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Squarylium-based π-electronic cation with an augmented dipole was synthesized by methylation of zwitterionic squarylium. The cation formed various ion pairs in combination with anions, and the ion pairs exhibited distinct photophysical properties in the dispersed state, ascribed to the formation of J- and H-aggregates. The ion pairs provided solid-state assemblies based on cation stacking. It is noteworthy that complete segregation of cations and anions was observed in a pseudo-polymorph of the ion pair with pentacyanocyclopentadienide as a π-electronic anion. In the crystalline state, the ion pairs exhibited photophysical properties and electric conductivity derived from cation stacking. In particular, the charge-segregated ion-pairing assembly induces an electric conductive pathway along the stacking axis. The charge-segregated mode and fascinating properties were derived from the reduced electrostatic repulsion between adjacent π-electronic cations via dipole-dipole interactions.

Mimicking the interconvertible carbon allotropes of 2-dimensional (2D) graphene and 1-dimensional (1D) carbon nanotubes, herein we report the in-situ transformation of 2D conjugated covalent organic frameworks (COFs) sheet into 1D nanotubular structures via self-assembly the sheets at solvent interfaces. The facile “roll-the sheets” self-assembly resulted in coaxial nanotubes with uniform cross-sectional diameter, which was realized for aza-pyrene based COF instead of pyrene COF, although both possess very similar chemical structure. Upon replacing the carbon atoms at 2,7-positions of pyrene with nitrogen, contrasting optical and electronic properties was realized reflecting the rolled structure of the conjugated 2D sheets. The nanotubes exhibited semiconducting nature with stable conducting pathways at ambient conditions. The aza centers act as the point for charge carrier doping as evident from the photoconductivity and electrical conductivity results.

The critical dimension of semiconductor devices is approaching the single-nm regime, and a variety of practical devices of this scale are targeted for production. Planar structures of nano-devices are still the center of fabrication techniques, which limit further integration of devices into a chip. Extension into 3D space is a promising strategy for future; however, the surface interaction in 3D nanospace make it hard to integrate nanostructures with ultrahigh aspect ratios. Here we report a unique technique using high-energy charged particles to produce free-standing 1D organic nanostructures with high aspect ratios over 100 and controlled number density. Along the straight trajectory of particles penetrating the films of various sublimable organic molecules, 1D nanowires were formed with approximately 10~15 nm thickness and controlled length. An all-dry process was developed to isolate the nanowires, and planar or coaxial heterojunction structures were built into the nanowires. Electrical and structural functions of the developed standing nanowire arrays were investigated, demonstrating the potential of the present ultrathin organic nanowire systems., Extension of nanostructure fabrication in the single-nm regime is a promising but fabrication of nanostructures with high aspect ratios remains challenging. Here, the authors use high energy charged particles to produce free-standing 1D organic nanostructures with extremely high aspect ratios and controlled number density.

Ultrafast electronic-phase change in solids by light, called photoinduced phase transition, is a central issue in the field of non-equilibrium quantum physics, which has been developed very recently. In most of those phenomena, charge or spin orders in an original phase are melted by photocarrier generations, while an ordered state is usually difficult to be created from a non-ordered state by a photoexcitation. Here, we demonstrate that a strong terahertz electric-field pulse changes a Mott insulator of an organic molecular compound in κ-(ET)2Cu[N(CN)2]Cl (ET = bis(ethylenedithio)tetrathiafulvalene), to a macroscopically polarized charge-order state; herein, electronic ferroelectricity is induced by the collective intermolecular charge transfers in each dimer. In contrast, in an isostructural compound, κ-(ET)2Cu2(CN)3, which shows the spin-liquid state at low temperatures, a similar polar charge order is not stabilized by the same terahertz pulse. From the comparative studies of terahertz-field-induced second-harmonic-generation and reflectivity changes in the two compounds, we suggest the possibility that a coupling of charge and spin degrees of freedom would play important roles in the stabilization of polar charge order., Photoinduced phase transition is a central issue in the field of non-equilibrium quantum physics. Here, the authors demonstrate that a terahertz electric-field pulse changes a Mott insulator of an organic molecular compound to a macroscopically polarized charge-order state.

