the response of isolated single objects.

International audience; Homodimers of noble metal nanocubes form model plasmonic systems where the localized plasmon resonances sustained by each particle not only hybridize but also coexist with excitations of a different nature: surface plasmon polaritons confined within the Fabry−Perot cavity delimited by facing cube surfaces (i.e., gap plasmons). Destructive interference in the strong coupling between one of these highly localized modes and the highly radiating longitudinal dipolar plasmon of the dimer is responsible for the formation of a Fano resonance profile and the opening of a spectral window of anomalous transparency for the exciting light. We report on the clear experimental evidence of this effect in the case of 50 nm silver and 160 nm gold nanocube dimers studied by spatial modulation spectroscopy at the single particle level. A numerical study based on a plasmon mode analysis leads us to unambiguously identify the main cavity mode involved in this process and especially the major role played by its symmetry. The Fano depletion dip is red-shifted when the gap size is decreasing. It is also blue-shifted and all the more pronounced that the cube edge rounding is large. Combining nanopatch antenna and plasmon hybridization descriptions, we quantify the key role of the face-to-face distance and the cube edge morphology on the spectral profile of the transparency dip. T he optical excitation of localized surface plasmon resonances (LSPR) in single metallic nanoparticles or multicomponent nanostructures is responsible for efficient resonant far-field scattering and near-field concentration of light. 1,2 Such nanoantennas offer the opportunity to manipulate light at scales much shorter than the wavelength by making the best use of the LSPR sensitivity to variations in particle shape, size, chemical composition, and dielectric environment. 3,4 The electrostatic coupling between several plasmonic subunits is an additional tool for tailoring the optical response over a wide spectral range. 5,6 In this respect, much attention is paid to analogues of Fano resonances in classical electrostatics and especially those arising from the coupling between a " dark " plasmonic mode (weak dipole moment and narrow line width) and a degenerate mode that is highly radiative over a much broader spectral range (" bright " mode, large dipole moment). On either side of the resonance, the rapid phase shift of the " dark " mode polarizability relative to that of the bright mode and the exciting field may induce constructive or destructive interference in the net far field scattering process. They result in the formation of a dip in the broad spectral band of the far field scattered light with a typical dissymmetric profile and a narrow width related to the " dark " resonance lifetime. 7−11 Fano resonances open sharp and transparent windows in the plasmonic response of metallic nanostructures. 12−14 Their high sensitivity to relative changes in the nanostructure dielectric environment can be efficiently exploited for chemical and biological sensing. 15,16 Most of the studies in this field deal with noble metal nanoantennas built from the assembly and coupling of subunits of various size, shape, and orientation: oligomers of colloidal particles (DNA assembled, 17,18 heterodimers 19) and predominantly objects engraved by electron-beam lithography. 20−22 This method offers considerable flexibility for designing the spectral response of intricate structures with an advantageous symmetry breaking. 13,23 In the far field, they act as wide band

We study the fluid mechanics of removing a passive tracer contained in small, viscous drops attached to a flat inclined substrate using thin gravity-driven film flows. A convective mass transfer establishes across the drop-film interface and the tracer in the drop diffuses into the film flow. The Peclet number for the tracer in the film is large. The Peclet number Pe_d in the drop varies from 0.01 to 1. The characteristic transport time in the drop is much larger than in the film. We model the mass transfer of the tracer from the drop bulk into the film using an empirical model based on Newton's law of cooling. This model is supported by a theoretical model solving the quasi-steady 2D advection-diffusion equation in the film coupled with a time-dependent 1D diffusion equation in the drop. We find excellent agreement between our experimental data and the 2 models, which predict an exponential decrease in time of the tracer concentration in the drop. The results are valid for all drop and film Peclet numbers studied. The transport characteristic time is related to the drop diffusion time scale, as diffusion within the drop is the limiting process. Our theoretical model predicts the well-known relationship between the Sherwood and Reynolds numbers in the case of a well-mixed drop Sh~Re_L^{1/3}=\gamma L^2/\nu_f, based on the drop length L, film shear rate \gamma and film kinematic viscosity \nu_f. We show that this relationship is mathematically equivalent to a more physically intuitive relationship Sh~Re_\delta, based on the diffusive boundary layer thickness \delta. The model also predicts a correction in the case of a non-uniform drop concentration, which depends on Re_\delta, the Schmidt number, the drop aspect ratio and the diffusivity ratio. This prediction is in agreement with experiments at low Pe_d. It also agrees as Pe_d approaches 1, although the influence of Re_\delta increases., Comment: Revised manuscript under review in Journal of Fluid Mechanics. 41 pages, 9 figures

