Self-Assembled Molecular Fibers Aligned by Compression in Water.

Molecular self-assembly has attracted much attention as a potential approach for fabricating nanostructured functional materials. To date, energy-efficient fabrication of nano-objects such as nanofibers, nanorings, and nanotubes is achieved using well-designed self-assembling molecules. However, the application of molecular self-assembly to industrial manufacturing processes remains challenging because regulating the positions and directions of self-assembled products is difficult. Non-covalent molecular assemblies are also too fragile to allow mechanical handling. The present work demonstrates the macroscopic alignment of self-assembled molecular fibers using compression. Specifically, the macroscopic bundling of self-assembled nanofibers is achieved following dispersion in water. These fiber bundles can also be chemically crosslinked without drastic changes in morphology via trialkoxysilyl groups. Subsequently, vertically oriented porous membranes can be produced rapidly by slicing the bundles. This technique is expected to be applicable to various functional self-assembled fibers and can lead to the development of innovative methods of producing anisotropic nanostructured materials.

Hybrid Surface Design of Organosilica Films for Laser Desorption/Ionization Mass Spectrometry: Low Free Energy Surface with Interactive Sites.

Laser desorption/ionization mass spectrometry (LDI-MS) assisted by solid substrates is useful for the facile and rapid analysis of low-molecular-weight compounds. The LDI performance of solid substrates depends on not only a surface morphology but also the surface functionalities dominating the surface-analyte interactions. In this study, we propose a hybrid surface design for LDI substrates, realizing both weak surface-analyte interaction and homogeneous distribution of analytes. The hybrid surface consisted of a mixture of fluoroalkylsilane (FAS), SiO2, and TiO2 and was formed on organosilica substrates containing UV-laser-absorbing naphthalimide moieties. To investigate the surface interactions, the hybrid surface as well as conventional hydrophobic surfaces treated with FAS only were prepared on flat organosilica films. Contact angle measurements and surface free energy analysis showed that the hybrid surface exhibited the highest hydrophobicity, while the contribution of the polar and hydrogen bonding terms in the surface free energy was clearly observed. The organosilica film with the hybrid surface demonstrated significant LDI performance for the detection of biorelated compounds (e.g., peptides, phospholipids, and medicines), and a high detection ability was particularly observed for peptides. The substrate surface promoted the desorption/ionization of analytes through a low surface free energy and uniform distribution of the analytes due to the interactive sites. The hybrid surface design was then applied to a nanostructured organosilica substrate consisting of a base film and a nanoparticle layer. The signal intensity of a peptide was further improved approximately 3-fold owing to the increased surface area of the nanostructured substrate, and the limit of detection reached the subfemtomole order. Our hybrid surface design is expected to improve the LDI performance of various nanostructured solid substrates.

TiN nanopillar-enhanced laser desorption and ionization of various analytes.

The present paper reports on the use of TiN nanopillars as a robust analytical substrate for laser desorption/ionization mass spectrometry (LDI-MS). TiN nanopillars were fabricated on silicon wafers through the dynamic oblique deposition of titanium, followed by thermal treatment in an ammonia atmosphere. The TiN nanopillars were readily applicable to a simple "dried-droplet" method in the LDI-MS without surface modification or pre-treatment. A broad range of analytes were investigated, including a small drug molecule, a synthetic polymer, sugars, peptides, and proteins. Intact molecular signals were detected with low noise interference and no fragmentation. The developed TiN-nanopillar-based approach extends the applicable mass limit to 150 kDa (immunoglobulin G) and was able to detect trypsinogen (24 kDa) at levels as low as 50 fmol µL-1 with adequate shot-to-shot signal reproducibility. In addition, we carried out MS analysis on biomolecule-spiked human blood plasma and a mixture of standard samples to investigate the promise of the TiN nanopillars for clinical research. The experimental observations are validated using electromagnetic and heat-transfer simulations. The TiN nanopillars show a reduced reflection and exhibit surges in the TiN surface temperature upon irradiation with electromagnetic radiation. Localization of thermal energy at the tips of the TiN pillars is likely to be responsible for the superior LDI performance. Our results suggest that the development of nanostructured TiN substrates will contribute to the widespread implementation of nanostructured solid substrates for biomedical and clinical applications with simple processes.