Summary Grain-boundary engineering is pivotal to fully utilize the mechanical, electrical, and thermal-transport properties of various materials. However, current methods in metallurgy rely almost exclusively on top-down approaches, making precise grain-boundary engineering, especially at nanoscale, difficult to achieve. Herein, we report a method to produce tailored grain-boundary conditions with nanoscale precision from colloidal metal nanocrystals through surface treatment followed by a pressure-sintering process. The resulting bulk grain-boundary materials (which we call “nanocrystal coins”) possess a metal-like appearance and conductivity while inheriting the original domain features of the nanocrystal building blocks. Nanoindentation measurements confirmed the superior mechanical hardness of the obtained materials. Further, we use this method to fabricate, for the first time, a single-component bulk metallic glass from amorphous palladium nanoparticles. Our discovery may spur the development of new materials whose functionality crucially depends on the domain configuration at nanoscale, such as superhard materials, thermoelectric generators, and functional electrodes.

The chiral-induced spin selectivity effect enables the application of chiral organic materials for spintronics and spin-dependent electrochemical applications. It is demonstrated on various chiral monolayers, in which their conversion efficiency is limited. On the other hand, relatively high spin polarization (SP) is observed on bulk chiral materials; however, their poor electronic conductivities limit their application. Here, the design of chiral MoS

Four donor–acceptor (D–A) type organic semiconductors, consisting of 5-hexylthiophene with thiophene/furan flanked benzothiadiazole/naphthothiadiazole, were investigated for organic field effect transistor (OFET) application. Despite being an analogue of thiophene, furan has received less attention in organic electronics due to its dissimilar properties to thiophene and instability in photochemical oxidation. Nevertheless, this study determines that furan could display comparable charge transport properties to its analogue. The extension of the electron-accepting thiadiazole core with the benzo group and different heteroatom flanking groups were investigated to show that the performance of OFETs is dependent on the molecular orbital, geometry, and packing. Bottom-gate bottom-contact device configuration was used to study the OFET transport properties of all the molecules. We successfully proved that a furan unit is a promising building block with a mobility (μmax) of 0.0122 cm2 V−1 s−1 for devices employing furan-substituted benzothiadiazole as the channel layer.

We investigate the effect of strong electronic correlation on the massless Dirac fermion system, $\alpha$-(BEDT-TTF)$_2$I$_3$, under pressure. In this organic salt, one can control the electronic correlation by changing pressure and access the quantum critical point between the massless Dirac fermion phase and the charge ordering phase. We theoretically study the electronic structure of this system by applying the slave-rotor theory and find that the Fermi velocity decreases without creating a mass gap upon approaching the quantum critical point from the massless Dirac fermion phase. We show that the pressure-dependence of the Fermi velocity is in good quantitative agreement with the results of the experiment where the Fermi velocity is determined by the analysis of the Shubnikov-de Haas oscillations in the doped samples. Our result implies that the massless Dirac fermion system exhibits a quantum phase transition without creating a mass gap even in the presence of strong electronic correlations., Comment: 5 pages, 4 figures

Chirality-induced spin transport phenomena are investigated at room temperature without magnetic fields in a monoaxial chiral dichalcogenide CrNb_{3}S_{6}. We found that spin polarization occurs in these chiral bulk crystals under a charge current flowing along the principal c axis. Such phenomena are detected as an inverse spin Hall signal which is induced on the detection electrode that absorbs polarized spin from the chiral crystal. The inverse response is observed when applying the charge current into the detection electrode. The signal sign reverses in the device with the opposite chirality. Furthermore, the spin signals are found over micrometer length scales in a nonlocal configuration. Such a robust generation and protection of the spin-polarized state is discussed based on a one-dimensional model with an antisymmetric spin-orbit coupling.

