Roles of SiH4 and SiF4 in growth and structural changes of poly-Si films

The structural properties of polycrystalline silicon films, prepared by plasma enhanced chemical vapor deposition system, with different flow rates of SiH₄/SiF₄ mixtures at 300 °C were investigated. This study indicates that the low hydrogen coverage on the growing surface, under optimum fluorine radicals, will be leaded to an improvement of crystallized area as compared with case of high hydrogen coverage surface. Moreover, the studies of the role of SiH₄ and SiF₄ radicals show that the SiH₄ radicals are important in the nucleation and growth of grains. However, SiF₄ radicals are effective in the structural change of grain boundaries regions and by this way, in the present system, establish the growth of grains under the dominant 〈1 1 0〉 direction. The stress investigation indicates that addition of high flow rate of SiF₄ in amorphous film, results in the nearly stress free films. Finally, we found that the changes in g-value reflect the changes in the intrinsic compressive and tensile stress in the both polycrystalline and amorphous silicon films.     

Synthesis of endogenous sperm-activating and attracting factor isolated from ascidian Ciona intestinalis

A chemoattractant candidate named sperm-activating and attracting factor (SAAF) from the eggs of ascidian Ciona intestinalis, was synthesized from chenodeoxycholic acid in 16 steps. The present synthesis led to the unambiguous structure determination of SAAF to be (3R,4R,7R,25S)-3,4,7,26-tetrahydroxycholestane-3,26-disulfate. The synthetic pure specimen was also used to confirm the dual sperm-activating and attracting activity.     

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.     

Symmetry-Breaking Phenomena in an Optimization Problem for some Nonlinear Elliptic Equation

Let $\Omega$ be a bounded domain in ${\bf R^n}$ with Lipschitz boundary, $\lambda >0,$ and $1\le p \le (n+2)/(n-2)$ if $n\ge 3$ and $1\le p< +\infty$ if $n=1,2$. Let $D$ be a measurable subset of $\Omega$ which belongs to the class $ {\cal C}_{\beta}=\{D\subset \Omega \quad | \quad |D|=\beta\} $ for the prescribed $\beta\in (0, |\Omega|).$ For any $D\in{\cal C}_{\beta}$, it is well known that there exists a unique global minimizer $u\in H^1_0(\Omega)$, which we denote by $u_D$, of the functional \[\quad J_{\Omega,D}(v)=\frac12\int_{\Omega}|\nabla v|^2\, dx+\frac{\lambda}{p+1}\int_{\Omega}|v|^{p+1}\, dx -\int_{\Omega}\chi_Dv\,dx \] on $H^1_0(\Omega)$. We consider the optimization problem $ E_{\beta,\Omega}=\inf_{D\in {\cal C}_{\beta}} J_D(u_D) $ and say that a subset $D^*\in {\cal C}_{\beta}$ which attains $E_{\beta,\Omega}$ is an optimal configuration to this problem. In this paper we show the existence, uniqueness and non-uniqueness, and symmetry-preserving and symmetry-breaking phenomena of the optimal configuration $D^*$ to this optimization problem in various settings.     

The color reactions of sulfonazo-III isomers with lanthanum and alkaline earth metal ions

Six sulfonazo-III isomers were synthesized, and their color reactions with alkaline earth metals and lanthanum investigated. All six reagents had good sensitivities for lanthanum (? = 1.9–5.0·10⁴), but the sensitivities for alkaline earth metals were fairly low except for the barium chelate of sulfonazo-III (? = 2.8 · 10⁴). The position of the sulfo group on the phenyl ring and the symmetry of the reagent are important for the barium reactions, but of little significance for the lanthanum reactions. The effects of water-miscible solvents are also described.     