Re(bpy)(CO)3 Cl Immobilized on Bipyridine-Periodic Mesoporous Organosilica for Photocatalytic CO2 Reduction.

This paper describes the physicochemical properties of a rhenium (Re) complex [Re(bpy)(CO)3 Cl] immobilized on a bipyridine-periodic mesoporous organosilica (BPy-PMO) acting as a solid support. The immobilized Re complex generated a metal-to-ligand charge transfer absorption band at 400 nm. This wavelength is longer than that exhibited by Re(bpy)(CO)3 Cl in the polar solvent acetonitrile (371 nm) and is almost equal to that in nonpolar toluene (403 nm). The photocatalytic activity of this heterogeneous Re complex was lower than that of a homogeneous Re complex due to the reduced phosphorescence lifetime resulting from immobilization. However, the catalytic activity was enhanced by the co-immobilization of the ruthenium (Ru) photosensitizer [Ru(bpy)3 ]2+ on the PMO pore surfaces. Quantum chemical calculations suggest that electron transfer between the Ru and Re complexes occurs through interactions between the molecular orbitals in the pore walls. These results should have applications to the design of efficient heterogeneous CO2 reduction photocatalysis systems.

Simple and scalable preparation of master mold for nanoimprint lithography.

Nanoimprint lithography (NIL) is one of the most prominent bottom-up techniques for duplicating nanostructures with a high throughput. However, fabrication of starting master mold commonly requires expensive equipment of top-down techniques, or additional steps to transfer the fabricated patterns from bottom-up methods. Here we demonstrate that a SiO2 nanostructure manufactured from a self-assembled block copolymer, polystyrene-b-polydimethylsiloxane (PS-b-PDMS), directly serves as a master mold for NIL without further modification. A hexagonally aligned pattern over the entire substrate is established using a simple technique; solvent annealing and etching. Etching also plays an important role in endowing fluorine on the surface of SiO2, thus promoting smooth demolding upon imprinting. The obtained pattern of the SiO2 nanostructure is transferred to a polymer surface using UV nanoimprint. Identical patterns of the SiO2 nanostructure are elaborately reproduced on Ni and Cu nanodot arrays via electroplating on the polymer transcript, which was verified by morphological observations. The uniformity of the replicated Ni nanodot array is evaluated using spectroscopic ellipsometry. The measured optical response of the Ni nanodot is validated by electromagnetically simulated results, indicating that the pattern transfer is not limited to a small local area. In addition, the durability of the SiO2 mold pattern is corroborated after the imprinting process, thus guaranteeing the reusability of the fabricated nanostructure as a master mold. The proposed approach does not require any high-end lithographic techniques; this may result in significant cost and time reductions in future nanofabrication.

A solid chelating ligand: periodic mesoporous organosilica containing 2,2'-bipyridine within the pore walls.

Synthesis of a solid chelating ligand for the formation of efficient heterogeneous catalysts is highly desired in the fields of organic transformation and solar energy conversion. Here, we report the surfactant-directed self-assembly of a novel periodic mesoporous organosilica (PMO) containing 2,2'-bipyridine (bpy) ligands within the framework (BPy-PMO) from a newly synthesized organosilane precursor [(i-PrO)3Si-C10H6N2-Si(Oi-Pr)3] without addition of any other silane precursors. BPy-PMO had a unique pore-wall structure in which bipyridine groups were densely and regularly packed and exposed on the surface. The high coordination ability to metals was also preserved. Various bipyridine-based metal complexes were prepared using BPy-PMO as a solid chelating ligand such as Ru(bpy)2(BPy-PMO), Ir(ppy)2(BPy-PMO) (ppy = 2-phenylpyridine), Ir(cod)(OMe)(BPy-PMO) (cod = 1,5-cyclooctadiene), Re(CO)3Cl(BPy-PMO), and Pd(OAc)2(BPy-PMO). BPy-PMO showed excellent ligand properties for heterogeneous Ir-catalyzed direct C-H borylation of arenes, resulting in superior activity, durability, and recyclability to the homogeneous analogous Ir catalyst. An efficient photocatalytic hydrogen evolution system was also constructed by integration of a Ru-complex as a photosensitizer and platinum as a catalyst on the pore surface of BPy-PMO without any electron relay molecules. These results demonstrate the great potential of BPy-PMO as a solid chelating ligand and a useful integration platform for construction of efficient molecular-based heterogeneous catalysis systems.