We prepared 2 types of crosslinked liquid-crystalline polymers (CLCPs) (polyacrylates) with the same side-chain length but a different position of an azobenzene moiety in the side chain. We...

We have employed 1,7-dibromo-N,N’-ditridecyl-3,4,9,10-perylenetetra carboxylic diimide (DB-PTCDI-C13) for the development of novel n-type monolayer field-effect-transistor (FET). Functionalization of PTCDI core with long alkyl chain and bulky bromine atoms improved the solubility and made n-type monolayer FET performance possible via solution deposition processes. Annealing effect of spin coated films and drop casted films have been discussed. Liquid crystalline phase of DB-PTCDI-C13 turned out to be playing an important role in controlling the film quality and mobility. The highest mobility was 5.8 × 10−3 cm2 V−1 s−1 after annealing, of which device has been then tested for doping by potassium.

The ability to manipulate the behavior of electrons at organic–inorganic interfaces is of crucial importance in the development of future molecular devices. It has been shown that interface dipoles, created by the chemisorption of a self-assembled organic monolayer (SAM) on a solid surface, induce carrier injection effects. This means that the interface electronic properties can be manipulated by designing the molecular dipoles and arrangements in the SAMs. In this study, a novel strategy to photo-control molecular dipoles through the use of photochromic SAMs is proposed, and a number of photo-controllable molecular devices have been developed based on this strategy. This account provides a review of the basic concept of the photo-control of interface dipoles and the recent advances in the development of photo-controllable molecular devices.

Self-assembled monolayer FET based on a TTF derivative is described (FET = field-effect-transistor, TTF = tetrathiafulvalene). The molecule is anchored on an alumina dielectric layer through covalent bonding of a phosphonic acid linker. A p-type monolayer FET device is achieved and subsequent chemical doping of this monolayer with F4TCNQ dopants results in an ambipolar device. (F4TCNQ = 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane) Several strange behaviors including a gate voltage shift upon doping seem to be consistent with organic monolayer Mott FET. Finally, temperature dependence of the FET performance, which also fit the anticipated Mott FET behavior, is discussed.

The transition of a Mott insulator to metal, the Mott transition, can occur via carrier doping by elemental substitution, and by photoirradiation, as observed in transition-metal compounds and in organic materials. Here, we show that the application of a strong electric field can induce a Mott transition by a new pathway, namely through impulsive dielectric breakdown. Irradiation of a terahertz electric-field pulse on an ET-based compound, κ-(ET)

Artificial molecular switches and machines that enable the directional movements of molecular components by external stimuli have undergone rapid advances over the past several decades. Particularly, overcrowded alkene-based artificial molecular motors are highly attractive from the viewpoint of chirality switching during rotational steps. However, the integration of these molecular switches into solid-state devices is still challenging. Herein, we present an example of a solid-state spin-filtering device that can switch the spin polarization direction by light irradiation or thermal treatment. This device utilizes the chirality inversion of molecular motors as a light-driven reconfigurable spin filter owing to the chiral-induced spin selectivity effect. Through this device, we found that the flexibility at the molecular scale is essential for the electrodes in solid-state devices using molecular machines. The present results are beneficial to the development of solid-state functionalities emerging from nanosized motions of molecular switches., The chirality provides new route for organic materials to be implemented in the spintronics applications. Here the authors show a solid-state spin-filtering device in an organic spin-valve structure enabled by light irradiation induced change in the chirality of molecule.

This paper describes basic characteristics of the quartz crystal sensor with interdigitated electrodes (IDE quartz crystal sensor) which is for simultaneous monitoring of mass, viscosity, conductivity and dielectric changes of liquids or thin films. As the IDE quartz crystal sensor has three terminals for a pair of IDEs on the one side and a counter electrode on the other side, the resonance properties have been analyzed using the electrical equivalent circuit models and measured experimentally for all connecting types of electrode pairs. The IDE quartz crystal has shown clear resonance curves for calculating the resonance frequency and resonance resistance values as well as normal quartz crystal in the air and in contact with liquid. Small shifts in the resonance frequency and resonance resistance depending on the connecting types have been obtained and analyzed using the equivalent circuit models. We have found the integrated quartz crystal and IDE sensors could be monitored simultaneously by only one impedance analyzer. Finally, two types of measuring systems have been demonstrated for continuous measuring methods.

