Electrostatically crosslinked cellulose nanocrystal and polyelectrolyte complex sponges with pH responsiveness.

This work focuses on the development of a responsive sponge made of an anionic cellulose nanocrystal (CNC) skeleton that is electrostatically crosslinked by a pH-responsive poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) polyelectrolyte complex (PEC). The results prove the formation of a global percolated network comprised of disordered CNC rods crosslinked by PEC clusters. The bulk density of the freeze-dried CNC-PEC sponges increases from 35 to 93 mg/cm3 with PEC concentration, while the compression modulus of dry specimens increases from 7 up to 62 kPa. At the lowest PEC concentration of 1 wt%, at pH 2.0, the compression modulus decreases to 0.9 kPa, whereas at pH 5.5, it increases to 42 kPa. The intensive complexation between sponge constituents is also reflected in a reduced ability to bind charged dyes at neutral pH values. Decreasing the pH results in an increased adsorption efficiency for anionic dyes, while raising the pH improves the cationic dye adsorption.

A universal ultrasound diagnostic system developed to support urology and coloproctological applications.

In this study, we sought to describe a novel imaging apparatus that is lightweight, inexpensive, and highly effective for use in colorectal diagnostic and treatment settings. Typical probes for use in colorectal ultrasonic imaging applications are developed for surgeons to diagnose and stage rectal tumors and image the rectum and anus. Here we outline a new technique and use it for colorectal imaging in an animal. This technique involves use of an ultrasound array module positioned along the axis of rotation such that improved rotation is possible. This module is in the shape of a linear rod with a rotary linear component that allows for emission of focused ultrasonic echo signals from a linear section of the probe. The usability of the transducer and rectal image quality are satisfactory in a porcine model with the technique proposed here, axial/lateral resolution as 0.96/2.24 mm with 6 dB applied through the contour map using the point spread function. When compared to currently available methods, this technique provides superior diagnostic 3D volumetric image quality with reduced acquisition time. Given this, the ultrasound device proposed here may prove a viable and preferable method to those currently available for urology and colorectal imaging applications.

Self-Cleaning Anticondensing Glass via Supersonic Spraying of Silver Nanowires, Silica, and Polystyrene Nanoparticles.

We have sequentially deposited layers of silver nanowires (AgNWs), silicon dioxide (SiO2) nanoparticles, and polystyrene (PS) nanoparticles on uncoated glass by a rapid low-cost supersonic spraying method to create antifrosting, anticondensation, and self-cleaning glass. The conductive silver nanowire network embedded in the coating allows electrical heating of the glass surface. Supersonic spraying is a single-step coating technique that does not require vacuum. The fabricated multifunctional glass was characterized by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), ultraviolet-visible spectroscopy, and transmission electron microscopy (TEM). The thermal insulation and antifrosting performance were demonstrated using infrared thermal imaging. The reliability of the electrical heating function was tested through extensive cycling. This transparent multifunctional coating holds great promise for use in various smart window designs.

Supersonically Spray-Coated Colloidal Quantum Dot Ink Solar Cells.

Controlling the thickness of quantum dot (QD) films is difficult using existing film formation techniques, which employ pre-ligand-exchanged PbS QD inks, because of several issues: 1) poor colloidal stability, 2) use of high-boiling-point solvents for QD dispersion, and 3) limitations associated with one-step deposition. Herein, we suggest a new protocol for QD film deposition using electrical double-layered PbS QD inks, prepared by solution-phase ligand exchange using methyl ammonium lead iodide (MAPbI3). The films are deposited by the supersonic spraying technique, which facilitates the rapid evaporation of the solvent and the subsequent deposition of the PbS QD ink without requiring a post-deposition annealing treatment for solvent removal. The film thickness could be readily controlled by varying the number of spraying sweeps made across the substrate. This spray deposition process yields high-quality n-type QD films quickly (within 1 min) while minimizing the amount of the PbS QD ink used to less than 5 mg for one device (300-nm-thick absorbing layer, 2.5 × 2.5 cm2). Further, the formation of an additional p-layer by treatment with mercaptopropionic acid allows for facile hole extraction from the QD films, resulting in a power conversion efficiency of 3.7% under 1.5 AM illumination.

Scalable Binder-Free Supersonic Cold Spraying of Nanotextured Cupric Oxide (CuO) Films as Efficient Photocathodes.