International audience; Anisotropic gold nanoparticles and in particular with shapes exhibiting tips are known to present an extremely strong localized electromagnetic field. This field is mostly located at the top of the tips and can be used in various optical applications. Moreover, as a consequence of their anisotropy, they present two plasmon resonance bands corresponding to the transverse and longitudinal resonance modes. Tuning the aspect ratio it becomes possible to display SPR bands near the near infrared region. This was particularly investigated in the case of nanorods and also for bipyramids. In this paper we report a high yield synthesis approach that allows one to precisely control the aspect ratio of bipyramids and to elongate the structure until they adopt a javelin-like aspect. We were able to prepare nano-javelins with surface plasmon resonances up to 1850 nm, opening important perspectives in terms of optical applications in the NIR and IR regions. The synthetic methods are fully reported and the optical properties were correlated with the theoretical approach, taking into consideration not only the aspect ratio but also the truncation of the nano-objects.

WO3 nanorods and wires were obtained via hydrothermal synthesis using sodium tungstate as a precursor and either oxalic acid, citric acid, or poly(methacrylic acid) as a stabilizing agent. Transmission electron microscopy images showed that the organic acids with different numbers of carboxylic groups per molecule influence the final sizes and stacking nanostructures of WO3 wires. Three-dimensional electron diffraction tomography of a single nanocrystal revealed a hexagonal WO3 structure with preferential growth along the c-axis, which was confirmed by high-resolution transmission electron microscopy. WO3 nanowires were also spin-coated onto an indium tin oxide/glass conducting substrate, resulting in the formation of a film that was characterized by scanning electron microscopy. Finally, cyclic voltammetry measurements performed on the WO3 thin film showed voltammograms typical for the WO3 redox process.

International audience; A great number of studies focus their interest on the photophysical properties of fluorescent hybrid gold nanoparticles for potential applications in biotechnologies such as imaging and/or treatment. Spherical gold nanoparticles are known to quench a chromophore fluorescent signal, when moieties are located in their close vicinity. The use of a polymer spacer on such a system allowed only partial recovery of the dye emission by controlling the surface to dye distance. Gold-based anisotropic sharp nanostructures appear to exhibit more interesting features due to the strong electric field generated at their edges and tips. In this paper, a complete study of hybrid fluorescent bipyramidal-like gold nanostructures is presented. We describe the chemical synthesis of gold bipyramids functionalized with fluorescent water-soluble polymers and their photophysics both in solution and on a single object. We show that the use of a bipyramidal shape instead of a spherical one leads to total recovery of the fluorescence and even to an enhancement of the emission of the dyes by a factor of 1.4.

International audience; The use of microfluidic devices for the handling and analysis of suspensions of colloidal gold particles is presented. The plasmonic particles are detected via their resonant light scattering (RLS) in a simple and versatile LED-based dark field illumination geometry. RLS enables both microscopic imaging and microspectroscopy. The measurement of the diffusion coefficient of nanoparticles in this type of devices is demonstrated. Nanoparticles are separated from small (free ligand) molecules in a continuous flow process. Reversible aggregation of functionalized particles is detected in microflow by means of RLS, which opens perspectives for the development of microfluidic bioplasmonic detection schemes.