Sample miniaturization has been recognized to be helpful in obtaining deeply supercooled liquids or metastable crystalline solids. Here, the authors generalize the idea of the size effect with phenomenological simulations, and show that it certainly works in two distinct correlated electron systems. Because the validity of the size effects does not rely on microscopic details of each material, they are expected to be applicable to other correlated electron systems, potentially facilitating the creation of metastable electronic states.

Light switch for superconductivity The conducting properties of materials sensitively depend on the available carrier concentration. Physicists can vary this concentration by inducing carriers in the material; for example, by placing it next to an ionic liquid in an electric field. Suda et al. instead used a layer of the molecule spiropyran, which changes from a non-ionic to an ionic form when it is irradiated by ultraviolet (UV) light. The authors placed the layer on top of a thin crystal of an organic material. When they shone UV light on the spiropyran, the adjacent material became superconducting, thanks to the carriers induced at the interface. Science , this issue p. 743

Stimulated by the discovery of high-temperature superconductivity in 1986, band-filling control of strongly correlated electron systems has been a persistent challenge over the past three decades in condensed matter science. In particular, recent efforts have been focused on electrostatic carrier doping of these materials, utilising field-effect transistor (FET) structures to find novel superconductivity. Our group found the first field-induced superconductivity in an organic-based material in 2013 and has been developing various types of superconducting organic FETs. In this perspective, we summarise our recent results on the development of novel superconducting organic FETs. In addition, this perspective describes novel functionality of superconducting FETs, such as strain- and light-responsivity. We believe that the techniques and knowledge described here will contribute to advances in future superconducting electronics as well as the understanding of superconductivity in strongly correlated electron systems.

International audience; We report experimental measurements and theoretical analysis of Shubnikov-de Haas (SdH) oscillations in a Dirac cone system: the α-(BEDT-TTF)2I3 organic metal under hydrostatic pressure. The measured SdH oscillations reveal anomalies at high magnetic fields B where the 1/B oscillations periodicity is lost above 7 T. We interpret these unusual results within a theoretical model that takes into account intrinsic distortions of the α-(BEDT-TTF)2I3 Dirac cones such as a parabolic particle-hole asymmetric correction. Others possible causes, such as a cone tilting or a Zeeman effect, are carefully ruled out. The observations are consistent among α-(BEDT-TTF)2I3 samples with different Fermi levels.

We present the carrier transport properties in the vicinity of a doping-driven Mott transition observed at a field-effect transistor (FET) channel using a single crystal of the typical two-dimensional organic Mott insulator $\kappa$-(BEDT-TTF)$_2$CuN(CN)$_2$Cl ($\kappa$-Cl).The FET shows a continuous metal$-$insulator transition (MIT) as electrostatic doping proceeds. The phase transition appears to involve two-step crossovers, one in Hall measurement and the other in conductivity measurement. The crossover in conductivity occurs around the conductance quantum $e^2/h$ , and hence is not associated with "bad metal" behavior, which is in stark contrast to the MIT in half-filled organic Mott insulators or that in doped inorganic Mott insulators. Through in-depth scaling analysis of the conductivity, it is found that the above carrier transport properties in the vicinity of the MIT can be described by a high-temperature Mott quantum critical crossover, which is theoretically argued to be a ubiquitous feature of various types of Mott transitions. [This document is the unedited Authors' version of a Submitted Work that was subsequently accepted for publication in Nano Letters, copyright \copyright American Chemical Society after peer review. To access the final edited and published work see http://dx.doi.org/10.1021/acs.nanolett.6b03817], Comment: 40 pages, 16 figures in Nano Letters, ASAP (2017)

