Hybrid CdSe/ZnS Quantum Dot-Gold Nanoparticle Composites Assembled by Click Chemistry: Toward Affordable and Efficient Redox Photocatalysts Working with Visible Light.

A new modular, easy-to-synthesize photocatalyst was prepared by assembling colloidal CdSe/ZnS quantum dots (QD) and gold nanoparticles (AuNP) via their ligands thanks to copper-catalyzed azide to alkyne cycloaddition (CuAAC) click chemistry. The resulting composite (QD-AuNP) photocatalyst was tested with a benchmark photoredox system previously reported by our group, for which QD alone acted as a photocatalyst but with a modest quantum yield (QY = 0.06%) and turnover number (TON = 350 in 3 h) due to poor charge separation. After optimization, the QD-AuNP composites exhibited much improved photocatalytic performances: up to five times higher TON (2600 in 3 h) and up to 24 times faster reaction in the first 10 min of visible irradiation. Such an improvement is attributed to an efficient electron transfer from QD to AuNP in the photoexcited QD-AuNP composites, which ensures a much better charge separation than that in QD alone. This was confirmed by studying both (i) the quenching of the QD photoluminescence during the synthesis of the QD-AuNP composites and (ii) the blue shift of the AuNP plasmon absorption band due to the accumulation of up to 7400 electrons per AuNP in QD-AuNP composites under visible light irradiation in the presence of electron donors.

Determinants and Characterization of Locomotion in Adults with Late-Onset Pompe Disease: New Clinical Biomarkers.

BACKGROUND: The late-onset form of Pompe disease (LOPD) is characterized by muscle weakness, locomotor limitations and a risk of falls. The mechanisms responsible for altered locomotion in adults with LOPD are unknown. The identification of clinical biomarkers is essential for clinical follow-up and research. OBJECTIVES: To identify muscle determinants of impaired locomotor performance, gait stability and gait pattern, and biomechanical determinants of falls in adults with LOPD. METHODS: In this cross-sectional, case-control study, LOPD and control participants underwent 3D gait analysis, locomotor performance tests and muscle strength measurements (isokinetic dynamometer). We explored the muscular determinants of locomotor performance (gait speed, 6-minute walk test distance and timed up and go test), gait stability (spatiotemporal gait variables) and the gait pattern. We also explored biomechanical gait determinants of falls. After intergroup comparisons, determinants were sought to use forward stepwise multiple regression. RESULTS: Eighteen participants with LOPD and 20 control participants were included. Locomotor performance, gait stability, and the gait pattern were significantly altered in LOPD compared to control participants. Hip abductor strength was the main common determinant of locomotor performance, gait stability and pelvic instability. Hip flexor strength was the main determinant of abnormal gait kinematics at the hip and knee. Percentage duration of single support phase during the gait cycle was the main determinant of falls. CONCLUSIONS: Hip abductor strength and percentage duration of single support during gait were the major determinants of locomotor performance, gait stability, falls and the gait pattern in LOPD. These new clinical biomarkers should therefore be systematically assessed using instrumented tools to improve the follow-up of adults with LOPD. They should also be considered in future studies to accurately assess the effects of new therapies. Hip abductor strength and single support phase should also be priority targets for rehabilitation.

Fine Tuning of Quantum Dots Photocatalysts for the Synthesis of Tropane Alkaloid Skeletons.

Several types of Quantum Dots (QDs) (CdS, CdSe and InP, as well as core-shell QDs such as type I InP-ZnS, quasi type-II CdSe-CdS and inverted type-I CdS-CdSe) were considered for generating α-aminoalkyl free radicals. The feasibility of the oxidation of the N-aryl amines and the generation of the desired radical was evidenced experimentally by quenching of the photoluminescence of the QDs and by testing a vinylation reaction using an alkenylsulfone radical trap. The QDs were tested in a radical [3+3]-annulation reaction giving access to tropane skeletons and that requires the completion of two consecutive catalytic cycles. Several QDs such as CdS core, CdSe core and inverted type I CdS-CdSe core-shell proved to be efficient photocatalysts for this reaction. Interestingly, the addition of a second shorter chain ligand to the QDs appeared to be essential to complete the second catalytic cycle and to obtain the desired bicyclic tropane derivatives. Finally, the scope of the [3+3]-annulation reaction was explored for the best performing QDs and isolated yields that compare well with classical iridium photocatalysis were obtained.

Universal generation of devil's staircases near Hopf bifurcations via modulated forcing of nonlinear systems.

The discrete circle map is the archetypical example of a driven periodic system, showing a complex resonance structure under a change of the forcing frequency known as the devil's staircase. Adler's equation can be seen as the direct continuous equivalent of the circle map, describing locking effects in periodic systems with continuous forcing. This type of locking produces a single fundamental resonance tongue without higher-order resonances, and a devil's staircase is not observed. We show that, with harmonically modulated forcing, nonlinear oscillations close to a Hopf bifurcation generically reproduce the devil's staircase even in the continuous case. Experimental results on a semiconductor laser driven by a modulated optical signal show excellent agreement with our theoretical predictions. The locking appears as a modulation of the oscillation amplitude as well as the angular oscillation frequency. Our results show that by proper implementation of an external drive, additional regions of stable frequency locking can be introduced in systems which originally show only a single Adler-type resonance tongue. The induced resonances can be precisely controlled via the modulation parameters.