AlveoMPU: Bridging the Gap in Lung Model Interactions Using a Novel Alveolar Bilayer Film.

The alveoli, critical sites for gas exchange in the lungs, comprise alveolar epithelial cells and pulmonary capillary endothelial cells. Traditional experimental models rely on porous polyethylene terephthalate or polycarbonate membranes, which restrict direct cell-to-cell contact. To address this limitation, we developed AlveoMPU, a new foam-based mortar-like polyurethane-formed alveolar model that facilitates direct cell-cell interactions. AlveoMPU features a unique anisotropic mortar-shaped configuration with larger pores at the top and smaller pores at the bottom, allowing the alveolar epithelial cells to gradually extend toward the bottom. The underside of the film is remarkably thin, enabling seeded pulmonary microvascular endothelial cells to interact with alveolar epithelial cells. Using AlveoMPU, it is possible to construct a bilayer structure mimicking the alveoli, potentially serving as a model that accurately simulates the actual alveoli. This innovative model can be utilized as a drug-screening tool for measuring transepithelial electrical resistance, assessing substance permeability, observing cytokine secretion during inflammation, and evaluating drug efficacy and pharmacokinetics.

Perfluoroalkyl Group-Covered Organosilica Films for the Sensitive Detection of Sulfonylurea Herbicides in Laser Desorption/Ionization Mass Spectrometry.

Simple and rapid screening of agrochemicals greatly contributes to food and environmental safety. Matrix-free laser desorption/ionization mass spectrometry (LDI-MS) is an effective tool for high-throughput analysis of low-molecular-weight compounds. In this study, we report a UV-laser-absorbing organosilica film for the sensitive detection of various sulfonylurea herbicides using LDI-MS. Organosilica films with fluoroalkyl groups on the organic part are fabricated, followed by additional modification of the silica moiety with a fluoroalkyl coupling agent to cover the film surface with hydrophobic fluoroalkyl groups. Nanoimprinting is conducted to impart nanostructures on the film surface to enhance the LDI performance. The fabricated nanostructured organosilica films accomplish sensitive detection of cyclosulfamuron and azimsulfuron at concentrations as low as 1 fmol µL-1. The applicability of the nanostructured organosilica films is confirmed by the recovery of cyclosulfamuron and ethametsulfuron-methyl from pea sprouts (Pisum sativum) hydroponically grown in herbicide-spiked water at concentrations of 0.5 ppm.

Study of the association between an anomalous superior vena cava and horseshoe kidney.

BACKGROUND: The incidence of inferior vena cava anomalies in patients with horseshoe kidney is higher than that reported in the general population. As far as we know, no studies have reported the incidence and variations of superior vena cava (SVC) anomalies using multidetector-row computed tomography (MDCT) in patients with horseshoe kidney. METHODS AND RESULTS: Using MDCT, 71 patients with a horseshoe kidney (group A: 45 males, 26 females; mean age, 60.1 ± 10.2 years) and 2,292 patients without a horseshoe kidney (group B: 1,385 males, 907 females; mean age, 61.1 ± 13.5 years) were retrospectively evaluated for the incidence and variations of SVC anomalies, and the incidence of an anomalous SVC was compared between groups. An anomalous SVC was identified in 3 group A patients (4.2%) (double SVC, n=2; persistent left SVC without a right SVC, n=1) and 5 group B patients (0.22%) (double SVC, n=3; persistent left SVC without a right SVC, n=2). MDCT revealed a significantly higher incidence of anomalous SVC in patients with a horseshoe kidney than in those without a horseshoe kidney (P<0.001). CONCLUSIONS: Patients with horseshoe kidney frequently have an anomalous SVC. Although the incidence of horseshoe kidney is related in some way to that of an anomalous SVC, the reasons for their coexistence remain unclear.

Self-assembled single-crystal bimodal porous GaN exhibiting a petal effect: application as a sensing platform and substrate for optical devices.