The presence of interface dipoles in self-assembled monolayers (SAMs) gives rise to electric-field effects at the device interfaces. SAMs of spiropyran derivatives can be used as photoactive interface dipole layer in field-effect transistors because the photochromism of spiropyrans involves a large dipole moment switching. Recently, light-induced p-type superconductivity in an organic Mott insulator, κ-(BEDT-TTF)2 Cu[N(CN)2 ]Br (κ-Br: BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene) has been realized, thanks to the hole carriers induced by significant interface dipole variation in the spiropyran-SAM. This report explores the converse situation by designing a new type of spiropyran monolayer in which light-induced electron-doping into κ-Br and accompanying n-type superconducting transition have been observed. These results open new possibilities for novel electronics utilizing a photoactive SAMs, which can design not only the magnitude but also the direction of photoinduced electric-fields at the device interfaces.

Water-dispersible biotin-modified biofunctional ferromagnetic L1o FePt nanoparticles (NPs) have been synthesized by using a silica nanoreactor strategy. The coercivity field of the NPs was 16 kOe a...

Superconducting (SC) devices are attracting renewed attention as the demands for quantum-information processing, meteorology, and sensing become advanced. The SC field-effect transistor (FET) is one of the elements that can control the SC state, but its variety is still limited. Superconductors at the strong-coupling limit tend to require a higher carrier density when the critical temperature (TC ) becomes higher. Therefore, field-effect control of superconductivity by a solid gate dielectric has been limited only to low temperatures. However, recent efforts have resulted in achieving n-type and p-type SC FETs based on organic superconductors whose TC exceed liquid He temperature (4.2 K). Here, a novel "ambipolar" SC FET operating at normally OFF mode with TC of around 6 K is reported. Although this is the second example of an SC FET with such an operation mode, the operation temperature exceeds that of the first example, or magic-angle twisted-bilayer graphene that operates at around 1 K. Because the superconductivity in this SC FET is of unconventional type, the performance of the present device will contribute not only to fabricating SC circuits, but also to elucidating phase transitions of strongly correlated electron systems.

Three novel N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,3-diaminopropane dimeric lanthanide complexes, namely, [{H2L}Sm(NO3)3]2·H2O (1), [{H2L}Gd(NO3)3]4·CH3OH (2), [{H2L}Lu(NO3)3]4·H2O (3) (H2L = N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,3-diaminopropane) and three new N,N′-bis(2-hydroxy-3-methoxybenzylidene)-1,3-diaminopropane 3d-Gd heterodinuclear complexes, namely, [{LCo}(CH3COO)(CH3COOH)Gd(NO3)2] (4), [{LNi(MeOH)2}Gd(NO3)3]·2MeOH (5) and [{(L)Zn(HNO3)}Gd(NO3)3]·NO3·H3O·MeOH (6) have been synthesized and isolated. X-ray crystallographical analysis reveals that complexes 1–3 are isomorphic with unique dimeric topology. Complexes 4–6 are of discrete 3d–4f dinuclear cores. Magnetic properties of complexes 2 and 4–6 are systematically investigated. Complexes 4 and 5 are ferromagnetic, while 2 and 6 are antiferromagnetic.

