Microstructure and physical properties of black-aluminum antireflective films.

The microstructure and physical properties of reflective and black aluminum were compared for layers of different thicknesses deposited by magnetron sputtering on fused silica substrates. Reflective Al layers followed the Volmer-Weber growth mechanism classically observed for polycrystalline metal films. On the contrary, the extra nitrogen gas used to deposit the black aluminum layers modified the growth mechanism and changed the film morphologies. Nitrogen cumulated in the grain boundaries, favoring the pinning effect and stopping crystallite growth. High defect concentration, especially vacancies, led to strong columnar growth. Properties reported for black aluminum tend to be promising for sensors and emissivity applications.

Silver Nanoparticles for Fluorescent Nanocomposites by High-Pressure Magnetron Sputtering.

We report on the formation of silver nanoparticles by gas aggregation in a reaction chamber at room temperature. The size distribution of nanoparticles deposited on a silicon substrate for various lengths of an aggregation (high-pressure) chamber was investigated by atomic force microscopy. Nanoparticles were characterized by scanning and transmission electron microscopy and spectral ellipsometry. The physical shape of the nanoparticles and its distribution was correlated with their optical properties. Metal-dielectric nanocomposites were deposited employing simultaneous deposition of Ag NPs via high-pressure magnetron sputtering and the dielectric matrix was deposited via thermal evaporation. Pure and Eu-, Er-, and Yb-doped lithium fluoride was used as the dielectric host matrix. Optical transmittance of lithium fluoride containing silver nanoparticles was measured and their theoretical absorption cross-section calculated. The nanoparticles were also embedded in Eu3+-doped downshifting and Er3+- and Yb3+-doped up-conversion materials to study their influence on emission spectra. Spectra of identical layers with and without nanoparticles were compared. Their transmittance at various annealing temperatures is also presented.

Ultra-short helix pitch and spiral ordering in cholesteric liquid crystal revealed by resonant soft X-ray scattering.

The spontaneous formation of chiral structures offers a variety of liquid crystals (LC) phases that could be further tailored for practical applications. In our work, the characteristic features of spiral ordering in the cholesteric phase of EZL10/10 LC were evaluated. To disclose resonant reflections related to a nanoscale helix pitch, resonant soft X-ray scattering at the carbon K edge was employed. The angular positions of the observed element-specific scattering peaks reveal a half-pitch of the spiral ordering p/2 ≈ 52 nm indicating the full pitch of about 104 nm at room temperature. The broadening of the peaks points to a presence of coherently scattering finite-size domains formed by cholesteric spirals with lengths of about five pitches. No scattering peaks were detectable in the EZL10/10 isotropic phase at higher temperatures. The characteristic lengths extracted from the resonant soft X-ray scattering experiment agree well with the periodicity of the surface "fingerprint" pattern observed in the EZL10/10 cholesteric phase by means of atomic force microscopy. The stability of LC molecules under the incident beam was proven by X-ray absorption spectroscopy in transmission geometry.

A Label-Free Diamond Microfluidic DNA Sensor Based on Active Nitrogen-Vacancy Center Charge State Control.

We propose a label-free biosensor concept based on the charge state manipulation of nitrogen-vacancy (NV) quantum color centers in diamond, combined with an electrochemical microfluidic flow cell sensor, constructed on boron-doped diamond. This device can be set at a defined electrochemical potential, locking onto the particular chemical reaction, whilst the NV center provides the sensing function. The NV charge state occupation is initially prepared by applying a bias voltage on a gate electrode and then subsequently altered by exposure to detected charged molecules. We demonstrate the functionality of the device by performing label-free optical detection of DNA molecules. In this experiment, a monolayer of strongly cationic charged polymer polyethylenimine is used to shift the charge state of near surface NV centers from negatively charged NV- to neutral NV0 or dark positively charged NV+. Immobilization of negatively charged DNA molecules on the surface of the sensor restores the NV centers charge state back to the negatively charged NV-, which is detected using confocal photoluminescence microscopy. Biochemical reactions in the microfluidic channel are characterized by electrochemical impedance spectroscopy. The use of the developed electrochemical device can also be extended to nuclear magnetic resonance spin sensing.

Self-Assembling Behavior of Smart Nanocomposite System: Ferroelectric Liquid Crystal Confined by Stretched Porous Polyethylene Film.