We demonstrate production of nanotextured p-type cupric oxide (CuO) films via a low-cost scalable supersonic cold spray method in open air conditions. Simply sweeping the spray nozzle across a substrate produced a large-scale CuO film. When used as hydrogen evolution photocathodes, these films produced photocurrent densities (PCD) of up to 3.1 mA/cm(2) under AM1.5 illumination, without the use of a cocatalyst or any additional heterojunction layers. Cu2O particles were supersonically sprayed onto an indium tin oxide (ITO) coated soda lime glass (SLG) substrate, without any solvent or binder. Annealing in air converted the Cu2O films to CuO, with a corresponding decrease in the bandgap and increase in the fraction of the solar spectrum absorbed. Annealing at 600 °C maximized the PCD. Increasing the supersonic gas velocity from ∼450 to ∼700 m/s produced denser films with greater surface roughness, in turn producing higher PCD. The nanoscale texture of the films, which resembles the skin of a dinosaur, enhanced their performance, leading to one of the highest PCD values in the literature. We characterized the films by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, and transmission electron microscopy to elucidate the origins of their outstanding performance. This supersonic cold spraying deposition has the potential to be used on a commercial scale for low cost mass production.

Supersonically blown nylon-6 nanofibers entangled with graphene flakes for water purification.

Water purification membranes, capable of purifying a few to tens of milliliters of aqueous methylene blue solution in a minute, were produced by supersonically blowing graphene flakes with a nylon-6 polymeric solution. The solution-blown nylon-6 nanofibers became entangled with graphene flakes thereby locking the graphene flakes within the frame of the bendable two-dimensional film structure. This method, which yielded a 5 × 7 cm(2)-sized membrane in less than 10 seconds, is commercially viable owing to fast fabrication and scalability. We show that our water purification device allows a flow rate range of 0.3-4 L h(-1) with a membrane area of just 5 cm(2), under a pressure difference of 0.5-3.5 bar. If the membrane were scaled up to 0.5 m(2), it could provide 300-4000 L h(-1) flow rate, an ample supply for home use.

A prototype hand-held tri-modal instrument for in vivo ultrasound, photoacoustic, and fluorescence imaging.

Multi-modality imaging is beneficial for both preclinical and clinical applications as it enables complementary information from each modality to be obtained in a single procedure. In this paper, we report the design, fabrication, and testing of a novel tri-modal in vivo imaging system to exploit molecular/functional information from fluorescence (FL) and photoacoustic (PA) imaging as well as anatomical information from ultrasound (US) imaging. The same ultrasound transducer was used for both US and PA imaging, bringing the pulsed laser light into a compact probe by fiberoptic bundles. The FL subsystem is independent of the acoustic components but the front end that delivers and collects the light is physically integrated into the same probe. The tri-modal imaging system was implemented to provide each modality image in real time as well as co-registration of the images. The performance of the system was evaluated through phantom and in vivo animal experiments. The results demonstrate that combining the modalities does not significantly compromise the performance of each of the separate US, PA, and FL imaging techniques, while enabling multi-modality registration. The potential applications of this novel approach to multi-modality imaging range from preclinical research to clinical diagnosis, especially in detection/localization and surgical guidance of accessible solid tumors.

Thermally induced superhydrophilicity in TiO2 films prepared by supersonic aerosol deposition.

Superhydrophilic and superhydrophobic surfaces enable self-cleaning phenomena, either forming a continuous water film or forming droplets that roll off the surface, respectively. TiO2 films are well-known for their extreme hydrophilicity and photocatalytic characteristics. Here, we describe nanostructured TiO2 thin films prepared by supersonic aerosol deposition, including a thorough study of the effects of the annealing temperature on the crystal structure, surface morphology, surface roughness, and wetting properties. Powder X-ray diffraction showed that supersonic deposition resulted in fragmentation and amorphization of the micrometer-size anatase (60%)-rutile (40%) precursor powder and that, upon annealing, a substantial fraction of the film (~30%) crystallized in the highly hydrophilic but metastable brookite phase. The film morphology was also somewhat modified after annealing. Scanning electron microscopy and atomic force microscopy revealed rough granular films with high surface roughness. The as-deposited TiO2 films were moderately hydrophilic with a water contact angle (θ) of ~45°, whereas TiO2 films annealed at 500 °C became superhydrophilic (θ ~ 0°) without UV illumination. This thermally induced superhydrophilicity of the TiO2 films can be explained on the basis of the combined effects of the change in the crystal structure, surface microstructure, and surface roughness. Supersonic aerosol deposition followed by annealing is uniquely able to produce these nanostructured films containing a mixture of all three TiO2 phases (anatase, rutile, and brookite) and exhibiting superhydrophilicity without UV illumination.