Cholesterol is reportedly abundant in the endocrine secretory granule (SG) membrane. In this study, we examined the involvement of cholesterol biosynthesis intermediates and inhibitors in insulin secretion and SG formation mechanisms. There are two routes for the supply of cholesterol to the cells: one via de novo biosynthesis and the other via low-density lipoprotein receptor-mediated endocytosis. We found that insulin secretion and content are diminished by β-hydroxy-β-methylglutaryl-coenzyme A inhibitor lovastatin but not by lipoprotein depletion from the culture medium in MIN6 β-cells. Cholesterol biosynthesis intermediates mevalonate, squalene, and geranylgeranyl pyrophosphate enhanced glucose-stimulated insulin secretion, and the former two increased insulin content. The glucose-stimulated insulin secretion-enhancing effect of geranylgeranyl pyrophosphate was also confirmed in perifusion with rat islets. Morphologically, mevalonate and squalene increased the population of SGs without affecting their size. In contrast, lovastatin increased the SG size with reduction of insulin-accumulating dense cores, leading to a decrease in insulin content. Furthermore, insulin was secreted in a constitutive manner, indicating disruption of regulated insulin secretion. Because secretogranin III, a cholesterol-binding SG-residential granin-family protein, coincides with SG localization based on the cholesterol composition, secretogranin III may be associated with insulin-accumulating mechanisms. Although the SG membrane exhibits a high cholesterol composition, we could not find detergent-resistant membrane regions using a lipid raft-residential protein flotillin and a fluorescent cholesterol-Si-pyrene probe as markers on a sucrose-density gradient fractionation. We suggest that the high cholesterol composition of SG membrane with 40–50 mol% is crucial for insulin secretion and SG formation functions.

Three Salen-like gadolinium complexes, namely, mononuclear (4f) complex [{H2L}Gd(NO3)3] (1), heterodinuclear (3d–4f) complex [{LCu}Gd(NO3)3]·0.25H2O (2) and dimeric heterotrinuclear (3d–4f–3d′) complex [{LCu}Gd(H2O)3{Fe(CN)6}]2·6H2O (3) [H2L = N,N′-ethylene-bis(3-methoxysalicylideneimine)] have been synthesized by stepwise reactions. X-ray diffraction analysis reveals that 1 is of a discrete structure in which H2L coordinates to gadolinium ion through O2O2 moiety. Then, addition of Cu(Ac)2·H2O to the mononuclear lanthanide complex yields expected heterodinuclear (3d–4f) complexes [{LCu}Gd(NO3)3]. 3 features a unique 1D ladder-like topology structure through the intermolecular double links of Cu–N bonds. The measurement of variable-temperature magnetic susceptibility reveals that complex 1 exhibits antiferromagnetic interaction while 2 and 3 exhibit ferromagnetic interaction between spin carriers. The correlations between the structure and magnetism are described and discussed.

Two lanthanide-containing 2D coordination polymers, [Ln(H2salen)1.5(NO3)3]n [H2salen = N,N′- ethylenebis(salicylideneimine); Ln = Gd (1), Dy (2)], have been prepared by self-assembly method. The molecular magnetism and luminescence of the metal complexes had been studied. Complex 1 exhibits antiferromagnetic interaction between spin carriers. Complex 2 emits the H2salen ligand luminescence.

Phase transitions show large responses in physical properties including electrical conductivity changes caused by thermodynamic parameter control or by external stimuli. Thus, an element that shows electronic phase changes in response to input signal may help to provide efficient electronic devices. Strongly correlated electron systems such as Mott insulators are promising candidates for this purpose because they exhibit a large number of electronic phase transitions. Recently, much progress has been made in phase-transition transistors based on organic Mott insulators. In this paper, we review organic transistors that exhibit an insulator-to-metal or an insulator-to-superconductor transition induced by external stimuli such as electric fields, strain, and light.

Treatments of p-ferrocenylbenzoate [p-NaOOCH4C6Fc, Fc=(η5-C5H5)Fe(η5-C5H4)] with Ln(NO3)3·nH2O afford seven p-ferrocenylbenzoate lanthanide complexes {[Ln(OOCH4C6Fc)2(μ2-OOCH4C6Fc)2(H2O)2](H3O)}n [Ln=Ce (1), Pr (2), Sm (3), Eu (4), Gd (5), Tb (6) and Dy (7)]. X-ray crystallographic analysis reveals that the isomorphous complexes {[Ce(OOCH4C6Fc)2(μ2-OOCH4C6Fc)2(H2O)2](H3O)}n (1) and {[Pr(OOCH4C6Fc)2(μ2-OOCH4C6Fc)2(H2O)2](H3O)}n (2) form a unique 1D double-bridged infinite chain structure bridged by μ2-OOCH4C6Fc groups. Each Ln(III) ion adopts a dodecahedron coordination environment with eight coordinated oxygen atoms from two terminal monodentate coordinated FcC6H4COO− units, two terminal monodentate coordinated H2O molecules and four μ2-−OOCH4C6Fc units. The luminescent spectra reveal that only 4 and 6 exhibit characteristic emissions of lanthanide ions, Eu(III) and Tb(III) ions, respectively. The variable-temperature magnetic properties of 5 and 7 suggest that a ferromagnetic coupling between spin carriers may exist in 5.