International audience; Dark field resonant light scattering by gold and silver nanoparticles enables the detection and spectroscopy of such particles with high sensitivity, down to the single-particle level, and can be used to implement miniaturised optical detection schemes for chemical and biological analysis. Here, we present a straightforward optical spectroscopic methodology for the quantitative spectrometric study of resonant light scattering (RLS) by nanoparticles. RLS spectroscopy is complementary to UV-visible absorbance measurements, and we apply it to the characterisation and comparison of different types of gold, silver and gold-silver alloy nanoparticles. The potential of gold and silver particles as alternatives for fluorescent probes in certain applications is discussed. RLS spectroscopy is shown to be useful for studying analyte-induced gold nanoparticle assembly and nanoparticle chemistry, which can induce radical changes in the plasmonic resonances responsible for the strong light scattering. Furthermore, the feasibility of dark field RLS detection and quantitation of metal nanoparticles in microfluidic volumes is demonstrated, opening interesting possibilities for the further development of microfluidic detection schemes.

International audience; A great number of works have focused their research on the synthesis, design and optical properties of gold nanoparticles for potential biological applications (bioimaging, biosensing). For this kind of application, sharp gold nanostructures appear to exhibit the more interesting features since their surface plasmon bands are very sensitive to the surrounding medium. In this paper, a complete study of PEGylated gold nanostars and PEGylated bipyramidal-like nanostructures is presented. The nanoparticles are prepared in high yield and their surfaces are covered with a biocompatible polymer. The photophysical properties of gold bipyramids and nanostars, in suspension, are correlated with the optical response of single and isolated objects. The resulting spectra of isolated gold nanoparticles are subsequently correlated to their geometrical structure by transmission electron microscopy. Finally, the PEGylated gold nanoparticles were incubated with melanoma B16-F10 cells. Dark-field microscopy showed that the biocompatible gold nanoparticles were easily internalized and most of them localized within the cells.

International audience; Dry aqueous foams made of anionic surfactant (SDS) and spherical gold nanoparticles are studied by small angle X-ray scattering and by optical techniques. To obtain stable foams, the surfactant concentration is well above the critical micelle concentration. The specular reflectivity signal obtained on a very thin film (thickness 20 nm) shows that functionalized nanoparticles (17 nm typical size) are trapped within the film in the form of a single monolayer. In order to isolate the film behavior, investigations are made on a single film confined in a tube. The film thinning according to the ratio of functionalized nanoparticle and SDS micelles (1:1, 1:10, 1:100) is mainly governed by the structural arrangement of SOS micelles. In thick films, nanoparticles tend to form aggregates that disappear during drainage. In particular self-organization of nanoparticles (with different surface charge) inside the film is not detected.

International audience; A great number of works focus their interest on the study of gold nanoparticle plasmonic properties. Among those, sharp nanostructures appear to exhibit the more interesting features for further developments. In this paper, a complete study on bipyramidal-like gold nanostructures is presented. The nano-objects are prepared in high yield using an original method. This chemical process enables a precise control of the shape and the size of the particles. The specific photophysical properties of gold bipyramids in suspension are ripened by recording the plasmonic response of single and isolated objects. Resulting extinction spectra are precisely correlated to their geometrical structure by mean of electron tomography at the single-particle level. The interplay between the geometrical structure and the optical properties of twisted gold bipyramids is further discussed on the basis of numerical calculations. The influence of several parameters is explored such as the structural aspect ratio or the tip truncation. In the case of an incident excitation polarized along the particle long axis, this study shows how the plasmon resonance position can be sensitive to these parameters and how it can then be efficiently tuned on a large wavelength range.

International audience; A simple and versatile methodology has been developed for the simultaneous measurement of multiple concentration profiles of colourants in transparent microfluidic systems, using a conventional transmitted light microscope, a digital colour (RGB) camera and numerical image processing combined with multicomponent analysis. Rigorous application of the Beer-Lambert law would require monochromatic probe conditions, but in spite of the broad spectral bandwidths of the three colour channels of the camera, a linear relation between the measured optical density and dye concentration is established under certain conditions. An optimised collection of dye solutions for the quantitative optical microscopic characterisation of microfluidic devices is proposed. Using the methodology for optical concentration measurement we then implement and validate a simplified and robust method for the microfluidic measurement of diffusion coefficients using an H-filter architecture. It consists of measuring the ratio of the concentrations of the two output channels of the H-filter. It enables facile determination of the diffusion coefficient, even for non-fluorescent molecules and nanoparticles, and is compatible with non-optical detection of the analyte.