Antibacterial and water purification activities of self-assembled honeycomb structure of aerosol deposited titania film.

A simple and rapid room-temperature aerosol deposition method was used to fabricate TiO(2) films for photokilling/photdegradation applications. TiO(2) particles were accelerated to supersonic speeds and fractured upon impacting a glass substrate to form a functional thin film, a process known as aerosol deposition. After deposition, the films were annealed at various temperatures, and their photokilling/photodegradation performances following ultraviolet (UV) exposure were evaluated by counting the number of surviving bacterial colonies, and by a methylene blue decolorization test. The photocatalytic performances of all TiO(2) films were obtained under weak UV exposure (0.6 mW/cm(2)). The film density, crystalline phase, and surface roughness (morphology) were measured by scanning electron microscopy, X-ray diffraction, UV-visible spectroscopy, and atomic force microscopy. The unique, self-assembled honeycomb structure of the aerosol deposited films contributed to the increase in surface area because of extreme roughness, which enhances the photokilling and photodegradation performance. Nonannealed films yielded the best photocatalytic performance due to their small crystalline sizes and large surface areas due to increased surface roughness.

Polar structures in binary mixtures of bent-core liquid crystals showing ferroelectric and antiferroelectric B2 phases.

We have studied the polar structures in the binary mixtures of bent-core liquid crystals P-n-O-PIMB(n-2)*-(n-4)O showing the ferroelectric smectic- CAPF (Sm-CAPF) (n=8 and 10) and antiferroelectric Sm-CSPA (n=9) B2 phase. Although the polar structure of the one-to-one mixture is governed by the compound with longer end chains, it is much more complicated in the mixtures with slightly less fraction of compounds with longer end chains. Even if the mixtures show the antiferroelectric phase before field application, the ferroelectric domains remain once the field is applied and coexist with the antiferroelectric domains. The coexistence structure was modeled by comparing the microscope real image with that of second-harmonic generation. The fraction of the ferroelectric domains is larger at higher temperature region of the B2 phase and decreases with decreasing temperature. The stable phase structures were discussed based on the phenomenological theory. We suggest that the coupling energy of the layer chirality is higher than the energies of the orientation correlations of tilts and polarizations between adjacent layers.

Interpretation of the odd-even behavior for the emergence of ferroelectricity and antiferroelectricity in bent-core mesogens.

Simple theoretical interpretation has been made on the previously reported odd-even behavior of the emergence of ferroelectricity and antiferroelectricity in homologous series of bent-core mesogens with the same chiral end chains (S,S) ; compounds with even and odd carbon numbers (including oxygen) exhibit ferroelectric and antiferroelectric B2 phases, respectively. The odd-even behavior was confirmed in newly synthesized racemic compounds with chiral end chains of R and S forms (R,S) together with (R,R) and (S,S) forms. According to our theoretical interpretation, ferroelectricity should be more stable in (R,S) compounds than in (S,S) compounds. Actually, the transition temperature from the isotropic phase to the Sm-CP phase was higher and the temperature range of the B2 phase was broader in the (R,S) compound than in the (S,S) compound.

Odd-even behavior of ferroelectricity and antiferroelectricity in two homologous series of bent-core mesogens.

Two chiral bent-core mesogens Pn-O-PIMB(n - 2)* (n = 9 and 10) and their oxygen analogues Pn-O-PIMB(n - 2)*-(n - 4)O (n = 8, 9, and 10) with omega-[(S)-amyloxy]alkoxy terminal groups were prepared, and their phase structures were investigated by means of electro-optic, polarization reversal current and second harmonic generation measurements in order to clarify the effect of the interlayer steric interaction on the emergence of polar orderings. The odd-even behavior for the alternative appearance of ferroelectricity and antiferroelectricity was observed in two homologous series; the bent-core mesogens P10-O-PIMB8*, P8-O-PIMB6*-4O, and P10-O-PIMB8*-6O in addition to the previously reported P6-O-PIMB4* and P8-O-PIMB6*, where the length of chains n is even, exhibited ferroelectric phases. On the contrary, the mesogens P7-O-PIMB5*, P9-O-PIMB7*, and P9-O-PIMB7*-5O, where n is odd, showed antiferroelectric phases. It is obvious that the interlayer steric interaction plays a major role for the emergence of a variety of phase structures.