Functionalizing Surfaces by Physical Vapor Deposition To Measure the Degree of Nanoscale Contact Using FRET.

Adhesion between solid materials is caused by intermolecular forces that only take place if the adhering surfaces are at nanoscale contact (NSC) (i.e., 0.1-0.4 nm. To study adhesion, NSC can be evaluated with Förster Resonance Energy Transfer (FRET). FRET uses the interaction of compatible fluorescence molecules to measure the nanometer distance between bonded surfaces. For this, each surface is labeled with one fluorescence dye, named the Donor or Acceptor. If these molecules are in NSC, a nonradiative Donor-Acceptor energy transfer will occur and can be detected using FRET spectroscopy. Here, for the first time, we introduce an innovative concept of a FRET-based NSC measurement employing dye-nanolayer films prepared by a physical vapor deposition (PVD). The dye nanolayers were prepared by PVD from the vaporization of the Donor and Acceptor molecules separately. The selected molecules, 7-Amino-4-methyl-cumarin (C120) and 5(6)-Carboxy-2',7'-dichlor-fluorescein (CDCF), present high quantum yields (QY, QYD = 0.91 and QYA = 0.64) and a low FRET distance range of 0.6-2.2 nm, adequate for the study of NSC. The produced dye-nanolayer films exhibit a uniform dye distribution (verified by atomic force microscopy) and suitable fluorescence intensities. To validate the NSC measurements, FRET spectroscopy experiments were performed with bonded dye-nanolayer films prepared under different loads (from 1.5 to 140 bar), thus creating different degrees of NSC. The results show an increase in FRET intensity (R 2 = 0.95) with the respective adhesion energy between the films, which is directly related to the degree of NSC. Hence, this work establishes FRET as an experimental technique for the measurement of NSC, and its relation to surface adhesion. Additionally, thanks to the FRET dye-nanolayer approach, the method can be employed on arbitrary surfaces. Essentially, any sufficiently transparent substrate can be functionalized with FRET compatible dyes to evaluate NSC, which represents a breakthrough in contact mechanics investigations of soft and hard solid materials.

Enhancement of the Sensing Performance of Devices based on Multistimuli-Responsive Hybrid Materials.

Capturing environmental stimuli is an essential aspect of electronic skin applications in robotics and prosthetics. Sensors made of temperature- and humidity-responsive hydrogel and piezoelectric zinc oxide (ZnO) core-shell nanorods have shown the necessary sensitivity. This is achieved by using highly conformal and substrate independent deposition methods for the ZnO and the hydrogel, i.e., plasma enhanced atomic layer deposition (PEALD) and initiated chemical vapor deposition (iCVD). In this work, we demonstrate that the use of a multichamber reactor enables performing PEALD and iCVD, sequentially, without breaking the vacuum. The sequential deposition of uniform as well as conformal thin films responsive to force, temperature, and humidity improved the deposition time and quality significantly. Proper interlayer adhesion could be achieved via in situ interface activation, a procedure easily realizable in this unique multichamber reactor. Beyond the fabrication method, also the mechanical properties of the template used to embed the core-shell nanorods and the cross-linker density in the hydrogel were optimized following the results of finite element models. Finally, galvanostatic electrochemical impedance spectroscopy measurements showed how temperature and humidity stimuli have different effects on the device impedance and phase, and these differences can be the basis for stimuli recognition.

Measurements of Temperature and Humidity Responsive Swelling of Thin Hydrogel Films by Interferometry in an Environmental Chamber.

Thin film thermo-responsive hydrogels have become a huge interest in applications such as smart drug-delivery systems or sensor/actuator technology. So far, mostly, the response of such hydrogels has been measured only by varying the temperature in a liquid environment, but studies of the response towards humidity and temperature are rare because of experimental limitations. Often the swelling measurements are performed on samples placed on a stage that can be heated/cooled, while vapors enter the permeation chamber at their own temperature. This thermal difference leads to some uncertainties on the exact relative humidity to which the sample is exposed to. In this study, we explored the possibility of performing swelling measurements under thermal equilibrium by placing the sample and an interferometer, as a detector, in an environmental chamber and therefore exposing the smart hydrogel to adjustable temperatures and relative humidity conditions while measuring the hydrogel's thin film thickness changes. As a case study, we used thin films of the thermo-responsive hydrogel, poly N-vinylcaprolactam deposited by initiated chemical vapor deposition (iCVD). Similar thin films were previously characterized by in situ ellipsometry while the sample was heated on a stage and exposed to humid air produced at room temperature. The comparison between the two measurement methods showed that while measurements in the presence of thermal gradients are limited mostly to low humidity, measurements in thermal equilibrium are restricted only by the operation limits of the used environmental chamber.

