Design,preparation, and characterization of new high-refractive index hybrid organic–inorganic polysiloxanes: Innovative coatings for optoelectronic applications

The current demand for high-refractive index materials is very high due to their importance in optoelectronic applications. Such materials already exist in the market, but they present many disadvantages. They might contain toxic metals; their preparation can be challenging or produce high quantity of waste. Consequently, there is an urgent need to produce new friendly coatings with high-refractive index. Hybrid organic–inorganic polysiloxanes can offer a solution to this problem. They can be easily prepared from nontoxic alkoxy silanes using the sol–gel chemistry process. Herein, a series of new hybrid polysiloxanes are synthesized from the monomer 1–(2–(triethoxysilyl)ethyl)triphenylsilane and other silanes. The preparation of the macromolecules is optimized at both stages of the sol–gel process. The polymers are characterized by gel permeation chromatography and NMR spectroscopy. Spin coating of the materials on silicon wafers, followed by film thickness and refractive index measurements, indicates that the new polysiloxanes can have refractive indexes as high as 1.6 with thicknesses varying from 2200 to 3700 nm. Consequently, it is expected that the new materials described in this report are valuable for optoelectronic applications such as high-dielectric constant (high-k) gate oxides, interlayer high-k dielectrics, or high-refractive index abrasion resistant coatings.     

Design,synthesis, characterization,and aging properties of a new end-capped three-dimensional high-refractive index hybrid organic–inorganic polysiloxane

The actual need for hybrid organic–inorganic polysiloxanes is very high due to their importance in optoelectronic applications, especially for the preparation of anti- and low-reflection layers, photopatterned overcoats, flexible hard coats, and glass and metal coatings. However, such three-dimensional hybrid polysiloxanes have very often a limited shelf life and aged very rapidly. Consequently, this type of polymer may require to be stored at cold temperatures and needs to be dilute in organic solvent to a very low solid content, which are unprofitable conditions for commercialization purposes. Therefore, there is an urgent demand to prepare three-dimensional polysiloxanes, which are more resistant toward aging processes. Herein, a new hybrid three-dimensional polysiloxane has been designed and synthesized from three different silane precursors using the sol–gel technology, and characterized using gel permeation chromatography, ¹H, ¹³C, and ²⁹Si nuclear magnetic resonance and MS spectroscopies. One-fourth of the silanol groups present in the polysiloxane have been protected with chlorotrimethylsilane. The refractive index of the silicon wafer coated with the new polysiloxane was found to be 1.53, which is higher compare to traditional values. Importantly, the new protected three-dimensional polysiloxane did not age after being stored at T = 40°C for 3 weeks.     

The dorsolateral pre‑frontal cortex bi‑polar error‑related potential in a locked‑in patient implanted with a daily use brain–computer interface

While brain computer interfaces (BCIs) offer the potential of allowing those suffering from loss of muscle control to once again fully engage with their environment by bypassing the affected motor system and decoding user intentions directly from brain activity, they are prone to errors. One possible avenue for BCI performance improvement is to detect when the BCI user perceives the BCI to have made an unintended action and thus take corrective actions. Error-related potentials (ErrPs) are neural correlates of error awareness and as such can provide an indication of when a BCI system is not performing according to the user’s intentions. Here, we investigate the brain signals of an implanted BCI user suffering from locked-in syndrome (LIS) due to late-stage ALS that prevents her from being able to speak or move but not from using her BCI at home on a daily basis to communicate, for the presence of error-related signals. We first establish the presence of an ErrP originating from the dorsolateral pre-frontal cortex (dLPFC) in response to errors made during a discrete feedback task that mimics the click-based spelling software she uses to communicate. Then, we show that this ErrP can also be elicited by cursor movement errors in a continuous BCI cursor control task. This work represents a first step toward detecting ErrPs during the daily home use of a communications BCI.     

Influence of Unmodified and β-Glycerophosphate Cross-Linked Chitosan on Anti-Candida Activity of Clotrimazole in Semi-Solid Delivery Systems

The combination of an antifungal agent and drug carrier with adjunctive antimicrobial properties represents novel strategy of complex therapy in pharmaceutical technology. The goal of this study was to investigate the unmodified and ion cross-linked chitosan’s influence on anti-Candida activity of clotrimazole used as a model drug in hydrogels. It was particularly crucial to explore whether the chitosans’ structure modification by β-glycerophosphate altered its antifungal properties. Antifungal studies (performed by plate diffusion method according to CLSI reference protocol) revealed that hydrogels obtained with chitosan/β-glycerophosphate displayed lower anti-Candida effect, probably as a result of weakened polycationic properties of chitosan in the presence of ion cross-linker. Designed chitosan hydrogels with clotrimazole were found to be more efficient against tested Candida strains and showed more favorable drug release profile compared to commercially available product. These observations indicate that novel chitosan formulations may be considered as promising semi-solid delivery system of clotrimazole.     