Self-aggregation of synthetic zinc oxo-bacteriochlorins bearing substituents characteristic of chlorosomal chlorophylls

We prepared novel zinc 8-ethyl-8-methyl-7-oxo- and 7-ethyl-7-methyl-8-oxo-bacteriochlorins 1 and 2 possessing substituents characteristic of chlorosomal chlorophylls, exclusively observed in extramembraneous light-harvesting antennas of photosynthetic green bacteria. The electronic absorption spectra of monomeric 1 and 2 in THF were obviously different: the Q(y) maximum of the former was 724 and that of the latter was 683 nm. This observed spectral difference was clearly explained by theoretical ZINDO/S calculation of their energetically minimized molecules. The optical properties of monomeric 1/2 were controlled by the electronic effect of the 7/8-oxo groups. Specific spectral changes in the electronic, CD, and FT-IR absorption spectra by dilution of the monomeric THF solutions of 1/2 with a 100/200-fold volume of cyclohexane showed the formation of chlorosomal self-aggregation species constructed by 13-C=O...H-O(3(1))...Zn and pi-pi stacking. Especially, the red-shift values in the Q(y) band of 1/2 by self-aggregation were 2450/1970 cm(-1), indicating that exciton interaction among the composite molecules in the self-aggregation of 1 was stronger than in those of 2. Molecular model calculations for dodecamers of 1/2 based on a parallel chain arrangement gave partially different supramolecular structures; the specific hydrogen-bonding distances in 2-dodecamer were larger than those of 1-dodecamer, while both coordinations gave the same Zn-O distance. These modeling results showed that 1 was more tightly packed in the self-aggregates to give a larger red-shift value in the Q(y) band by self-aggregation than 2. The difference in the supramolecular structures is mainly ascribable to the steric effect of 8/7-dialkyl groups in self-aggregates of 1/2.     

Amphotericin B covalent dimers forming sterol-dependent ion-permeable membrane channels

Polyenemacrolides such as amphotericin B (AmB) were thought to assemble together and form an ion channel across plasma membranes. Their antimicrobial activity has been accounted for by this assemblage, whose stability and activity are dependent on sterol constituents of lipid bilayer membranes. The structure of this channel-like assemblage formed in biomembranes has been a target of extensive investigations for a long time. For the first step to this goal, we prepared several AmB dimers with various linkers and tested for their channel-forming activity. Among these, AmB dimers that bore an aminoalkyl-dicarboxylate tether covalently linked between amino groups of AmB showed potent hemolytic activity. Furthermore, K+ influx actions monitored by measuring the pH of the liposome lumen by 31P NMR revealed that the dimers formed the molecular assemblage similar to that of AmB in phospholipid membrane. Judging from changes in 31P NMR spectra, the dimers appeared to induce "all-or-none"-type ion flux across the liposome membrane in the presence of ergosterol, which suggested that the ion channel formed by ergosterol/dimer is similar to that of AmB. With these data in hand, we are now trying to elucidate the structure of the ion-channel complex by making the labeled conjugates of AmB for NMR measurements.     

Mycosamine orientation of amphotericin B controlling interaction with ergosterol: sterol-dependent activity of conformation-restricted derivatives with an amino-carbonyl bridge

Amphotericin B (AmB 1) is known to assemble together and form an ion channel across biomembranes. The antibiotic consists of mycosamine and macrolactone moieties, whose relative geometry is speculated to be determinant for the drug's channel activity and sterol selectivity. To better understand the relationship between the amino-sugar orientation and drug's activity, we prepared conformation-restricted derivatives 2-4, in which the amino and carboxyl groups were bridged together with various lengths of alkyl chains. K+ influx assays across the lipid-bilayer membrane revealed that ergosterol selectivity was markedly different among derivatives; short-bridged derivative 2 almost lost the selectivity, while 3 showed higher ergosterol preference than AmB itself. Monte Carlo conformational analysis of 2-4 based on NOE-derived distances indicated that the amino-sugar moiety of 2 comes close to C41 because of the short bridge, whereas those of 3 and 4 are pointing outward. The mutual orientation of the amino-sugar moiety and macrolide ring is so rigid in derivatives 2 and 3 that these conformations should be unchanged upon complex formation in lipid membranes. These results strongly suggest that the large difference in sterol preference between derivatives 2 and 3 is ascribed to the different orientation of amino-sugar moieties. These findings allowed us to propose a simple model accounting for AmB-sterol interactions, in which hydrogen bonding between 2'-OH of AmB and 3beta-OH of ergosterol plays an important role.