Rapid ellipsometric imaging characterization of nanocomposite films with an artificial neural network.

Imaging ellipsometry is an optical characterization tool that is widely used to investigate the spatial variations of the opto-geometrical properties of thin films. As ellipsometry is an indirect method, an ellipsometric map analysis requires a modeling step. Classical methods such as the Levenberg-Marquardt algorithm (LM) are generally too time consuming to be applied on a large data set. In this way, an artificial neural network (ANN) approach was introduced for the analysis of an ellipsometric map. As a proof of concept this method was applied for the characterization of silver nanoparticles embedded in a poly-(vinyl alcohol) film. We demonstrate that the LM and ANN give similar results. However, the time required for the ellipsometric map analysis decreases from 15 days for the LM to 1 s for the ANN. This suggests that the ANN is a powerful tool for fast spectroscopic-ellipsometric-imaging analysis.

Analysis of accuracy and ambiguities in spatial measurements of birefringence in uniaxial anisotropic media.

Accuracy and ambiguities in retardance and optical axis orientation spatial measurements are analyzed in detail in the context of the birefringence imaging method introduced by Shribak and Oldenbourg [Appl. Opt.42, 3009 (2003)APOPAI0003-693510.1364/AO.42.003009]. An alternative formula was derived in order to determine the optical axis orientation more accurately, and without indetermination in the case of a quarter-wave plate sample. Following Shribak and Oldenbourg's experimental configuration using two variable retarders, a linear polarizer, and five polarization probes, we examined the effect of the swing angle χ, which selected the ellipticity of each polarization state, on the accuracy of retardance (Δ) and axis orientation (ϕ) measurements. Using a quarter-wave plate, excellent agreement between measured and expected values was obtained for both the retardance and the axis orientation, as demonstrated by the statistical analysis of Δ and ϕ spatial distributions. The intrinsic ambiguity in the determination of Δ and ϕ for superimposed layers of transparent anisotropic cello-tape is discussed in detail, and solutions are provided to remove this ambiguity. An example of application of the method on geological samples is also presented. We believe our analysis will guide researchers willing to exploit this long-standing method in their laboratories.

Analysis of accuracy and ambiguities in spatial measurements of birefringence in uniaxial anisotropic media: publisher's note.

This publisher's note corrects an error in Appl. Opt.61, 8081 (2022)APOPAI0003-693510.1364/AO.463657.

Biomarkers for Early Diagnosis of Hemophagocytic Lymphohistiocytosis in Critically Ill Patients.

Many biomarkers have been proposed for the diagnosis of secondary hemophagocytic lymphohistiocytosis (HLH) in adults, but comparative studies are lacking. We analyzed ferritin, glycosylated ferritin, soluble CD25, CD163 and CD14, IL-6, IFN-γ, IL-18, IL-10, IL-1ß, IL-12p70, IL-17α, IP-10, and CXCL9 levels to differentiate HLH from sepsis in critically ill patients. Of 120 patients, HLH was confirmed for 14 patients. Among the biomarkers tested, ferritin, IL-18, and glycosylated ferritin were the most efficient parameters for early diagnosis of HLH. With a sensitivity set at 85%, ferritin, IL-18, and glycosylated ferritin were the biomarkers with the highest specificity: 84, 79, and 71% respectively. Combining IL-18 with the HScore provided a new score with an increased specificity compared to the HScore alone, 86% compared to 70% with a sensitivity set at 100%. A distinct cytokine pattern was highlighted in patients with malignancy-triggered HLH, with highly increased levels of INF-É£ and CXCL9, compared to HLH secondary to infection. This is the largest study available to date, comparing diagnostic biomarkers for HLH on a cohort of critically ill adult patients. Serum ferritin was the most discriminating parameter for early diagnosis of secondary HLH. IL18*HScore was identified as a highly potential score.

Growth dynamics and light scattering of gold nanoparticles in situ synthesized at high concentration in thin polymer films.

Background: Numerous optical applications of nano-objects require a dispersion of the nanoparticles in a dielectric matrix. In order to achieve high particle concentrations, one can, as an alternative, directly grow the particles in a polymer or an inorganic film by, e.g., thermal annealing. Results: Simple laser reflection experiments showed that this growth process induced light scattering at the film/air interface. We report on this phenomenon, considering the growth dynamics of gold nanoparticles in a polymer film. The scattering of light was studied by measuring the bi-directional reflection distribution function. In parallel with the observation of enhanced scattering, imaging ellipsometry in dynamics mode showed that local values of the ellipsometric angles Ψ and Δ were strongly modified by the annealing process. Conclusion: A diffraction pattern corresponding to local modifications of the optical properties of the film gradually appeared, which turned out to be the signature of the growth of the Au nanoparticles. Moreover, the monitoring of the statistical distribution of the ellipsometric angles during annealing helped evidencing two regimes in the dynamics of the nanoparticle growth and in the optical response of the nanocomposite.