We have observed size-reduction induced ferromagnetism and significant photo-magnetic effects in azobezene-thiol-modified gold nanoparticles. When the particle size was reduced to 1.7 nm, ferromagnetism even at room temperature was observed while diamagnetism was dominating with the particle size of 5.0 nm. Furthermore, reducing the particles size to 1.7 nm also gave rise to photo-magnetic properties because the decrease in particle size provided free volume between each of the azobenzene ligands. This photo-magnetic effect could be attributed to photo-induced changes in the values of d-charge losses due to the photoisomerization of azo-ligands, which were accompanied by the inversion of surface dipole values to the opposite sign.

Geordnete Verhaltnisse: Assoziate ferromagnetischer FePt-Nanopartikel mit groser senkrechter magnetischer Anisotropie wurden durch magnetfeldgestutzte schichtweise Abscheidung erhalten, und anschliesend wurden geschichtete Filme aus L10-FePt-Nanopartikeln und organischen Polymeren hergestellt. Diese Filme werden bei der Verwendung photochromer Molekule als Polymerschichten photodurchstimmbar.

Granin-family proteins, including chromogranin A and secretogranin III, are sorted to the secretory granules in neuroendocrine cells. We previously demonstrated that secretogranin III binds chromogranin A and targets it to the secretory granules in pituitary corticotrope-derived AtT-20 cells. However, secretogranin III has not been identified in adrenal chromaffin and PC12 cells, where chromogranin A is correctly sorted to the secretory granules. In this study, low levels of a large and noncleaved secretogranin III have been identified in PC12 cells and rat adrenal glands. Although the secretogranin III expression was limited in PC12 cells, when the FLAG-tagged secretogranin III lacking the secretory granule membrane-binding domain was expressed excessively, hemagglutinin-tagged chromogranin A was unable to target to the secretory granules at the tips and shifted to the constitutive secretory pathway. Secretogranin III was able to bind the aggregated form of chromogranin A, suggesting that a small quantity of secretogranin III is enough to carry a large quantity of chromogranin A. Furthermore, secretogranin III bound adrenomedullin, a major peptide hormone in chromaffin cells. Indeed, small interfering RNA-directed secretogranin III depletion impaired intracellular retention of chromogranin A and adrenomedullin, suggesting that they are constitutively released to the medium. We suggest that the sorting function of secretogranin III for chromogranin A is common in PC12 and chromaffin cells as well as in other endocrine cells, and a small amount of secretogranin III is able to sort chromogranin A aggregates together with adrenomedullin to secretory granules.

The behavior of plasma-induced defects deactivating Si donors in GaN has been studied by using Schottky diodes with the UV illumination. It is interesting that the UV irradiating for the deactivated GaN leads to an enhancement of reactivation of the donors even at room temperature. It is found that the donor-deactivated region in n-GaN shifts toward the bulk region with increasing the illumination time. The effect of the UV illumination is thought to be the direct photodissociation of the donor-defect complexes or the injection of holes as a minority carrier. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

