Photoluminescence decay dynamics of silver/porous-silicon nanocomposites formed by metal-assisted etching

We investigate the photoluminescence (PL) properties of silver/porous-silicon (Ag/PSi) nanocomposites prepared by metal-assisted etching in ${\mathrm{Ag}}_2\mathrm{O}/\mathrm{HF}$ solution, on the basis of steady-state and time-resolved PL spectroscopy measurements. The PL intensity and peak position are strongly dependent on the ${\mathrm{Ag}}_2\mathrm{O}$ concentration. Time-resolved PL measurements reveal that the nonradiative rate decreases with an increase in the ${\mathrm{Ag}}_2\mathrm{O}$ concentration for the Ag/PSi nanocomposites. It is found from x-ray photoelectron spectroscopy measurements that the decrease in the nonradiative rate is caused by the formation of ${\mathrm{SiO}}_2$ layers on the PSi surfaces. Further, the number of light-emitting Si nanocrystals in the nanocomposites, which is estimated from the PL decay rate and PL intensity, increases with the ${\mathrm{Ag}}_2\mathrm{O}$ concentration. From the wavelength dependence of the PL decay rate, it is found that the nonradiative rate is considerably dispersive, i.e., the shorter the wavelength, the higher the nonradiative rate.     

Synthesis of 4‐Aryl‐1,7‐naphthyridine‐2(1H)‐thiones by the Electrocyclic Reaction of 4‐(1‐Arylalk‐1‐enyl)‐3‐isothiocyanatopyridines Generated in situ from the Corresponding Isocyanides

A convenient synthis for 4‐substituted and 3,4‐disubstituted 1,7‐naphthyridine‐2(1H)‐thiones 7 has been developed. The method is based on the electrocyclic reaction of 4‐(1‐arylalk‐1‐enyl)‐3‐isothiocyanatopyridines 6 , generated in situ by the treatment of the respective isocyanides 5 with S₈ in the presence of a catalytic amount of selenium. The isocyanides 5 can be easily prepared from commercially available pyridin‐3‐amine by conventional organic reactions.     

One‐Pot Synthesis of 4‐Substituted 3,4‐Dihydro‐3‐methoxyisocoumarins via Carboxylation of α‐Substituted 2‐Lithio‐β‐methoxystyrenes with Carbon Dioxide

A new type of isocoumarins (=1H‐isochromen‐1‐ones=1H‐2‐benzopyran‐1‐ones), 4‐substituted 3,4‐dihydro‐3‐methoxyisocoumarins 2 , can be obtained by a one‐pot process from α‐substituted 2‐bromo‐β‐methoxystyrenes 1 . Thus, lithium 2‐(1‐aryl(or methyl)‐2‐methoxyethenyl)benzoates are conveniently generated via the Br/Li exchange between 1 and BuLi, followed by the action of CO₂ on the resulting α‐substituted 2‐lithio‐β‐methoxystyrenes. Upon treating with concentrated HCl at room temperature, these lithium benzoates undergo lactonization to provide the desired 3,4‐dihydroisocoumarins 2 in relatively good yields.     

Charge ordering and carrier generation by air oxidation of a nickel complex with selenium-containing extended-tetrathiafulvalenedithiolate ligands

The structures and electrical properties of ((n)Bu(4)N)[Ni(dmstfdt)(2)] (1), ((n)Bu(4)N)(2)[Ni(dmstfdt)(2)] (2), and ((n)Bu(4)N)(3)[Ni(dmstfdt)(2)](2) (3), where dmstfdt = extended-tetrathiafulvalenedithiolate ligand, were examined. The fresh crystal of 1 was found to be a Mott insulator, but the crystal gradually became highly conducting because of air oxidation. Compound 3 exhibited a semiconducting charge-ordering state.     

Three-dimensional solution structure of bottromycin A2: a potent antibiotic active against methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococci

The three-dimensional (3D) structure of bottromycin A(2), a natural anti-methicillin-resistant Staphylococcus aureus (MRSA) and anti-vancomycin-resistant Enterococci (VRE) agent consisting of seven amino acids, has been investigated through NMR spectroscopy. On the basis of 57 experimental constraints, a total of 34 converged structures were obtained. The average pairwise atomic root mean square difference is 0.74±0.59 ? for all heavy atoms. The resulting structure indicates an interesting feature in that the three C-terminal residues of bottromycin A(2) fold back on the 12-membered cyclic skeleton made by the four N-terminal residues. Thus, MePro(2) and Thia-β-Ala-OMe(7), modification of which significantly affects the antibacterial activities of bottromycin A(2), are located on one side of its 3D structure. These distinct structural features might be important for the binding of bottromycin A(2) with the bacterial ribosome.     