The Chloroplast Import Receptor Toc90 Partially Restores the Accumulation of Toc159 Client Proteins in the Arabidopsis thaliana ppi2 Mutant

Successful import of hundreds of nucleus-encoded proteins is essential for chloroplast biogenesis. The import of cytosolic precursor proteins relies on the Toc- (translocon at the outer chloroplast membrane) and Tic- (translocon at the inner chloroplast membrane) complexes. In Arabidopsis thaliana,precursor recognition is mainly mediated by outer membrane receptors belonging to two gene families: Toc34/33 and Toc159/132/120/90. The role in import and precursor selectivity of these receptors has been intensively studied,but the function of Toc90 still remains unclear. Here,we report the ability of Toc90 to support the import of Toc159 client proteins. We show that the overexpression of Toc90 partially complements the albino knockout of Toc159 and restores photoautotrophic growth. Several lines of evidence including proteome profiling demonstrate the import and accumulation of proteins essential for chloroplast biogenesis and functionality.     

Fluorescent Nanodiamonds Embedded in Biocompatible Translucent Shells

High pressure high temperature (HPHT) nanodiamonds (NDs) represent extremely promising materials for construction of fluorescent nanoprobes and nanosensors. However, some properties of bare NDs limit their direct use in these applications: they precipitate in biological solutions, only a limited set of bio‐orthogonal conjugation techniques is available and the accessible material is greatly polydisperse in shape. In this work, we encapsulate bright 30‐nm fluorescent nanodiamonds (FNDs) in 10–20‐nm thick translucent (i.e., not altering FND fluorescence) silica shells, yielding monodisperse near‐spherical particles of mean diameter 66 nm. High yield modification of the shells with PEG chains stabilizes the particles in ionic solutions, making them applicable in biological environments. We further modify the opposite ends of PEG chains with fluorescent dyes or vectoring peptide using click chemistry. High conversion of this bio‐orthogonal coupling yielded circa 2000 dye or peptide molecules on a single FND. We demonstrate the superior properties of these particles by in vitro interaction with human prostate cancer cells: while bare nanodiamonds strongly aggregate in the buffer and adsorb onto the cell membrane, the shell encapsulated NDs do not adsorb nonspecifically and they penetrate inside the cells.     

Phase Diagram, Short-Range Structure, and Amorphous Phases in the ZrO2-GeO2(-H2O) System

Gels of the ZrO₂-GeO₂(-H₂O) system have been prepared via the hydrolysis-polycondensation of zirconium and germanium isopropoxides. Phase relationships have been deduced from differential thermal analysis, thermogravimetric analysis, and shrinkage analysis and are discussed on the basis of X-ray diffractometry and Raman scattering studies. Emphasis has been given to understanding the short-range structure. A small glass-forming domain is observed in the temperature range of 600°−700°C for compositions of 30–40 mol% GeO₂.     

Carbon‐Nanotube–PDMS Composite Coatings on Optical Fibers for All‐Optical Ultrasound Imaging

Polymer–carbon nanotube composite coatings have properties that are desirable for a wide range of applications. However, fabrication of these coatings onto submillimeter structures with the efficient use of nanotubes has been challenging. Polydimethylsiloxane (PDMS)–carbon nanotube composite coatings are of particular interest for optical ultrasound transmission, which shows promise for biomedical imaging and therapeutic applications. In this study, methods for fabricating composite coatings comprising PDMS and multiwalled carbon nanotubes (MWCNTs) with submicrometer thickness are developed and used to coat the distal ends of optical fibers. These methods include creating a MWCNT organogel using two solvents, dip coating of this organogel, and subsequent overcoating with PDMS. These coated fibers are used as all‐optical ultrasound transmitters that achieve high ultrasound pressures (up to 21.5 MPa peak‐to‐peak) and broad frequency bandwidths (up to 39.8 MHz). Their clinical potential is demonstrated with all‐optical pulse‐echo ultrasound imaging of an aorta. The fabrication methods in this paper allow for the creation of thin, uniform carbon nanotube composites on miniature or temperature‐sensitive surfaces, to enable a wide range of advanced sensing capabilities.     

Towards efficient partial evaluation in logic programming

Partial evaluation is a symbolic manipulation technique used to produce efficient algorithms when part of the input to the algorithm is known. Other applications of partial evaluators such as universal compilation and compiler generation are also known to be possible. A partial evaluator receives as input a program and partially known input to that program, and outputs a residual program which should run at least as efficient as the input program with restricted input. In this paper we study the case where both the input and residual programs are logic programs, being the partial evaluator itself a logic program. Up to now, partial evaluators have failed to process large “non=toy” examples. Here we present extensions to partial evaluators whic will allow us to produce more efficient residual programs using less computing resources, during partial evaluation. First, the introduced extensions allow the processing of large examples, which is not possible with the previous techniques. This is now possible since the extensions use less CPU time and memory consumption during the partial evaluation process. Second, the extended partial evaluator produces smaller residual programs, producing important CPU time optimizing effects. With the standard techniques, a partial evaluator will most probably act as a pessimizer, not as an optimizer. Examples are given.     

Demonstration projects and sustainable housing

Because of the complicated structure of the built environment, it is frequently difficult to obtain good results on sustainable development projects. In The Netherlands, the Dutch government have used a range of new steering instruments which have cleverly enabled innovation to take place within a market economy. This imaginative governmental process uses covenants, network management and above all, demonstration projects to assess the feasibility of innovation. The authors describe the process and consider examples from energy efficient and sustainable housing, highlighting the importance of clear targets.