In electronic-type ferroelectrics, where dipole moments produced by the variations of electron configurations are aligned, the polarization is expected to be rapidly controlled by electric fields. Such a feature can be used for high-speed electric-switching and memory devices. Electronic-type ferroelectrics include charge degrees of freedom, so that they are sometimes conductive, complicating dielectric measurements. This makes difficult the exploration of electronic-type ferroelectrics and the understanding of their ferroelectric nature. Here, we show unambiguous evidence for electronic ferroelectricity in the charge-order (CO) phase of a prototypical ET-based molecular compound, α-(ET)2I3 (ET:bis(ethylenedithio)tetrathiafulvalene), using a terahertz pulse as an external electric field. Terahertz-pump second-harmonic-generation(SHG)-probe and optical-reflectivity-probe spectroscopy reveal that the ferroelectric polarization originates from intermolecular charge transfers and is inclined 27° from the horizontal CO stripe. These features are qualitatively reproduced by the density-functional-theory calculation. After sub-picosecond polarization modulation by terahertz fields, prominent oscillations appear in the reflectivity but not in the SHG-probe results, suggesting that the CO is coupled with molecular displacements, while the ferroelectricity is electronic in nature. The results presented here demonstrate that terahertz-pump optical-probe spectroscopy is a powerful tool not only for rapidly controlling polarizations, but also for clarifying the mechanisms of ferroelectricity.

Electric double layers (EDLs) of ionic liquids have been used in superconducting field-effect transistors as nanogap capacitors. Because of the freezing of the ionic motion below ~200 kelvin, modulations of the carrier density have been limited to the high-temperature regime. Here we observe carrier-doping-induced superconductivity in an organic Mott insulator with a photoinduced EDL based on a photochromic spiropyran monolayer. Because the spiropyran can isomerize reversibly between nonionic and zwitterionic isomers through photochemical processes, two distinct built-in electric fields can modulate the carrier density even at cryogenic conditions.

Neuroendocrine cells contain two types of secretagogue-regulated acidic compartments: secretory granules (SGs) and synaptic-like microvesicles (SLMVs), which can be identified by acidotropic probes such as acridine orange (AO) and DAMP. We investigated the accumulation of these probes in SGs and SLMVs as a function of glucose levels in the culture media using a pancreatic β-cell line MIN6. AO was accumulated in the low-glucose condition, but not in the high-glucose condition. The AO accumulation correlated well with the SLMV dynamics by glucose and DAMP was localized in the SGs. Because SG membranes are reportedly high in cholesterol, we prepared liposomes with increasing cholesterol levels. AO is well incorporated into liposomes having a 20 to 40 mol% cholesterol composition, whereas DAMP was so in those having over 40 mol% cholesterol levels. Indeed, when cholesterol was depleted from MIN6 SG membranes, DAMP incorporation decreased, instead AO was incorporated. In PC12 cells, AO incorporation into SGs was significant but DAMP incorporation was limited. Consistently, the cholesterol composition was found 37 to 39 mol% in the SG membrane of PC12 cells. We suggest that cholesterol-sensing probes, AO and DAMP, are useful tools for investigating cholesterol compositions in acidic organelle membranes.

Granin-family proteins, including chromogranin A (CgA) and secretogranin III (SgIII), are transported to secretory granules (SGs) in neuroendocrine cells. We previously showed that SgIII binds strongly to CgA in an intragranular milieu and targets CgA to SGs in pituitary and pancreatic endocrine cells. In this study, we demonstrated that with a sucrose density gradient of rat insulinoma-derived INS-1 cell homogenates, SgIII was localized to the SG fraction and was fractionated to the SG membrane (SGM) despite lacking the transmembrane region. With depletion of cholesterol from the SGM using methyl-beta-cyclodextrin, SgIII was impaired to bind to the SGM. Both SgIII and CgA were solubilized from the SGM by Triton X-100 in contrast to the Triton X-100 insolubility of carboxypeptidase E. SgIII and carboxypeptidase E strongly bound to the SGM-type liposome in intragranular conditions, but CgA did not. Instead, CgA bound to the SGM-type liposome only in the presence of SgIII. Immunocytochemical and pulse-chase experiments revealed that SgIII deleting the N-terminal lipid-binding region missorted to the constitutive pathway in mouse corticotroph-derived AtT-20 cells. Thus, we suggest that SgIII directly binds to cholesterol components of the SGM and targets CgA to SGs in pituitary and pancreatic endocrine cells.