This paper investigates the petal effect (hydrophobicity and strong adhesion) observed on single-crystal bimodal porous GaN (porous GaN), which has almost the same electrical properties as bulk GaN. The water contact angles of porous GaN were 100°-135° despite the intrinsic hydrophilic nature of GaN. Moreover, it was demonstrated that the petal effect of porous GaN leads to the uniform attachment of water solutions, enabling highly uniform and aggregation-free attachment of chemicals and quantum dots. These results indicate that porous GaN can be applied in quantum dot light-emitting diodes and as an analytical substrate.

Nanoporous Substrates with Molecular-Level Perfluoroalkyl/Alkylamide Surface for Laser Desorption/Ionization Mass Spectrometry of Small Proteins.

The rapid detection of biomolecules greatly contributes to health management, clinical diagnosis, and prevention of diseases. Mass spectrometry (MS) is effective for detecting and analyzing various molecules at high throughput. However, there are problems with the MS analysis of biological samples, including complicated separation operations and essential pretreatments. In this study, a nanostructured organosilica substrate for laser desorption/ionization mass spectrometry (LDI-MS) is designed and synthesized to detect peptides and small proteins efficiently and rapidly. The surface functionality of the substrate is tuned by perfluoroalkyl/alkylamide groups mixed at a molecular level. This contributes to both lowering the surface free energy and introducing weak anchoring sites for peptides and proteins. Analyte molecules applied onto the substrate are homogeneously distributed and readily desorbed by the laser irradiation. The organosilica substrate enables the efficient LDI of various compounds, including peptides, small proteins, phospholipids, and drugs. An amyloid ß protein fragment, which is known as a biomarker for Alzheimer's disease, is detectable at 0.05 fmol µL-1. The detection of the amyloid ß at 0.2 fmol µL-1 is also confirmed in the presence of blood components. Nanostructured organosilica substrates incorporating a molecular-level surface design have the potential to enable easy detection of a wide range of biomolecules.

Directional study of the optical properties of Tb3+- and Eu3+-doped nanoparticles embedded in silica photonic crystals.

The effects of the stop band (SB) in colloidal photonic crystals composed of silica spheres containing Eu(3+)- and Tb(3+)-doped yttria nanoparticles are analysed. Reflection and transmission spectra indicate movement of the stop band, due to the 111 series of planes, towards shorter wavelengths with increasing angle of observation. The profile of the emission spectra is modified by the presence of the SB depending on the angle of measurement. Such a modification is more effective for a narrow emission band and it is thus more evident in the case of Tb(3+) than Eu(3+). An angular effect is also observed in the lifetime, which presents two maxima and one minimum. In the case of Tb(3+) the maxima are at observation angles of 35 and 50 degrees, and the minimum at 45 degrees. We attribute this behaviour to penetration of the excitation beam at 475 nm modulated by the stop band. The ions excited in this way emit from different depths in the crystal, and therefore their lifetime will be affected differently by the same stop band, depending on the thickness of the crystal that must be crossed. Eu(3+) shows a similar but less pronounced effect for two reasons: first, the main stop band (due to the 111 planes) is not effective at the excitation wavelength of 392 nm; second, the broadness of the Eu(3+) emission is comparable to the width of the SB, and a decrease in the transition rate at the wavelength of the SB maximum is compensated by an increase at the sides of the SB.

Artificial black opal fabricated from nanoporous carbon spheres.

A nanocasting method via chemical vapor deposition of acetonitrile was successfully employed to fabricate porous carbon colloidal crystal using colloidal crystal from monodispersed mesoporous silica spheres (MMSS) as a sacrificial scaffold. The mesostructure as well as periodic arrays within (111) plane of MMSS were replicated for the carbon colloidal crystal (black opal) with the length scale in the centimeter range. Brilliant iridescent colors were clearly observed for the first time on the black carbon colloidal crystal fabricated from porous carbon spheres, and they changed dramatically in accordance with the observation angle, like natural black opals. Reflection spectra measurements based on 2D surface diffraction and Bragg diffraction in the mirror mode were conducted for the fabricated carbon periodic arrays. The periodicity in the (111) plane as well as in the direction perpendicular to the (111) plane of the colloidal crystal was evaluated by comparing the results obtained from these two measurements. It was found that the periodicity in the direction perpendicular to the (111) surface is not high for the obtained black carbon opal. On the other hand, the relationship between the incident angles and the peak wavelengths of the reflection spectra, collected in the condition where the incident light and the reflected light pass through in the same direction, is governed by an approximation based on 2D surface diffraction. The results imply that the origin of the iridescent colors on the fabricated black carbon opal is derived from the periodicity not in the direction perpendicular to the (111) plane but within the (111) plane.