The control and prediction of soft systems exhibiting self-organization behavior can be realized by different means but still remains a highlighted task. Novel advanced nanocomposite system has been designed by filling of a stretched porous polyethylene (PE) film with pore dimensions of hundreds of nanometers by chiral ferroelectric liquid crystalline (LC) compound possessing polar self-assembling behavior. Lactic acid derivative exhibiting the paraelectric orthogonal smectic A* and the ferroelectric tilted smectic C* phases over a broad temperature range is used as a self-assembling compound. The morphology of nanocomposite film has been checked by Atomic Force Microscopy (AFM). The designed nanocomposite has been studied by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), small and wide-angle X-ray scattering and broadband dielectric spectroscopy. The effect of a porous PE confinement on self-assembling, structural, and dielectric behavior of the chiral LC compound has been established and discussed. While the mesomorphic and structural properties of the nanocomposite are found not to be much influenced in comparison to that of a pure LC compound, the polar properties have been toughly suppressed by the specific confinement. Nevertheless, the electro-optic switching was clearly observed under applied electric field of low frequency (210 V, 19 Hz). The dielectric spectroscopy and X-ray results reveal that the helical structure of the ferroelectric liquid crystal inside the PE matrix is completely unwound, and the molecules are aligned along stretching direction. Obtained results demonstrate possibilities of using stretched porous polyolefins as promising matrices for the design of new nanocomposites.

Optical Contrast and Raman Spectroscopy Techniques Applied to Few-Layer 2D Hexagonal Boron Nitride.

The successful integration of few-layer thick hexagonal boron nitride (hBN) into devices based on two-dimensional materials requires fast and non-destructive techniques to quantify their thickness. Optical contrast methods and Raman spectroscopy have been widely used to estimate the thickness of two-dimensional semiconductors and semi-metals. However, they have so far not been applied to two-dimensional insulators. In this work, we demonstrate the ability of optical contrast techniques to estimate the thickness of few-layer hBN on SiO2/Si substrates, which was also measured by atomic force microscopy. Optical contrast of hBN on SiO2/Si substrates exhibits a linear trend with the number of hBN monolayers in the few-layer thickness range. We also used bandpass filters (500-650 nm) to improve the effectiveness of the optical contrast methods for thickness estimations. We also investigated the thickness dependence of the high frequency in-plane E2g phonon mode of atomically thin hBN on SiO2/Si substrates by micro-Raman spectroscopy, which exhibits a weak thickness-dependence attributable to the in-plane vibration character of this mode. Ab initio calculations of the Raman active phonon modes of atomically thin free-standing crystals support these results, even if the substrate can reduce the frequency shift of the E2g phonon mode by reducing the hBN thickness. Therefore, the optical contrast method arises as the most suitable and fast technique to estimate the thickness of hBN nanosheets.

Application of Advanced Microscopic Methods to Study the Interaction of Carboxylated Fluorescent Nanodiamonds with Membrane Structures in THP-1 Cells: Activation of Inflammasome NLRP3 as the Result of Lysosome Destabilization.

Nanodiamonds (ND), especially fluorescent NDs, represent potentially applicable drug and probe carriers for in vitro/in vivo applications. The main purpose of this study was to relate physical-chemical properties of carboxylated NDs to their intracellular distribution and impact on membranes and cell immunity-activation of inflammasome in the in vitro THP-1 cell line model. Dynamic light scattering, nanoparticle tracking analysis, and microscopic methods were used to characterize ND particles and their intracellular distribution. Fluorescent NDs penetrated the cell membranes by both macropinocytosis and mechanical cutting through cell membranes. We proved accumulation of fluorescent NDs in lysosomes. In this case, lysosomes were destabilized and cathepsin B was released into the cytoplasm and triggered pathways leading to activation of inflammasome NLRP3, as detected in THP-1 cells. Activation of inflammasome by NDs represents an important event that could underlie the described toxicological effects in vivo induced by NDs. According to our knowledge, this is the first in vitro study demonstrating direct activation of inflammasome by NDs. These findings are important for understanding the mechanism(s) of action of ND complexes and explain the ambiguity of the existing toxicological data.

Organic nanotubes created from mesogenic derivatives.

