CHOROIDAL VASCULAR DENSITY IN DIABETIC RETINOPATHY ASSESSED WITH SWEPT-SOURCE OPTICAL COHERENCE TOMOGRAPHY.

PURPOSE: We aimed to assess choroidal vascularity by diabetic retinopathy (DR) stage using the choroidal vascular density (CVD) obtained from swept-source optical coherence tomography en-face images. METHODS: This prospective, cross-sectional, multicenter study included patients from Niigata City General Hospital and Saiseikai Niigata Hospital between October 2016 and October 2017. Choroidal vascular density was obtained by binarizing swept-source optical coherence tomography en-face images of patients with diabetes and those with DR, patients without DR, and healthy age-matched volunteers. RESULTS: Patients were allocated to the healthy control (n = 28), no DR (n = 23), nonproliferative DR (NPDR) without diabetic macular edema (DME) (n = 50), NPDR + DME (n = 38), and proliferative DR (PDR) or any previous treatment with panretinal photocoagulation (n = 26) groups. Investigation of the choriocapillaris slab level indicated that the no DR group had significantly high CVD values ( P < 0.05), and the PDR groups had significantly low CVD values ( P < 0.01). Investigation of the large choroidal vessel level indicated that the NPDR + DME and PDR groups had significantly lower CVD values than the control group ( P < 0.05 and P < 0.01, respectively). CONCLUSION: We found that at the choriocapillaris slab level, the no DR group had a higher CVD and the NPDR with DME and PDR groups had a lower CVD than the control group. At the level of the large choroidal vessels, the NPDR with DME and PDR groups had a lower CVD than the control group. There were significant differences in choroidal vasculature found using CVD obtained from swept-source optical coherence tomography en-face images of patients with diabetes and DR.

Mechano- and Photoresponsive Behavior of a Bis(cyanostyryl)benzene Fluorophore.

The mechanoresponsive behavior and photochemical response of a new bis(cyanostyryl)benzene fluorophore (CSB-5) were investigated. Green fluorescence with λem,max of 507 nm was found for CSB-5 in chloroform solution, mirroring the behavior of a previously reported similar dye (CSB-6). Alternatively, crystalline samples of CSB-5 exhibited orange fluorescence with λem,max of 620 nm, attributable to excimer emission. Although the emission color change was not clearly noticeable by naked eye, CSB-5 exhibited mechanochromic luminescence, due to transformation into the amorphous state upon grinding the crystalline powder. Interestingly, rubbed films of CSB-5 prepared on glass substrates exhibited a pronounced emission color change from orange to green when exposed to UV light. This response is the result of a photochemical reaction that occurs in the amorphous state and which causes a decrease of the excimer emission sites so that the emission color changes from excimer to monomer. The crystalline material did not display such a photoinduced emission color change and the difference in photochemical reactivity between crystalline and amorphous states was exploited to pattern the emission color of rubbed films.

Photophysics and Inverted Solvatochromism of 7,7,8,8-Tetracyanoquinodimethane (TCNQ).

We report absorption, fluorescence, and Raman spectroscopy of 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a variety of solvents. The fluorescence quantum yields (QYs) of linear alkane solutions are similar to one another, but QY is shown to acutely decrease in other solvents with increasing polarities. The slope of the solvatochromic plot of absorption maxima is inverted from negative to positive with an increase in solvent polarity. A significant change in the frequency of carbon-carbon double bond stretching modes is not observed in Raman spectra of TCNQ in different solvents. The molar absorption coefficient is determined to calculate the oscillator strength of the absorption band. The radiative decay rate constant calculated from the oscillator strength is approximately ten times larger than that elucidated from the fluorescence lifetime and QY. These spectroscopic parameters reveal that the relaxation occurs from a Franck-Condon excited state to a distinct fluorescence emissive state with a smaller transition dipole moment.

Solid-State Electrochemistry of Copper(I) Coordination Polymers Containing Tetrafluoroborate Anions.

Host-guest materials based on coordination polymers (CPs) are currently emerging as potential candidates for battery applications. In this context, we describe the preparation of three-dimensional network structures containing BF4 anions and water molecules in the one-dimensional (1D) channels via hydrothermal reactions between Cu(BF4)2 and 4,4'-bipyridine or 1,2-di-4-pyridylethylene. A systematic characterization of the obtained CPs using single-crystal X-ray diffraction, X-ray absorption fine structure, and an electrochemical test was performed. The results showed that the BF4 anions were electrochemically reduced to BF3 in the cavities of the CPs, with concomitant elimination of a leaving fluoride at room temperature. Using this electrochemical property, a prototype battery, in which the CPs act as the anode and graphite as the cathode, was demonstrated. The cell exhibited a practical discharge potential of ∼1.5 V. This constitutes the first demonstration of CPs showing electrochemical B-F bond activation in the 1D channels and rocking-chair-type fluoride insertion and extraction by changes in the electric potential.

