Controlling chaos in dynamic-mode atomic force microscope

We successfully demonstrated the first experimental stabilization of irregular and non-periodic cantilever oscillation in the amplitude modulation atomic force microscopy using the time-delayed feedback control. A perturbation to cantilever excitation force stabilized an unstable periodic orbit associated with nonlinear cantilever dynamics. Instead of the typical piezoelectric excitation, the magnetic excitation was used for directly applying control force to the cantilever. The control force also suppressed the cantilever's occasional bouncing motions that caused artifacts on a surface image.     

Determination of REEs in seawater by ICP-MS after on-line preconcentration using a syringe-driven chelating column

A syringe-driven chelating column (SDCC) was applied to develop an on-line preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) method for preconcentration and determination of rare earth elements (REEs) in seawater samples. The present on-line preconcentration system consists of only one pump, two valves, an SDCC, an ICP-MS, several connectors, and Teflon tubes. Optimizations of adsorption pH condition, sample loading flow rate, and integration range were carried out to achieve optimum measurement conditions for REEs in seawater sample. Six minutes was enough for a preconcentration and measurement cycle using 10 mL of seawater sample, where the detection limits for different REEs were in the range of 0.005 pg mL⁻¹ to 0.09 pg mL⁻¹. Analytical results of REEs in a seawater certified reference material (CRM), NASS-5, confirmed the usefulness of the present method. Furthermore, concentrations of REEs in Nikkawa Beach coastal seawater were determined and discussed with shale normalized REE distribution pattern.     

Peripherally Monomial-Preserving Maps between Uniform Algebras

Let and be uniform algebras and p(z,w) = z^mwⁿ a twovariable monomial. We characterize maps T from certain subsets of into such that holds for all f and g in the domain of T; peripherally monomial-preserving maps. Furthermore and are proved to be isometrical isomorphic as Banach algebras. If the greatest common divisor of m and n is 1, then T is extended to an isometrical linear isomorphism; a weighted composition operator. An example of peripherally monomial-preserving surjections between uniform algebras which is not linear, nor multiplicative, nor injective is given when the greatest common divisor is strictly greater than 1. The first, third and fourth authors were partly supported by the Grantsin-Aid for Scientific Research, The Ministry of Education, Science, Sports and Culture, Japan.     

Particle design of three-component system for sustained release using a 4-fluid nozzle spray-drying technique

We prepared composite particles of acetaminophen (Act) with chitosan (Cht) and hydroxypropylmethylcellulose phthalate (HPMCP) as a carrier using a newly developed 4-fluid nozzle spray-dryer. Cht dissolves in acid solutions and forms a gel, but it is insoluble in alkaline solutions. On the other hand, HPMCP is insoluble in acid solutions, but it dissolves in alkaline solutions. Therefore, we tested a preparation of controlled release composite particles using the characteristics of these carriers. Act and Cht mixtures in prescribed ratios were dissolved in an acid solution. Composite particles of Act and HPMCP in prescribed ratios were dissolved in alkaline solutions. We evaluated the composite particles of the three components (Act, Cht, and HPMCP) by preparing solid dispersions using a 4-fluid nozzle spray-dryer. Observation of particle morphology by scanning electron microscopy (SEM) revealed that the particles from the spray-drying process had atomized to several microns and had all become spherical. We investigated the physical properties of the composite particles by powder X-ray diffraction, differential scanning calorimetry, and dissolution rate analysis to clarify the effects of crystallinity on the dissolution rate. Powder X-ray diffraction peaks and the heat of fusion of Act in the spray-dried samples decreased in proportion to the carrier content, indicating that the drug was amorphous. These results indicate that the Act-Cht-HPMCP system formed a solid dispersion. Furthermore, we investigated the interaction between the drug and the carrier using FT-IR analysis. FT-IR spectroscopy of the Act solid dispersions suggested that the Act carbonyl and Cht amino groups formed a hydrogen bond. On the other hand, interaction by hydrogen bond was observed between the carbonyl group of HPMCP with the amino group of Act. In the three-component Act-Cht-HPMCP system, the 4-fluid nozzle spray-dried preparation with a mixing ratio of 1 : 2.5 : 2.5 obtained sustained release preparation in all pH test solutions.     

Novel oxygen chirality induced by asymmetric coordination of an ether oxygen atom to a metal center in a series of sugar-pendant dipicolylamine copperII complexes

Six sugar-pendant 2,2'-dipicolylamine (DPA) ligands (L1-3 and L'1-3) have been prepared. OH-protected and unprotected D-glucose, D-mannose, and D-xylose were attached to a DPA moiety via an O-glycoside linkage. X-ray crystallography of the copper(II) complexes (1-5) with these ligands revealed that the anomeric oxygen atom is coordinated to the metal center in the solid state, generating a chiral center at the oxygen atom. The CD spectra of these copper complexes in methanol or aqueous solution exhibit Cotton effects in the d-d transition region, which indicates that the ether oxygen atoms remain coordinated to the metal center and the oxygen-atom chirality is preserved even in solution. For complexes 1 and 2, the inverted oxygen-atom chirality and chelate-ring conformation in the solid state are well correlated with the mirror-image CD spectra in methanol solution. The concomitant inversion of the asymmetric configuration around the copper center was also observed in a methanol solution of complex 3 and a pyridine solution of complex 2. The square-pyramidal/octahedral copper(II) centers also exhibited characteristic absorption and CD spectra.     