New strategy using glycol-modified silane to synthesize monodispersed mesoporous silica spheres applicable to colloidal photonic crystals.

A new approach focusing on the reactivity of a silica source was developed for the particle size control of monodispersed mesoporous silica spheres (MMSSs). A glycol-modified silanes, tetrakis(2-hydroxyethyl) orthosilicate was chosen as the silica source and successfully applied in the surfactant-templated synthesis of MMSSs in a very dilute alkaline alcohol-water mixture. Due to its higher hydrolysis rate compared with tetraalkyl orthosilicates, it took less time for the primary particles to come out, resulting in the formation of small particles with diameters falling in the low submicrometer range. The resultant spheres possessed a well-ordered mesoporous structure, which was typically MCM-41-type hexagonal. The MCM-48-type cubic spheres could also be obtained by changing the reaction condition. The monodispersity and particle size of the spheres were precisely controlled by the adjustment of the solvent composition in the methanol-ethanol-water system. Furthermore, ionic colloidal crystals exhibiting a well-defined stop band in the visible light region could be fabricated from the resultant MMSSs for the first time. This work encourages the further utilization of MMSSs in photonics as well as in catalysis or biochemistry.

Direct nanoimprinting of nanoporous organosilica films consisting of covalently crosslinked photofunctional frameworks.

Nanoimprinting methods have been used widely to prepare various patterned or nanostructured thin films from inorganic or organic components. However, the accumulation of large functional aromatic groups in covalently crosslinked nanoimprints is challenging, due to the difficulty in controlling the fluidity and reactivity of the precursor films. In this work, nanoimprinting of naphthalimide-silica sol-gel films results in vertically oriented nanoporous structures consisting of covalently crosslinked UV-absorbing frameworks. The nanoimprinted films demonstrate potential as robust analytical substrates for laser desorption/ionization mass spectrometry (LDI-MS). The sol-gel polycondensation behavior of the precursors is examined using 29Si NMR spectroscopy to determine reaction conditions suitable for nanoimprinting. The inorganic-organic hybrid frameworks containing a high density of naphthalimide groups exhibit small volume shrinkage during the polycondensation reactions, which leads to desired nanoimprinting. Various bio-related compounds on the order of picomole to femtomole quantities are detectable by LDI-MS measurements using the nanoimprinted substrates. To improve their user-friendliness and signal intensity in LDI-MS analysis, the nanoimprinted substrates are patterned with surface-modified silica nanoparticles. The direct formation of surface nanostructures by nanoimprinting of functional organosilica films may open a new path to developing optically and electronically functional materials, thereby widening their utility.

Manipulation of the spontaneous emission in mesoporous synthetic opals impregnated with fluorescent guests.

The spontaneous emission of light from light-emitting materials adsorbed within the ordered pores of monodispersed mesoporous silica spheres (MMSS) has been investigated. By taking advantage of the ordered starburst pores of MMSS, we can provide a simple strategy for fabricating synthetic opals consisting of homogeneous individual building blocks in which fluorescent guests are uniformly and stably impregnated. In this study, tris(8-hydroxyquinolinato)aluminum(III) (Alq(3)) and Rhodamine B (Rh B) are selected as the fluorescent guests. The former has a wider emission band than the reflection spectrum of MMSS synthetic opals, whereas the emission band of the latter is considerably narrower than the reflection spectrum of the opals. The spontaneous emissions of these functionalized synthetic opals are clearly influenced by the stop band governed by the Bragg equation. In the case of the Alq(3)-MMSS conjugate, the shape of the Alq(3) emission spectrum varies in accordance with the shift in the stop band. The emission of the Rh B-MMSS conjugate is noticeably narrowed, and its intensity is enhanced when the excitation intensity is increased. These results are well explained by an inhibition of spontaneous emission caused by a reduction in the density of optical states within the stop band. The results of this study indicate that MMSS synthetic opals are promising for use in novel optical applications in which the spontaneous emission can be manipulated.