Tuning the Porosity of Piezoelectric Zinc Oxide Thin Films Obtained from Molecular Layer-Deposited "Zincones".

Porous zinc oxide (ZnO) thin films were synthesized via the calcination of molecular layer-deposited (MLD) "zincone" layers. The effect of the MLD process temperature (110 °C, 125 °C) and of the calcination temperature (340 °C, 400 °C, 500 °C) on the chemical, morphological, and crystallographic properties of the resulting ZnO was thoroughly investigated. Spectroscopic ellipsometry reveals that the thickness of the calcinated layers depends on the MLD temperature, resulting in 38-43% and 52-56% of remaining thickness for the 110 °C and 125 °C samples, respectively. Ellipsometric porosimetry shows that the open porosity of the ZnO thin films depends on the calcination temperature as well as on the MLD process temperature. The maximum open porosity of ZnO derived from zincone deposited at 110 °C ranges from 14.5% to 24%, rising with increasing calcination temperature. Compared with the 110 °C samples, the ZnO obtained from 125 °C zincone yields a higher porosity for low calcination temperatures, namely 18% for calcination at 340 °C; and up to 24% for calcination at 500 °C. Additionally, the porous ZnO thin films were subjected to piezoelectric measurements. The piezoelectric coefficient, d33, was determined to be 2.8 pC/N, demonstrating the potential of the porous ZnO as an, e.g., piezoelectric sensor or energy harvester.

Glucose-Responsive Boronic Acid Hydrogel Thin Films Obtained via Initiated Chemical Vapor Deposition.

Glucose-responsive materials are of great importance in the field of monitoring the physiological glucose level or smart insulin management. This study presents the first vacuum-based deposition of a glucose-responsive hydrogel thin film. The successful vacuum-based synthesis of a glucose-responsive hydrogel may open the door to a vast variety of new applications, where, for example, the hydrogel thin film is applied on new possible substrates. In addition, vacuum-deposited films are free of leachables (e.g., plasticizers and residual solvents). Therefore, they are, in principle, safe for in-body applications. A hydrogel made of but-3-enylboronic acid units, a boronic acid compound, was synthesized via initiated chemical vapor deposition. The thin film was characterized in terms of chemical composition, surface morphology, and swelling response toward pH and sucrose, a glucose-fructose compound. The film was stable in aqueous solutions, consisting of polymerized boronic acid and the initiator unit, and had an undulating texture appearance (rms 2.1 nm). The hydrogel was in its shrunken state at pH 4-7 and swelled by increasing the pH to 9. The pKa was 8.2 ± 0.2. The response to glucose was observed at pH 10 and resulted in thickness shrinking.

Deep tissue localization and sensing using optical microcavity probes.

Optical microcavities and microlasers were recently introduced as probes inside living cells and tissues. Their main advantages are spectrally narrow emission lines and high sensitivity to the environment. Despite numerous novel methods for optical imaging in strongly scattering biological tissues, imaging at single-cell resolution beyond the ballistic light transport regime remains very challenging. Here, we show that optical microcavity probes embedded inside cells enable three-dimensional localization and tracking of individual cells over extended time periods, as well as sensing of their environment, at depths well beyond the light transport length. This is achieved by utilizing unique spectral features of the whispering-gallery modes, which are unaffected by tissue scattering, absorption, and autofluorescence. In addition, microcavities can be functionalized for simultaneous sensing of various parameters, such as temperature or pH value, which extends their versatility beyond the capabilities of standard fluorescent labels.

Conformal Coating of Powder by Initiated Chemical Vapor Deposition on Vibrating Substrate.

Encapsulation of pharmaceutical powders within thin functional polymer films is a powerful and versatile method to modify drug release properties. Conformal coating over the complete surface of the particle via chemical vapor deposition techniques is a challenging task due to the compromised gas-solid contact. In this study, an initiated chemical vapor deposition reactor was adapted with speakers and vibration of particles was achieved by playing AC/DC's song "Thunderstruck" to overcome the above-mentioned problem. To show the possibilities of this method, two types of powder of very different particle sizes were chosen, magnesium citrate (3-10 µm, cohesive powder) and aspirin (100-500 µm, good flowability), and coated with poly-ethylene-glycol-di-methacrylate. The release curve of coated magnesium citrate powder was retarded compared to uncoated powder. However, neither changing the thickness coating nor vibrating the powder during the deposition had influence on the release parameters, indicating, that cohesive powders cannot be coated conformally. The release of coated aspirin was as well retarded as compared to uncoated aspirin, especially in the case of the powder that vibrated during deposition. We attribute the enhancement of the retarded release to the formation of a conformal coating on the aspirin powder.

