Electrical properties and memory effect in the field effect transistor based on organic ferroelectric insulator and pentacene

We have fabricated a field effect transistor (FET) based on an organic ferroelectric insulator and molecular conductor, and investigated the electrical properties and memory effects on the PEN-FET. We have observed a drastic change in the drain current at around the coercive electric fieldE _c of the organic ferroelectric insulator in not only a FET (PEN-FET) based on a pentacene (PEN) film but also a FET (IPEN-FET) based on an iodine doped PEN film. The magnitude of the change of the drain current for the IPEN-FET is 200 times larger than that for the PEN-FET. It is expected from these results that the PEN-FET (especially the IPEN-FET) is an improvement in such devices, since it operates at a low gate electric field accompanied by the appearance of the spontaneous polarization in the organic ferroelectric insulator. In addition, we have found that the drain current for the PEN-FET does not return to the initial drain current ofE _G =0 V/cm for more than one week, even if the gate electric field is changed to 0 V/cm from 500 V/cm(>E _c ). From these results, it is suggested that the PEN-FET becomes a memory device.     

Time-resolved cavity ringdown spectroscopy on nanoparticle generation in a SiH4–H2 VHF plasma

Time-resolved cavity ringdown (τ-CRD) spectroscopy has been applied to monitor the silyl (SiH₃) radicals and nanoparticles in a pulsed very high frequency (VHF) silane-hydrogen plasma under microcrystalline silicon (μc-Si:H) deposition conditions. The measured cavity loss reveals four time intervals (I up to VI) in the first 4 s of the plasma pulse. By variation of the laser wavelength, it is demonstrated that the small cavity loss at 220 nm reflects the SiH₃ absorption in interval I. In intervals II and III, an additional cavity loss appears. This additional cavity loss corresponds to Rayleigh and Mie scattering by growing nanoparticles. Interval IV reflects the loss of nanoparticles between the electrodes during the afterglow of the plasma pulse. The evolution of the nanoparticle generation determined from the τ-CRD measurements are further confirmed by additional scanning electron microscopy analyses on the nanoparticles created in the plasma pulse.     

Microchannel-assisted thermal-lens spectrometry for microchip analysis

We present a new method for homocysteine quantitation in human plasma based on in-capillary reaction of homocysteine with 2,2′-dipyridyl disulfide. Homocysteine is in this so-called thiol-exchange reaction quantitatively transformed in mixed disulfide concomitantly with formation of an equimolar amount of 2-thiopyridone that is further separated by micellar electrokinetic chromatography and determined specifically at 343 nm. The concentration of homocysteine is thus estimated indirectly from the result of 2-thiopyridone determination. The linear detection range for concentration versus peak area for the assay was from 0.03–3 mM (correlation coefficient 0.994) with a detection limit of 6 μM and a limit of quantitation 20 μM. The inter-day reproducibility of the peak area and the migration time were 1.37% and 0.05%, respectively. The method is simple, relatively rapid and can be easily automated. Moreover the common capillary electrophoresis apparatus with a UV detector can be used to distinguish between normal and pathological hyperhomocysteinemia plasma samples.     

The roles of hetero atoms in solvolytic reactions—II: Transannular participation by neighbouring sulphur atom

Esters of sulphur-containing 5- and 6-membered heterocycles, tetrahydro-3- and 4-thiopyranol and their 3- and 4-methyl, phenyl derivatives, and tetrahydro-2-thiophenemethanol, were synthesized. The solvolysis of β-thioesters in 80% aqueous acetone resulted in strong transannular S-participation and the products of solvolysis substantiated formation of bicyclic episulphonium ion intermediates. Such participation is considered to be present even in a tertiary system. On the other hand, γ-thioesters were solvolysed without any transannular S-participation,     

Synthesis and ion selectivity of macrocyclic metacyclophanes analogous to spherand-type calixarenes

Novel macrocyclic compounds, hexahydroxy[1.0.1.0.1.0]- (2b) and octahydroxy[1.0.1.0.1.0.1.0]metacyclophane (2c) have been prepared in 50–70% yield by base-catalyzed condensation of 5,5-di-tert-butyl-2,2-dihydroxybiphenyl (1) with formaldehyde in refluxing xylene. An attempted alkylation of the flexible macrocycles2b and2c with ethyl bromoacetate in the presence of Cs₂CO₃ under acetonitrile reflux gave only one pure stereoisomer3 and4, respectively, while other possible isomers were not observed. The structural characterization of these products is also discussed. The two-phase solvent extraction data indicated that hexaethyl ester3 and octaethyl ester4 show strong metal affinity, comparable with that of the corresponding calix[n]arenes, and a high K⁺ selectivity was observed for octaethyl ester4.¹H-NMR titration of hexaethyl ester3 and octaethyl ester4 with KSCN clearly demonstrate that a 11 complex is formed which is stable on the NMR time scale.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Spectroscopic and Electrochemical Characterization of Cytochrome P450st‐DDAB Films on a Plastic‐Formed Carbon Electrode

We have studied the characterization of thermophilic cytochrome P450 (P450st)‐didodecyldimethylammonium bromide (DDAB) films by using UV‐vis absorption, resonance Raman spectroscopy, and electrochemical methods. The observed Raman spectrum indicated near‐native conformation of the heme iron in DDAB film on the surface of a glass slide, while on the surface of a plastic‐formed carbon (PFC) electrode, the conformation of P450st‐DDAB was very similar to that of heme‐DDAB film, suggesting the release of heme from P450st in DDAB films on PFC electrodes. When NaBr was added as salt to the casting solution, the result of Raman spectrum indicated near‐native conformation of P450st in DDAB film even on the PFC electrode, but no redox potential of P450st which has near native structure was observed. This study suggests the essential experimental conditions when working with heme protein‐DDAB films as, in some cases, heme iron from proteins is released on the surface of the electrode.