Chemical modification of group IV graphene analogs.

Mono-elemental two-dimensional (2D) crystals (graphene, silicene, germanene, stanene, and so on), termed 2D-Xenes, have been brought to the forefront of scientific research. The stability and electronic properties of 2D-Xenes are main challenges in developing practical devices. Therefore, in this review, we focus on 2D free-standing group-IV graphene analogs (graphene quantum dots, silicane, and germanane) and the functionalization of these sheets with organic moieties, which could be handled under ambient conditions. We highlight the present results and future opportunities, functions and applications, and novel device concepts.

Isolation of Hypervalent Group-16 Radicals and Their Application in Organic-Radical Batteries.

Using a newly prepared tridentate ligand, we isolated hypervalent sulfur and selenium radicals for the first time and characterized their structures. X-ray crystallography, electron spin resonance spectroscopy, and density functional theory calculations revealed a three-coordinate hypervalent structure. Utilizing the reversible redox reactions between hypervalent radicals and the corresponding anions bearing Li(+), we developed organic radical batteries with these compounds as cathode-active materials. Furthermore, an all-radical battery, with these compounds as the cathode and a silyl radical as the anode, was developed that exhibited a practical discharge potential of ∼ 1.8 V and stable cycle performance, demonstrating the potential of these materials for use in metal-free batteries that can replace conventional Li-ion batteries where Li is used in the metal form.

Biotic and human vulnerability to projected changes in ocean biogeochemistry over the 21st century.

Ongoing greenhouse gas emissions can modify climate processes and induce shifts in ocean temperature, pH, oxygen concentration, and productivity, which in turn could alter biological and social systems. Here, we provide a synoptic global assessment of the simultaneous changes in future ocean biogeochemical variables over marine biota and their broader implications for people. We analyzed modern Earth System Models forced by greenhouse gas concentration pathways until 2100 and showed that the entire world's ocean surface will be simultaneously impacted by varying intensities of ocean warming, acidification, oxygen depletion, or shortfalls in productivity. In contrast, only a small fraction of the world's ocean surface, mostly in polar regions, will experience increased oxygenation and productivity, while almost nowhere will there be ocean cooling or pH elevation. We compiled the global distribution of 32 marine habitats and biodiversity hotspots and found that they would all experience simultaneous exposure to changes in multiple biogeochemical variables. This superposition highlights the high risk for synergistic ecosystem responses, the suite of physiological adaptations needed to cope with future climate change, and the potential for reorganization of global biodiversity patterns. If co-occurring biogeochemical changes influence the delivery of ocean goods and services, then they could also have a considerable effect on human welfare. Approximately 470 to 870 million of the poorest people in the world rely heavily on the ocean for food, jobs, and revenues and live in countries that will be most affected by simultaneous changes in ocean biogeochemistry. These results highlight the high risk of degradation of marine ecosystems and associated human hardship expected in a future following current trends in anthropogenic greenhouse gas emissions.

Stark Spectroscopy of Rubrene. I. Electroabsorption Spectroscopy and Molecular Parameters.

Electroabsorption spectroscopy investigation and the determination of molecular parameters for rubrene dispersed in a poly(methyl methacrylate) (PMMA) matrix are reported. The features of the band system in the absorption spectrum in PMMA are analogous to those in solutions. The changes in the electric dipole moment and the polarizability between the excited and ground states are determined from analysis of the Stark effect in the absorption band. The change in the transition dipole moment in the presence of an external electric field is also observed. Although rubrene is predicted to be classified as a nonpolar molecule, there is a contribution of the difference in the electric dipole moment between the excited and ground states to the electroabsorption spectrum. The origin of the nonzero difference in the electric dipole moment is argued. Stark fluorescence spectroscopy investigation is reported in Part II of this series.

Mechanofluorochromism of 1-Alkanoylaminopyrenes.

To create a new series of mechanofluorochromic materials and to elucidate the mechanism of the phenomenon of mechanofluorochromism, 1-alkanoylaminopyrenes including 1-acetylaminopyrene (AAPy), 1-octanoylaminopyrene (OAPy), and 1-stearoylaminopyren (SAPy) were prepared. It was found that these materials exhibited mechanofluorochromism with emission colors in the crystalline samples changing reversibly from bluish purple to yellowish green, which could be induced by mechanical grinding. X-ray crystal structure analysis, electronic absorption, and fluorescence spectroscopies, as well as fluorescence lifetime analysis and powder X-ray diffraction analysis of AAPy suggested that the present mechanofluorochromism was caused by developing crystal defects through grinding. Intermolecular hydrogen bonds were suggested to play an important role in the occurrence of mechanofluorochromism, suppressing the face-to-face overlapping of pyrene moieties to form excimers in the pristine crystal.