A facile route to prepare nanotubes from rod-like mesogens dissolved in typical organic solvents is reported. For selected types of chiral rod-like molecules, nanotubes were formed from both enantiomers and racemic mixtures by slow evaporation from solution, regardless of the solvent, concentration or deposition type. The obtained supramolecular assemblies were studied using AFM, TEM and SEM techniques, and other experimental techniques (IR, UV-Vis spectroscopy and X-ray diffraction) were also applied. The difference in the surface tension at opposite crystallite surfaces is suggested as a possible mechanism for nanotube nucleation. We propose a quite new rolling-up mechanism related to the surface tension difference at opposite crystallite surfaces.

Diamond/Porous Titanium Nitride Electrodes With Superior Electrochemical Performance for Neural Interfacing.

Robust devices for chronic neural stimulation demand electrode materials which exhibit high charge injection (Q inj) capacity and long-term stability. Boron-doped diamond (BDD) electrodes have shown promise for neural stimulation applications, but their practical applications remain limited due to the poor charge transfer capability of diamond. In this work, we present an attractive approach to produce BDD electrodes with exceptionally high surface area using porous titanium nitride (TiN) as interlayer template. The TiN deposition parameters were systematically varied to fabricate a range of porous electrodes, which were subsequently coated by a BDD thin-film. The electrodes were investigated by surface analysis methods and electrochemical techniques before and after BDD deposition. Cyclic voltammetry (CV) measurements showed a wide potential window in saline solution (between -1.3 and 1.2 V vs. Ag/AgCl). Electrodes with the highest thickness and porosity exhibited the lowest impedance magnitude and a charge storage capacity (CSC) of 253 mC/cm2, which largely exceeds the values previously reported for porous BDD electrodes. Electrodes with relatively thinner and less porous coatings displayed the highest pulsing capacitances (C pulse), which would be more favorable for stimulation applications. Although BDD/TiN electrodes displayed a higher impedance magnitude and a lower C pulse as compared to the bare TiN electrodes, the wider potential window likely allows for higher Q inj without reaching unsafe potentials. The remarkable reduction in the impedance and improvement in the charge transfer capacity, together with the known properties of BDD films, makes this type of coating as an ideal candidate for development of reliable devices for chronic neural interfacing.

Ultrashort pulse laser ablation of dielectrics: Thresholds, mechanisms, role of breakdown.

In this paper, we establish connections between the thresholds and mechanisms of the damage and white-light generation upon femtosecond laser irradiation of wide-bandgap transparent materials. On the example of Corning Willow glass, evolution of ablation craters, their quality, and white-light emission were studied experimentally for 130-fs, 800-nm laser pulses. The experimental results indicate co-existence of several ablation mechanisms which can be separated in time. Suppression of the phase explosion mechanism of ablation was revealed at the middle of the irradiation spots. At high laser fluences, air ionization was found to strongly influence ablation rate and quality and the main mechanisms of the influence are analysed. To gain insight into the processes triggered by laser radiation in glass, numerical simulations have been performed with accounting for the balance of laser energy absorption and its distribution/redistribution in the sample, including bremsstrahlung emission from excited free-electron plasma. The simulations have shown an insignificant role of avalanche ionization at such short durations of laser pulses while pointing to high average energy of electrons up to several dozens of eV. At multi-pulse ablation regimes, improvement of crater quality was found as compared to single/few pulses.

Electrochemical Platform for the Detection of Transmembrane Proteins Reconstituted into Liposomes.

The development of new methods and strategies for the investigation of membrane proteins is limited by poor solubility of these proteins in an aqueous environment and hindered by a number of other problems linked to the instability of the proteins outside lipid bilayers. Therefore, current research focuses on an analysis of membrane proteins incorporated into model lipid membrane, most frequently liposomes. In this work, we introduce a new electrochemical methodology for the analysis of transmembrane proteins reconstituted into a liposomal system. The proposed analytical approach is based on proteoliposomal sample adsorption on the surface of working electrodes followed by analysis of the anodic and cathodic signals of the reconstituted proteins. It works based on the fact that proteins are electroactive species, in contrast to the lipid components of the membranes under the given experimental conditions. Electroanalytical experiments were performed with two transmembrane proteins; the Na(+)/K(+)ATPase that contains transmembrane as well as large extramembraneous segments and the mitochondrial uncoupling protein 1, which is a transmembrane protein essentially lacking extramembraneous segments. Electrochemical analyses of proteoliposomes were compared with analyses of both proteins solubilized with detergents (C12E8 and octyl-PoE) and supported by the following complementary methods: microscopy techniques, protein activity testing, molecular model visualizations, and immunochemical identification of both proteins. The label-free electrochemical platform presented here enables studies of reconstituted transmembrane proteins at the nanomolar level. Our results may contribute to the development of new electrochemical sensors and microarray systems applicable within the field of poorly water-soluble proteins.