Harmonic frequency locking and tuning of comb frequency spacing through optical injection.

We show, both experimentally and theoretically, that a slave laser injected with an optical frequency comb can undergo two distinct locking mechanisms, both of which decrease the output optical comb's frequency spacing. We report that, for certain detuning and relative injection strengths, slave laser relaxation oscillations can become undamped and lock to rational frequencies of the optical comb spacing, creating extra comb tones by nonlinear dynamics of the injected laser. We also study the frequency locking of the slave laser at detunings in between the injected comb lines, which add the slave laser's frequency to the comb. Our results demonstrate the effect of the α parameter and stability of the locked states and indicate how the frequency of the relaxation oscillations affect both of these locking mechanisms. These optical locking mechanisms can be applied to regenerate or multiply optical combs.

In Situ Identification of Spherical Ag Monomers and Dimers at Zeptomole Adsorbate Concentrations by Surface-Enhanced Raman Scattering Correlation Spectroscopy.

We have developed a bright optical setup, especially optimized for surface-enhanced Raman scattering (SERS) correlation spectroscopy. We show that the brightness of the experiment combined with the correlation approach permits in situ access to the size and shape of the SERS-active aggregates in solution despite a very weak SERS signal of the adsorbed molecules. As a result, we demonstrate that dimers and larger SERS-active aggregates can be identified through the temporal fluctuations of the SERS signal of only a few hundred of adsorbed molecules, that is, at zeptomole adsorbate concentrations. Monomers covered by a monolayer of MBA were also identified. These results open a way for single nanoparticle sensing, for single-molecule SERS-active aggregate characterization, or for quantitative monitoring of functionalization processes on metallic objects.

Vaccination coverage in the context of the emerging Yellow Fever threat in French Guiana.

BACKGROUND: French Guiana, a French overseas department located in South America between Brazil and Surinam, is the only European territory geographically located in the Amazonian forest complex and is considered endemic for yellow fever (YF). In the context of the emergent threat of YF in Latin America, we conducted a large household cross-sectional survey from June to October 2017 to estimate vaccination coverage in the population and to determine associations with sociodemographic and geographical characteristics. METHODOLOGY/PRINCIPAL FINDINGS: In total, 1,415 households and 2,697 individuals were included from the 22 municipalities of French Guiana. YF vaccination coverage was estimated at 95.0% (95% CI: 93.4-96.2) in the entire territory but was spatially heterogeneous, with the lowest levels estimated in the western part of the territory along the Surinamese cross-border region, particularly in children under 16 years who were not enrolled in school, immigrant adults and disadvantaged populations with low socioeconomic indexes. CONCLUSIONS/SIGNIFICANCE: Despite the good vaccination coverage against YF in the general population of French Guiana resulting from the compulsory nature of YF vaccination for residents and travelers, there is an urgent need to improve vaccination coverage in vulnerable populations living in the northwestern part of the territory to limit the risk of transmission in the context of the emerging YF threat in South America. Despite the relative rarity of YF and the significant number of infectious and tropical diseases in French Guiana, clinicians should adopt a high index of suspicion for YF, particularly in vulnerable and at-risk populations.

Modeling mutually coupled non-identical semiconductor lasers on photonic integrated circuits.

We model the situation of two lasers in a face-to-face arrangement, optically coupled through an attenuating element, where the distance between the lasers is on a scale typical in photonic integration (hundreds of micrometers to millimeters). We account for the existence of a frequency difference between the two single-mode lasers. Modified versions of the Lang-Kobayashi equations were employed to describe the interaction. By solving this delay differential equation system, we characterized different dynamical regimes including one- and two-color states and self-pulsations. We focus on the effect varying coupling strength and detuning between the lasers has on the frequencies of the lasers. Using the results of this frequency study, we identify the bifurcations causing changes between the different frequency regimes.

NIR-to-NIR Two-Photon Scanning Laser Microscopy Imaging of Single Nanoparticles Doped by Yb(III) Complexes.

The photophysical and nonlinear optical properties of water-soluble chromophore-functionalised tris-dipicolinate complexes [LnL3](3-) (Ln=Yb and Nd) are thoroughly studied, revealing that only the Yb(III) luminescence can be sensitized by a two-photon excitation process. The stability of the complex in water is strongly enhanced by embedding in dispersible organosilicate nanoparticles (NPs). Finally, the spectroscopic properties of [NBu4]3 [YbL3] are studied in solution and in the solid state. The high brightness of the NPs allows imaging them as single objects using a modified two-photon microscopy setup in a NIR-to-NIR configuration.

In situ electron-beam polymerization stabilized quantum dot micelles.

A polymerizable amphiphile polymer containing PEG was synthesized and used to encapsulate quantum dots in micelles. The quantum dot micelles were then polymerized using a "clean" electron beam process that did not require any post-irradiation purification. Fluorescence spectroscopy revealed that the polymerized micelles provided an organic coating that preserved the quantum dot fluorescence better than nonpolymerized micelles, even under harsh conditions.

Oligomeric PEG-phospholipids for solubilization and stabilization of fluorescent nanocrystals in water.

Water soluble fluorescent nanocrystals were obtained by encapsulation of hydrophobic quantum dots (QDs) with amphiphilic phospholipids derived from the ring opening metathesis of norbornene-based monomers. The robustness of the newly coated quantum dots was assessed by comparative studies under various ionic conditions which indicated an overall enhancement of their fluorescence stability.