High-power electrochemical energy storage system employing stable radical pseudocapacitors.

The development of electrical energy storage devices that can operate at high charge and discharge rates is fundamentally important, however although electrochemical capacitors (ECs) can charge and discharge at high rates, their electrochemical storage capacity remains an order of magnitude lower than that of conventional lithium-ion batteries. Novel pseudocapasitors are developed, based on the stable persilyl-susbtituted free radicals of the heavy group 14 elements, (tBu2 MeSi)3 E(.) [E=Si (1), Ge (2), and Sn (3)], as anode materials for energy storage system. Such systems showed a remarkable cycle stability without significant loss of power density, in comparison with similar characteristics of the known organic radical batteries, the dual carbon cell, and the electrochemical capacitor. Particularly important is that these novel electrochemical energy storage systems employing stable heavy group 14 element radicals are lithium-free. The electrochemical properties and structures of the reduced and oxidized species were studied by the cyclic voltammetry (CV), electron paramagnetic resonance (EPR) spectroscopy, and X-ray diffraction (XRD).

Fluorescence color change of aggregation-induced emission of 4-[bis(4-methylphenyl)amino]benzaldehyde.

Together we shine: Fluorescence color change of 4-[bis(4-methylphenyl)amino]benzaldehyde (BMABA) could be induced by vigorous stirring and heating of the suspension. This is attributed to a morphological change of the particles from an amorphous state to a crystalline state; therefore, BMABA is identified as a new aggregation-induced emission material.

Cold- versus warm-season-forced variability of the Kuroshio and North Pacific subtropical mode water.

The ocean responds to atmospheric variations. Changes in sea surface winds, surface air temperature, and surface air humidity cause upper ocean variability by modulating air-sea momentum and heat exchanges. Upper ocean variability in the mid-latitudes on inter-annual and longer timescales has previously been considered to be attributable to atmospheric variations in the cold season, because atmospheric forcing is stronger in the cold season than in the warm season. However, this idea has not been sufficiently confirmed yet. Although the ocean model is a useful tool to evaluate the impact of the atmospheric forcing in each season, there are no past studies having examined ocean model responses respectively to the cold- and warm-season atmospheric forcing. In this study, we performed numerical experiments with an eddy-resolving ocean general circulation model and investigated oceanic responses to cold- and warm-season atmospheric forcing, focusing on the Kuroshio and North Pacific subtropical mode water (STMW) in the western mid-latitude North Pacific. We found that temporal variations of net Kuroshio transport and STMW distribution/temperature are dominantly controlled by atmospheric forcing in the cold season. These results suggest that cold-season atmospheric variations are key to obtaining insights into large-scale upper ocean variability in the North Pacific subtropical gyre.

Northward shift of the Kuroshio Extension during 1993-2021.

The Kuroshio Extension (KE) flows eastward at the northern boundary of the North Pacific subtropical gyre. By transporting large amounts of seawater with heat, the KE contributes significantly to the formation of sea surface temperature (SST) fields. Recently, poleward shifts of major ocean gyres in the world ocean, including the North Pacific subtropical gyre, have been highlighted based on basin-scale changes in SST and sea surface height (SSH) distributions. However, a detailed investigation of the long-term meridional KE movement has not been presented. Investigation of KE path changes helps provide insights into long-term changes in the physical fields in the western North Pacific. In this study, we identified the KE path from satellite-derived SSH and surface current velocity data using a front identification method and showed that the KE migrated northward by approximately 210 km during 1993-2021. We further explored the cause of the northward KE shift based on atmospheric reanalysis data and numerical experiments using a high-resolution ocean general circulation model. It was revealed that the northward KE shift is mostly caused by the trend of wind stress curl in the North Pacific during 1993-2021.

Effective generation mechanisms of tropical instability waves as represented by high-resolution coupled atmosphere-ocean prediction experiments.

Cusp-shaped fluctuations of the sea surface temperature (SST) front in the tropical Pacific, now known as tropical instability waves (TIWs), were discovered by remote sensing in the 1970s. Their discovery was followed by both theoretical and analytical studies, which, along with in situ observations, identified several possible generation mechanisms. Although modeling studies have shown that TIWs strongly influence the heat budget, their influence on local variations of realistically initialized predictions is not yet understood. We here evaluate a series of medium-range (up to ~ 10 days) coupled atmosphere-ocean predictions by a coupled model with different horizontal resolutions. Observational SST, surface wind stress, heat flux, and pressure data showed that representation of temporally and spatially local variations was improved by resolving fine-scale SST variations around the initialized coarse-scale SST front fluctuations of TIWs. Our study thus demonstrates the advantage of using high-resolution coupled models for medium-range predictions. In addition, analysis of TIW energetics showed two dominant sources of energy to anticyclonic eddies: barotropic instability between equatorial zonal currents and baroclinic instability due to intense density fronts. In turn, the eddy circulation strengthened both instabilities in the resolved simulations. This revealed feedback process refines our understanding of the generation mechanisms of TIWs.