Resistance to protein adsorption and adhesion of fibroblasts on nanocrystalline diamond films: the role of topography and boron doping.

Boron-doped nanocrystalline diamond (BNCD) films exhibit outstanding electrochemical properties that make them very attractive for the fabrication of electrodes for novel neural interfaces and prosthetics. In these devices, the physicochemical properties of the electrode materials are critical to ensure an efficient long-term performance. The aim of this study was to investigate the relative contribution of topography and doping to the biological performance of BNCD films. For this purpose, undoped and boron-doped NCD films were deposited on low roughness (LR) and high roughness (HR) substrates, which were studied in vitro by means of protein adsorption and fibroblast growth assays. Our results show that BNCD films significantly reduce the adsorption of serum proteins, mostly on the LR substrates. As compared to fibroblasts cultured on LR BNCD films, cells grown on the HR BNCD films showed significantly reduced adhesion and lower growth rates. The mean length of fibronectin fibrils deposited by the cells was significantly increased in the BNCD coated substrates, mainly in the LR surfaces. Overall, the largest influence on protein adsorption, cell adhesion, proliferation, and fibronectin deposition was due to the underlying sub-micron topography, with little or no influence of boron doping. In perspective, BNCD films displaying surface roughness in the submicron range may be used as a strategy to reduce the fibroblast growth on the surface of neural electrodes.

Molecular adjuvants based on nonpyrogenic lipophilic derivatives of norAbuMDP/GMDP formulated in nanoliposomes: stimulation of innate and adaptive immunity.

PURPOSE: The aim of this work was to demonstrate an immunostimulatory and adjuvant effect of new apyrogenic lipophilic derivatives of norAbuMDP and norAbuGMDP formulated in nanoliposomes. METHODS: Nanoliposomes and metallochelating nanoliposomes were prepared by lipid film hydration and extrusion methods. The structure of the liposomal formulation was studied by electron microscopy, AF microscopy, and dynamic light scattering. Sublethal and lethal γ-irradiation mice models were used to demonstrate stimulation of innate immune system. Recombinant Hsp90 antigen (Candida albicans) bound onto metallochelating nanoliposomes was used for immunisation of mice to demonstrate adjuvant activities of tested compounds. RESULTS: Safety and stimulation of innate and adaptive immunity were demonstrated on rabbits and mice. The liposomal formulation of norAbuMDP/GMDP was apyrogenic in rabbit test and lacking any side effect in vivo. Recovery of bone marrow after sublethal γ-irradiation as well as increased survival of mice after lethal irradiation was demonstrated. Enhancement of specific immune response was demonstrated for some derivatives incorporated in metallochelating nanoliposomes with recombinant Hsp90 protein antigen. CONCLUSIONS: Liposomal formulations of new lipophilic derivatives of norAbuMDP/GMDP proved themselves as promising adjuvants for recombinant vaccines as well as immunomodulators for stimulation of innate immunity and bone-marrow recovery after chemo/radio therapy of cancer.

A complex study of the fast blue luminescence of oxidized silicon nanocrystals: the role of the core.

Silicon nanocrystals (SiNCs) smaller than 5 nm are a material with strong visible photoluminescence (PL). However, the physical origin of the PL, which, in the case of oxide-passivated SiNCs, is typically composed of a slow-decaying red-orange band (S-band) and of a fast-decaying blue-green band (F-band), is still not fully understood. Here we present a physical interpretation of the F-band origin based on the results of an experimental study, in which we combine temperature (4-296 K), temporally (picosecond resolution) and spectrally resolved luminescence spectroscopy of free-standing oxide-passivated SiNCs. Our complex study shows that the F-band red-shifts only by 35 meV with increasing temperature, which is almost 6 times less than the red-shift of the S-band in a similar temperature range. In addition, the F-band characteristic decay time obtained from a stretched-exponential fit decreases only slightly with increasing temperature. These data strongly suggest that the F-band arises from the core-related quasi-direct radiative recombination governed by slowly thermalizing photoholes.