High-aspect-ratio mushroom-like silica nanopillars immersed in air: epsilon-near-zero metamaterials mediated by a phonon-polaritonic anisotropy.

Epsilon-near-zero metamaterials offer opportunities for intriguing electromagnetic-wave phenomena. Here we experimentally demonstrate that silica perpendicular nanopillars immersed in air exhibit a uniaxial epsilon-near-zero response mediated by phonon polaritons in the mid-infrared range. Unique mushroom-shaped heads on nanopillars play a crucial role to realize SiO2 metamaterials over a large area in our self-assembled fabrication process with block copolymers, polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS). SiO2 nanopillars having heights of 80 nm, 200 nm, and 300 nm (aspect ratios up to ∼13) are obtained after calcination at 450 °C and the electromagnetic responses are evaluated using a mid-infrared ellipsometric apparatus. For nanopillars with 200 nm height, the permittivity of the perpendicular component ε ⊥ approaches to near zero (0.2) while the parallel component ε ‖ shows a value of 1.8. The measured uniaxial epsilon-near-zero responses are excellently reproduced by the effective medium theory. Our results, therefore, indicate that SiO2 nanopillars/air uniaxial epsilon-near-zero metamaterials in the mid-infrared range can be amenable to large scale fabrication.

Acute Liver Failure Due to Severe Hepatic Metastasis of Small-cell Lung Cancer Producing Adrenocorticotropic Hormone Complicating Ectopic Cushing Syndrome.

A 72-year-old man was admitted to a general hospital with progressive liver dysfunction, hypokalemia, hyperglycemia, and nodules in the lung and liver and then transferred to our institution on the seventh hospital day. Plasma levels of adrenocorticotropic hormone (ACTH), cortisol, and neuron-specific enolase concentrations were extremely high. He developed acute liver failure, his consciousness and general condition deteriorated rapidly, and he died on Day 11. At the postmortem examination, he was found to have extensive metastases from small-cell lung cancer, including advanced hepatic metastases. This is the first reported case of acute liver failure caused by metastases derived from an ACTH-producing pulmonary small-cell carcinoma.

Pore-expansion of monodisperse mesoporous silica spheres by a novel surfactant exchange method.

By adapting a novel surfactant exchange method, in which surfactants inside mesopores are completely exchanged by surfactants with longer alkyl chain lengths, pore-expansion of monodisperse mesoporous silica spheres (MMSS) with radially ordered hexagonal regularity was attained while retaining spherical morphology and high monodispersity.

Efficacy and safety of sofosbuvir and ledipasvir in Japanese patients aged 75 years or over with hepatitis C genotype 1.

AIM: To evaluate the efficacy and safety of a regimen containing sofosbuvir (SOF) and ledipasvir (LDV) in Japanese patients aged ≥ 75 years with hepatitis C genotype 1. METHODS: This multicenter, retrospective study consisted of 246 Japanese patients with HCV genotype 1 at nine centers in Miyazaki prefecture in Japan. Demographic, clinical, virological, and adverse effects (AE)-related data obtained during and after SOF/LDV therapy were collected from medical records. These patients were divided into two groups, younger (aged < 75 years) and elderly (aged ≥ 75 years). Virological data and AEs were analyzed by age group. RESULTS: The sustained virological response (SVR) rates at 12 wk after treatment were 99.2%, 99.4%, and 98.7% in the overall population and in patients aged < 75 and ≥ 75 years, respectively. Common AEs during therapy were headache, pruritus, constipation, and insomnia. These occurred in fewer than 10% of patients, and their incidence was not significantly different between the younger and elderly groups. Two patients discontinued treatment, one due to a skin eruption and the other due to cerebral bleeding. CONCLUSION: Compared with younger patients, elderly patients had a similar virological response and tolerance to SOF/LDV therapy.