Particle design using a 4-fluid-nozzle spray-drying technique for sustained release of acetaminophen

We prepared matrix particles of acetaminophen (Act) with chitosan (Cht) as a carrier using a newly developed 4-fluid-nozzle spray dryer. Cht dissolves in acid solutions and forms a gel, but it does not dissolve in alkaline solutions. Therefore, we tested the preparation of controlled release matrix particles using the characteristics of this carrier. Act and Cht mixtures in prescribed ratios were dissolved in an acid solution. We evaluated the matrix particles by preparing a solid dispersion using a 4-fluid-nozzle spray dryer. Observation of the particle morphology by scanning electron microscopy (SEM) revealed that the particles from the spray drying process had atomized to several microns, and that they had become spherical. We investigated the physicochemical properties of the matrix particles by powder X-ray diffraction, differential scanning calorimetry, and dissolution rate analyses with a view to clarifying the effects of crystallinity on the dissolution rate. The powder X-ray diffraction peaks and the heat of the Act fusion in the spray-dried samples decreased with the increase of the carrier content, indicating that the drug was amorphous. These results indicate that the system formed a solid dispersion. Furthermore, we investigated the interaction between the drug and carrier using FT-IR analysis. The FT-IR spectroscopy for the Act solid dispersions suggested that the Act carboxyl group and the Cht amino group formed a hydrogen bond. In addition, the measurement results of the 13C CP/MAS solid-state NMR, indicated that a hydrogen bond had been formed between the Act carbonyl group and the Cht amino group. In the Act-Cht system, the 4-fluid-nozzle spray-dried preparation with a mixing ratio of 1 : 5 obtained a sustained release preparation in all pH test solutions.     

Sugar-dependent aggregation of glycoconjugated chlorins and its effect on photocytotoxicity in HeLa cells

In order to explore the influence of the sugar moieties of glycoconjugated chlorins on the photocytotoxicity, we studied the photochemical properties of four glycoconjugated chlorins in aqueous media such as cytoplasm and the concentration dependence of photocytotoxicity in HeLa cells. In phosphate-buffered saline, the fluorescence intensities of 5,10,15,20-tetrakis[3-(beta-D-glucopyranosyloxy)phenyl]chlorin (m-1a) and 5,10,15,20-tetrakis[3-(beta-D-galactopyranosyloxy)phenyl]chlorin (m-1b), i.e., chlorins having hexose groups, were about 2-fold greater than those of 5,10,15,20-tetrakis[3-(beta-d-xylopyranosyloxy)phenyl]chlorin (m-1c) and 5,10,15,20-tetrakis[3-(beta-d-arabinopyranosyloxy)phenyl]chlorin (m-1d), i.e., chlorins having pentose groups, owing to a sugar-dependent difference of aggregation behavior. While no cytotoxicity was found in the dark, the highest photocytotoxicity was shown by m-1a (82% inhibition) in HeLa cells. This was higher than those of m-1b, m-1c, m-1d and tetraphenylporphyrin tetrasulfonic acid. The glycoconjugated chlorins except for m-1b appeared to be distributed diffusely throughout the cytoplasm. Among the four photosensitizers, m-1a showed the highest intensity in confocal fluorescence images, in agreement with the in vitro photocytotoxicity results. For m-1c, no photocytotoxicity was found at drug concentrations from 0.2 to 0.04 microM. Hence, sugar-dependent aggregation is not the major reason for the unexpected lack of efficacy of m-1c, which is uptaken efficiently by HeLa cells. For the glycoconjugated chlorins, these results suggest the biological aspects of sugar moiety play much crucial role rather than chemical aspects.     

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.     

Advanced high-pressure plasma diagnostics with hairpin resonator probe surrounded by film and sheath

The hairpin probe using microwave resonance in plasma is applicable to high pressure 1.33×10 3-1.01×10 5 Pa)) as developed recently.In this work,an analytic model of the hairpin resonator probe surrounded by a thin dielectric layer and a sheath layer is proposed.The correction factor due to these surroundings is analytically found and confirmed by electromagnetic field finite difference time domain simulation,thus enabling the accurate measurement of electron density in a high-pressure non-equilibrium uniform discharge.     

Flavonoids from Sedum japonicum subsp. oryzifolium (Crassulaceae)

Twenty-two flavonoids were isolated from the leaves and stems of Sedum japonicum subsp. oryzifolium (Crassulaceae). Of these compounds, five flavonoids were reported in nature for the first time, and identified as herbacetin 3-O-xyloside-8-O-glucoside, herbacetin 3-O-glucoside-8-O-(2′′′-acetylxyloside), gossypetin 3-O-glucoside-8-O-arabinoside, gossypetin 3-O-glucoside-8-O-(2′′′-acetylxyloside) and hibiscetin 3-O-glucoside-8-O-arabinoside via UV, HR-MS, LC-MS, acid hydrolysis and NMR. Other seventeen known flavonoids were identified as herbacetin 3-O-glucoside-8-O-arabinoside, herbacetin 3-O-glucoside-8-O-xyloside, gossypetin 3-O-glucoside-8-O-xyloside, quercetin, quercetin 3-O-glucoside, quercetin 3-O-xylosyl-(1→2)-rhamnoside-7-O-rhamnoside, quercetin 3-O-rhamnoside-7-O-glucoside, kaempferol, kaempferol 3-O-glucoside, kaempferol 7-O-rhamnoside, kaempferol 3,7-di-O-rhamnoside, kaempferol 3-O-glucoside-7-O-rhamnoside, kaempferol 3-O-glucosyl-(1→2)-rhamnoside-7-O-rhamnoside, kaempferol 3-O-xylosyl-(1→2)-rhamnoside, kaempferol 3-O-xylosyl-(1→2)-rhamnoside-7-O-rhamnoside, myricetin 3-O-glucoside and cyanidin 3-O-glucoside. Some flavonol 3,8-di-O-glycosides were found in Sedum japonicum subsp. oryzifolium as major flavonoids in this survey. They were presumed to be the diagnostic flavonoids in the species. Flavonoids were reported from S. japonicum for the first time.