International audience; The binding of disulfides to gold nanoparticles was investigated using fluorescence spectroscopy and a perylene-monoimide dye coupled to a dissymmetric disulfide via a tetraethyleneglycolalkyl chain (PMImSS). Quantum chemical calculations using the polarizable continuum model (PCM) predict a strong quenching of perylene-monoimide fluorescence by gold nanoparticles as a result of efficient excitation energy transfer from the dye to the particle. Such quenching is indeed observed when unfunctionalised gold nanoparticles are added to a solution of PMImSS. The fluorimetric titration curves show behaviour indicative of the existence of an equilibrium between free and bound ligands (association constant 5 x 10^5 M-1 ), whereas the affinity of thiols and disulfide for gold surfaces is in general assumed to be much higher. Gold nanoparticles fully functionalised with PMImSS were synthesised and purified. Fluorescence correlation spectroscopy shows the appearance of free PMImSS ligands in dilute (approx. pM) suspensions of these PMImSS-functionalised nanoparticles over a period of several days.

International audience; The prediction of the rise speed of large buoyant bubbles is a fundamental fluid mechanics problem relevant to a number of applications ranging from carbon sequestration technology to chemical engineering or astrophysics. Single large bubbles typically have a spherical cap shape with bubbles of larger volume rising faster than the ones of smaller volume. However, except in well-controlled experiments, the released gas splits into a leading cap bubble, followed by a crown of satellite bubbles that can contain up to 50% of the total volume of gas. We find that in this case the satellite bubbles rearrange in a characteristic toroidal crown and the leading bubble takes a lenticular shape. The rise speeds of these multipart bubble systems and the ratios of the torus radii to the leading cap curvature radii are quite constant and predictable in the mean and are furthermore independent of the gas partitioning between the leading lenticular bubble and the crown of satellite bubbles. We also find that this multipart bubble system rises slightly faster than a single cap bubble with the same total injected volume of gas. © 2008 American Institute of Physics.

Lactate dehydrogenases (LDHs) are tetrameric enzymes of major significance in cancer metabolism as well as promising targets for cancer therapy. However, their wide and polar catalytic sites make them a challenging target for orthosteric inhibition. In this work, we conceived to target LDH tetramerization sites with the ambition of disrupting their oligomeric state. To do so, we designed a protein model of a dimeric LDH-H. We exploited this model through WaterLOGSY nuclear magnetic resonance and microscale thermophoresis for the identification and characterization of a set of α-helical peptides and stapled derivatives that specifically targeted the LDH tetramerization sites. This strategy resulted in the design of a macrocyclic peptide that competes with the LDH tetramerization domain, thus disrupting and destabilizing LDH tetramers. These peptides and macrocycles, along with the dimeric model of LDH-H, constitute promising pharmacological tools for the de novo design and identification of LDH tetramerizationdisruptors. Overall, our study demonstrates that disrupting LDH oligomerization state by targeting their tetramerization sites is achievable and paves the way toward LDH inhibition through this novel molecular mechanism.

We introduce an approach for solving the incompressible Navier-Stokes equations on a forest of Octree grids in a parallel environment. The methodology uses the p4est library of Burstedde et al. (2011) [15] for the construction and the handling of forests of Octree meshes on massively parallel distributed machines and the framework of Mirzadeh et al. (2016) [54] for the discretizations on Octree data structures. We introduce relevant additional parallel algorithms and provide performance analyses for individual building bricks and for the full solver. We demonstrate strong scaling for the solver up to 32,768 cores for a problem involving O ( 6.1 × 10 8 ) computational cells. We illustrate the dynamic adaptive capabilities of our approach by simulating flows past a stationary sphere, flows due to an oscillatory sphere in a closed box and transport of a passive scalar. Without sacrificing accuracy nor spatial resolution in regions of interest, our approach successfully reduces the number of computational cells to (at most) a few percents of uniform grids with equivalent resolution. We also perform a numerical simulation of the turbulent flow in a superhydrophobic channel with unparalleled wall grid resolution in the streamwise and spanwise directions.