Particle Monte Carlo simulation of string-like colloidal assembly in two and three dimensions

We simulate structural phase behavior of polymer-grafted colloidal particles by molecular Monte Carlo technique. The interparticle potential, which has a finite repulsive square-step outside a rigid core of the colloid, was previously confirmed via numerical self-consistent field calculation. This model potential is purely repulsive. We simulate these model colloids in the canonical ensemble in two and three dimensions and find that these particles containing no interparticle attraction self-assemble and align in a string-like assembly, at low temperature and high density. This string-like colloidal assembly is related to percolation phenomena. Analyzing the cluster size distribution and the average string length, we build phase diagrams and discover that the average string length diverges around the region where the melting transition line and the percolation transition line cross. This result is similar to Ising spin systems, in which the percolation transition line and the order-disorder line meet at a critical point.     

A Novel Synthesis of 4‐Pyridazineacetic Acids via Ring Expansion of N‐Cyanomethylated 3‐Pyrazoline‐4‐acetic Acids

A novel synthetic route to 4‐pyridazineacetic acids 10 – 12 has been achieved by the ring‐expansion reaction of N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 – 9 . 1H‐Pyrazole‐4‐acetic acids 1 – 3 were reacted with iodoacetonitrile in the presence of triethylamine in refluxing acetonitrile to give the corresponding C‐cyanomethylated 1H‐pyrazole‐4‐acetic acids 4 – 6 as major products together with N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 and 8 as minor products. On the other hand, reactions of 1 and 3 with chloroacetonitrile in the presence of triethylamine in refluxing chloroform afforded the corresponding N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 and 9 as major products. Thermal treatment of 7 – 9 with sodium hydride in N,N‐dimethylformamide caused ring expansion to yield the corresponding 4‐pyridazineacetic acids 10 – 12 .     

Critical Role of Spherulite Structure on Behavior of Stabilizers in Poly(propylene) Stabilization

Summary: We found that the spherulite structure of polypropylene (PP) significantly influences the stability of PP by affecting the behavior of stabilizers. Smaller spherulites resulted in more homogeneous dispersion of stabilizers and their slower release into air, so as to elongate the lifetime of PP. Moreover, chemically and physically weak spherulite boundaries were selectively oxidized in the presence of stabilizers. The significance to control higher order structures on the stabilization of PP is reported.     

Mineral composition of frozen taro for determination of geographic origin

The mineral composition of frozen food of taro [Colocasia esculenta (L.) Schott] was analyzed to categorize the geographical production place of taro. The concentrations of Co and H₂PO₄ ⁻ were found to be useful to separate the producing place between Japan and China. The analysis was performed by instrumental neutron activation analysis (INAA) and ion chromatography (IC). In the case of INAA, the samples were dried and sealed in a vinyl bag and irradiated with thermal neutrons from JRR3M, installed at Japan Atomic Energy Agency (JAEA). The activated samples were cooled down for a few weeks and the elements (Co, Cr, Fe, Rb, Zn) were determined. Cobalt concentration of frozen taro from China was higher than that from Japan. The tendency was the same in the fresh sample of taro. When concentration of H₂PO₄ ⁻ of frozen sample was measured, taro from Japanese product was higher than that of Chinese one, contrary to fresh sample. This result might be caused by the leakage of H₂PO₄ ⁻ during freezing process, indicating that we should be careful to apply the discrimination indicators. In addition to Co, there was a significant difference of Rb and Fe concentrations between frozen taro from Japan and China.     

A Chemo-Enzymatic Expeditious Route to Racemic Dihexanoyl (2R*,3R*,4R*)-Dehydroxymethylepoxyquinomycin (DHMEQ), the Precursor for Lipase-Catalyzed Synthesis of the Potent Nuclear Factor-κB Inhibitor, (2S,3S,4S)-DHMEQ

In order to synthesize the potent nuclear factor (NF)-κB inhibitor, (2S,3S,4S)-dehydroxymethylepoxyquinomycin (DHMEQ), in a large scale, a new route for its corresponding racemic precursor, dihexanoyl (2R*,3R*,4R*)-DHMEQ, was developed. By employing both hydroquinone and benzoquinone intermediates, the total yield, reproducibility, and synthetic steps were improved and the synthetic cost was reduced.