Initiated Chemical Vapor Deposition of Crosslinked Organic Coatings for Controlling Gentamicin Delivery.

A coating consisting of a copolymer of methacrylic acid and ethylene glycol dimethacrylate was deposited over a gentamicin film by initiated chemical vapor deposition with the aim of controlling the drug release. Gentamicin release in water was monitored by means of conductance measurements and of UV-vis Fluorescence Spectroscopy. The influence of the polymer chemical composition, specifically of its crosslinking density, has been investigated as a tool to control the swelling behavior of the initiated chemical vapor deposition (iCVD) coating in water, and therefore its ability to release the drug. Agar diffusion test and microbroth dilution assays against Staphylococcus aureus and Pseudomonas aeruginosa on cellulose coated substrates confirmed that the antibacterial activity of the drug released by the coating was retained, though the release of gentamicin was not complete.

Novel Light-Responsive Biocompatible Hydrogels Produced by Initiated Chemical Vapor Deposition.

A novel multiresponsive hydrogel has been synthesized by initiated chemical vapor deposition (iCVD). Hydrogels are known for their dynamic swelling response to aqueous environments. A chemical functionalization of the hydrogel surface was performed to add other stimuli-responsive functionalities and obtain a smart material that responds to two stimuli: light irradiation and exposure to aqueous environment. Modifying the hydrogel surface with solution-based methods is often problematic because of the damages caused by the permeation of solvents in the hydrogel. This issue is completely bypassed by the use of solvent-free techniques. Cross-linked polymers of 2-hydroxyethyl methacrylate (HEMA) were functionalized with azobenzene groups, as confirmed by IR spectroscopy and X-ray photoelectron spectroscopy (XPS). Through photoisomerization of the azobenzene, the polarity within the hydrogel is modified and as a consequence the affinity to water. Light irradiation modifies the degree of swelling within thin hydrogel films from 13% before exposure to UV light to 25% after exposure. The possibility of controlling the degree and rate of swelling by light irradiation was never reported before on these time scales and can have exceptional implications for light-induced drug delivery or light-controlled microfluidic systems. The light-responsive hydrogels showed also biocompatibility, which makes them suitable for a great variety of applications as biomaterials.

Metamorphosis and transition between developmental stages in European eel (Anguilla anguilla, L.) involve epigenetic changes in DNA methylation patterns.

The life history of the European eel (Anguilla anguilla, L.) is characterized by a series of metamorphoses and transitions that provoke drastic morphological changes. Most of these changes go along with the catadromous life cycle in eels, involving extensive physiologically adaptations. In this study it was investigated whether these drastic changes have an epigenetic basis by analyzing global methylation patterns in liver, gill and brain tissue from glass eels caught at the British coast as well as yellow and silver eels from River Rhine using methylation-sensitive amplified polymorphisms (MSAP). Analysis of molecular variance (AMOVA) on MSAP data derived from liver tissue revealed only minor differences in methylation patterns between glass, yellow and silver eels, reflecting uniform functioning of the liver throughout the investigated lifespan. In brain and gill tissue, however, marked differences in methylation patterns were found. Principal coordinates analysis (PCoA) revealed yellow eels being partially clustered with silver eels and a more distinct cluster of glass eels based on the methylation patterns in the brain. According to results found in the gills, glass eels were more similar to silver eels whereas yellow eels were found to be clustered separately. From these results it can be concluded that epigenetic changes in gill tissue most likely reflect and are linked with adaptation towards salt- and freshwater conditions. The observed differences in brain methylation patterns, however, might be linked to morphological and physiological changes during metamorphosis and transitions within the life history of European eels potentially affecting subsequent differential gene expression patterns required for such changes.

Absolute concentration of free volume-type defects in ultrafine-grained Fe prepared by high-pressure torsion.

A maximum excess volume ΔV/V ≈ 1.9 × 10(-3) in ultrafine-grained Fe prepared by high-pressure torsion is determined by measurements of the irreversible length change upon annealing employing a high-resolution differential dilatometer. Since dislocations and equilibrium-type grain boundaries cannot fully account for the observed released excess volume, the present study yields evidence for a high concentration of free volume-type defects inherent to nanophase materials, which is considered to be the main source of their particular properties, such as strongly enhanced diffusivities.