Preparation of alkyl-modified silicon nanosheets by hydrosilylation of layered polysilane (Si6H6).

Alkyl-modified crystalline silicon nanosheets 2 were synthesized and maintained the crystal structure of a Si(111) plane, in which the dangling silicon bond is stabilized by capping with the alkyl group. 2 was characterized using UV-vis, Fourier transform-infrared, and X-ray photoelectron spectroscopies; X-ray diffraction; and X-ray absorption near edge structure analysis. A model structure is proposed that has a periodicity through the nanosheet surface.

Synthesis of Si-Ge Nanosheets and Their Dispersion of Organic Solvents with Focus on the Hansen Solubility Parameters.

Two-dimensional (2D) materials combine the collective advantages of individual building blocks and synergistic properties and have spurred great interest as a new paradigm in materials science. Especially, exfoliation of 2D semiconductive materials into nanosheets is of significance for both fundamental and potential applications. In this report, silicon-germanium (Si-Ge) nanosheets were synthesized by sonication of porous Si-Ge powder. The raw material Si-Ge powder was obtained by leaching Li from Li13Si2Ge2 with ethanol; after that, it was crystallized by heat treatment at 500 °C. The thickness and the lateral size of the exfoliated Si-Ge nanosheets were about 3 nm and a few microns, respectively. The nanosheets were dispersed in 55 different organic solvents, and their Hansen solubility parameters were calculated and compared with those of the end member (Si and Ge) nanosheets and graphene.

Synthesis and modification of silicon nanosheets and other silicon nanomaterials.

Silicon nanomaterials and nanostructures exhibit different properties from those of bulk silicon materials based on quantum confinement effects. They are expected to lead to the development of new applications of silicon, in addition to wide use in semiconductor devices. Aside from industrial interest, intriguing issues of academic interest still remain with respect to the origins of their characteristic properties. Zero- and one-dimensional crystalline silicon nanomaterials have been synthesized, to date, by using many methods and there has been rapid progress in size control and modification procedures. However, there have been only a few examples of silicon nanomaterials with atomic-order thickness akin to carbon nanomaterials, such as two-dimensional silicon nanosheets. Moreover, mass production of silicon nanomaterials with relatively low cost is not easily achievable, due to the typically severe conditions required for fabrication, such as high temperature and ultralow pressure. Recently, we have developed a soft synthetic method for silicon nanosheets with chemical surface modification in a solution process. This review provides methods for the synthesis and modification of silicon nanosheets and other silicon nanomaterials with examples of their potential applications.

The electronic and structural properties of novel organomodified Si nanosheets.

We show that the properties of a new class of functional materials, silicon nanosheets modified with phenyl groups and H atoms, are highly promising for applications such as electronic devices. This novel material retains the sp(3) structure after functionalisation, resulting in a wide (direct) band gap of 1.92 eV.

Synthesis and optical properties of monolayer organosilicon nanosheets.

The synthesis of silicon nanosheets for fabricating electronic devices, without using conventional vacuum processes and vapor deposition, is challenging and is anticipated to receive significant attention for a wide range of applications. Here, we report the synthesis of oxygen-free, phenyl-modified organosilicon nanosheets with atomic thickness. In organic solvents, a consequence of this new silicon structure is its uniform dispersion and the possibility of exfoliation into unilamellar nanosheets. Light-induced photocurrent in [Si(6)H(4)Ph(2)] was observed, leading to the possibility of various organosilicon nonamaterials with useful properties.

Silicon nanosheets and their self-assembled regular stacking structure.

Silicon nanomaterials are encouraging candidates for application to photonic, electronic, or biosensing devices, due to their size-quantization effects. Two-dimensional silicon nanosheets could help to realize a widespread quantum field, because of their nanoscale thickness and microscale area. However, there has been no example of a successful synthesis of two-dimensional silicon nanomaterials with large lateral size and oxygen-free surfaces. Here we report that oxygen-free silicon nanosheets covered with organic groups can be obtained by exfoliation of layered polysilane as a result of reaction with n-decylamine and dissolution in an organic solvent. The amine residues are covalently bound to the Si(111) planes. It is estimated that there is ca. 0.7 mol of residue per mole of Si atoms in the reaction product. The amine-modified layered polysilane can dissolve in chloroform and exfoliate into nanosheets that are 1-2 microm wide in the lateral direction and with thicknesses on the order of nanometers. The nanosheets have very flat and smooth surfaces due to dense coverage of n-decylamine, and they are easily self-assembled in a concentrated state to form a regularly stacked structure. The nanosheets could be useful as building blocks to create various composite materials.