Fast IR-Actuated Shape-Memory Polymers Using in Situ Silver Nanoparticle-Grafted Cellulose Nanocrystals.

In recent years, shape-memory polymers (SMPs) have gained a key position in the realm of actuating applications from daily life products to biomedical and aeronautic devices. Most of these SMPs rely mainly on shape changes upon direct heat exposure or after stimulus conversion (e.g., magnetic field and light) to heat, but this concept remains significantly limited when both remote control and fine actuation are demanded. In the present study, we propose to design plasmonic silver nanoparticles (AgNPs) grafted onto cellulose nanocrystals (CNCs) as an efficient plasmonic system for fast and remote actuation. Such CNC- g-AgNPs "nanorod-like" structures thereby allowed for a long-distance and strong coupling plasmonic effect between the AgNPs along the CNC axis, thus ensuring a fast photothermal shape-recovery effect upon IR light illumination. To demonstrate the fast and remote actuation promoted by these structures, we incorporated them at low loading (1 wt %) into poly(ε-caprolactone) (PCL)-based networks with shape-memory properties. These polymer matrix networks were practically designed from biocompatible PCL oligomers end-functionalized with maleimide and furan moieties in the melt on the basis of thermoreversible Diels-Alder reactions. The as-produced materials could find application in the realm of soft robotics for remote object transportation or as smart biomaterials such as self-tightening knots with antibacterial properties related to the presence of the AgNPs.

Drop impact on soft surfaces: beyond the static contact angles.

The wettability of cross-linked poly(dimethylsiloxane) elastomer films and of octadecyltrichlorosilane self-assembled monolayers with water has been measured and compared using various methods. Contact angle hysteresis values were compared with values reported in the literature. A new method to characterize advancing, receding contact angles, and hysteresis using drop impact have been tested and compared with usual methods. It has been found that for the rigid surfaces the drop impact method is comparable with other methods but that for elastomer surfaces the hysteresis is function of the drop impact velocity which influences the extent of the deformation of the soft surface at the triple line.

Superhydrophobic aluminum surfaces by deposition of micelles of fluorinated block copolymers.

Superhydrophobic surfaces are generated by chemisorption on aluminum substrates of fluorinated block copolymers synthesized by reversible addition-fragmentation chain transfer in supercritical carbon dioxide. In an appropriate solvent, those block copolymers can form micelles with a fluorinated corona, which are grafted on the aluminum substrate thanks to the presence of carboxylic acid groups in the corona. Water contact angle and drop impact analysis were used to characterize the wettability of the films at the macroscale, and atomic force microscopy measurements provided morphological information at the micro- and nanoscale. The simple solvent casting of the polymer solution on a hydroxylated aluminum surface results in a coating with multiscale roughness, which is fully superhydrophobic over areas up to 4 cm(2).

Surface functionalization of germanium ATR devices for use in FTIR-biosensors.

Biosensors based on intrinsic detection methods have attracted growing interest. The use of Fourier transform infra-red (FTIR) spectroscopy with the attenuated internal total reflection (ATR) mode, in the biodetection context, requires appropriate surface functionalization of the ATR optical element. Here, we report the direct grafting of a thin organic layer (about 20 A depth) on the surface of a germanium crystal. This covering, constructed with novel amphiphilic molecules 2b (namely, 2,5,8,11,14,17,20-heptaoxadocosan-22-yl-3-(triethoxysilyl) propylcarbamate), is stable for several hours under phosphate buffered saline (PBS) flux and features protein-repulsive properties. Photografting of molecule 5 (namely, O-succinimidyl 4-(p-azidophenyl)butanoate) affords the activated ATR element, ready for the covalent fixation of receptors, penicillin recognizing proteins BlaR-CTD for instance. The different steps of the previous construction have been monitored by water contact angle (theta(w)) measurements, spectroscopic ellipsometry (covering depth), X-ray photoelectron spectroscopy (XPS) by using a fluorinated tag for the control of surface reactivity, and FTIR-ATR spectroscopy for the structural analysis of grafted molecules. Indeed, contrarily to silicon device, germanium device offers a broad spectral window (1000-4000 cm(-1)) and thus amide I and II absorption bands can be recorded. This work lays the foundations for the construction of novel FTIR biosensors.