Surface-Initiated Controlled Radical Polymerization Approach to In Situ Cross-Link Cellulose Nanofibrils with Inorganic Nanoparticles.

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.

Surface-Initiated Controlled Radical Polymerization Approach To Enhance Nanocomposite Integration of Cellulose Nanofibrils.

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.

Luminescent Nanocellulose Platform: From Controlled Graft Block Copolymerization to Biomarker Sensing.

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.

Multicolor fluorescent labeling of cellulose nanofibrils by click chemistry.

We have chemically modified cellulose nanofibrils (CNF) with furan and maleimide groups, and selectively labeled the modified CNF with fluorescent probes; 7-mercapto-4-methylcoumarin and fluorescein diacetate 5-maleimide, through two specific click chemistry reactions: Diels-Alder cycloaddition and the thiol-Michael reaction. Characterization by solid-state (13)C NMR and infrared spectroscopy was used to follow the surface modification and estimate the substitution degrees. We demonstrate that the two luminescent dyes could be selectively labeled onto CNF, yielding a multicolor CNF that was characterized by UV/visible and fluorescence spectroscopies. It was demonstrated that the multicolor CNF could be imaged using a confocal laser scanning microscope.

WO3 nanorods created by self-assembly of highly crystalline nanowires under hydrothermal conditions.

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.

Phase identification and structure solution by three-dimensional electron diffraction tomography: Gd-phosphate nanorods.

Hydrothermal synthesis of GdPO4 in the presence of poly(methacrylic acid) yields nanorods with a diameter of 15 nm and an aspect ratio of 20. Powder X-ray diffraction patterns showed that the GdPO4 nanorods display peaks characteristics for both monoclinic and hexagonal structures. Three-dimensional electron diffraction tomography (3D EDT) was used to determine the structures ab initio on the basis of reciprocal volume reconstruction of electron diffraction data sets collected from single nanorods. The crystal structure of the monoclinic form was shown to be P21/n, corroborating previous work. We were able to solve the 3D structure of the hexagonal P6222 form, which has not been reported previously. Our work shows that 3D EDT is a powerful method that can be used for solving structures of single nanocrystals.

Tuning dye-to-particle interactions toward luminescent gold nanostars.

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.

Resonant light scattering spectroscopy of gold, silver and gold-silver alloy nanoparticles and optical detection in microfluidic channels.

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.

3D Printable Hybrid Gel Made of Polymer Surface-Modified Cellulose Nanofibrils Prepared by Surface-Initiated Controlled Radical Polymerization (SI-SET-LRP) and Upconversion Luminescent Nanoparticles.

A cellulose nanofibril-based hybrid gel material was developed by grafting the polymerized stearyl acrylate (PSA) and upconversion nanoparticles (UCNPs) onto cellulose nanofibrils (CNFs) via Cu0-mediated radical polymerization (SET-LRP) to create a highly cross-linked CNF system. A two-step strategy was exploited to surface-exchange the ligand of the UCNPs from a hydrophobic ligand (oleic acid) to a hydrophilic small-molecule ligand (2-acrylamido-2-methyl-1-propanesulfonic acid, AMPS) and therefore be suitable for SET-LRP. The characteristics and properties of the hybrid material (UCNP-PSA-CNF) were monitored by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), rheology, X-ray diffraction (XRD), and microscopic analysis. Those characterization techniques prove the efficient modification of the CNF, with the presence of 1.8% UCNPs. The luminescence measurement was carried out using a homebuilt confocal microscope with a 980 nm laser source. The nanostructure of UCNPs and their incorporated CNF species were measured by small-angle X-ray scattering (SAXS). In addition, this CNF-based hybrid gel has decisive rheological properties, such as good viscoelasticity (loss tangent was below 0.35 for the UCNP-PSA-CNF gel, while the PSA-CNF gel reached the highest value of 0.42), shear-thinning behavior, and shape retention, and was successfully applied to three-dimensional (3D) gel printing throughout various 3D print models.

Synthesis, electron tomography and single-particle optical response of twisted gold nano-bipyramids.

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.

Synthesis of PEGylated gold nanostars and bipyramids for intracellular uptake.

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.

3D printing of a bio-based ink made of cross-linked cellulose nanofibrils with various metal cations.

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.

Probing the interactions between disulfide-based ligands and gold nanoparticles using a functionalised fluorescent perylene-monoimide dye.

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.

Multi-level toxicity assessment of engineered cellulose nanofibrils in Daphnia magna.

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.

Fano Transparency in Rounded Nanocube Dimers Induced by Gap Plasmon Coupling.

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.

The intrinsic luminescence of individual plasmonic nanostructures in aqueous suspension by photon time-of-flight spectroscopy.

We have studied the intrinsic one-photon excited luminescence of freely diffusing gold nanoparticles of different shapes in aqueous suspension. Gold nanospheres were used as a reference, since their luminescence has been investigated previously and their light absorption and scattering properties are described analytically by Mie theory. We then studied gold nanobipyramids and nanostars that have recently gained interest as building blocks for new plasmonic nanosensors. The aim of our study is to determine whether the luminescence of gold nanoparticles of complex shape (bipyramids and nanostars) is a plasmon-assisted process, in line with the conclusions of recent spectroscopic studies on spheres and nanorods. Our study has been performed on particles in suspension in order to avoid any artefact from the heterogeneous environment created when particles are deposited on a substrate. We employ a recently developed photon time-of-flight method in combination with correlation spectroscopy of the light scattered by the particles to probe the luminescent properties of individual particles based on a particle-by-particle spectral analysis. Furthermore, we have performed resonant light scattering spectroscopic measurements on the same samples. Our work demonstrates the power of our time-of flight method for uncovering the plasmonic signatures of individual bipyramids and nanostars during their brief passage in the focal volume of a confocal set-up. These spectral features of individual particles remain hidden in macroscopic measurements. We find that the intrinsic photoluminescence emission of gold bipyramids and gold nanostars is mediated by their localized surface plasmons.

Nanocarriers with ultrahigh chromophore loading for fluorescence bio-imaging and photodynamic therapy.

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).

Quantitative full-colour transmitted light microscopy and dyes for concentration mapping and measurement of diffusion coefficients in microfluidic architectures.

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.

Foam films in the presence of functionalized gold nanoparticles.

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 SDS 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.