Efficient topological chaos embedded in the blinking vortex system

We consider the particle mixing in the plane by two vortex points appearing one after the other, called the blinking vortex system. Mathematical and numerical studies of the system reveal that the chaotic particle mixing, i.e., the chaotic advection, is observed due to the homoclinic chaos, but the mixing region is restricted locally in the neighborhood of the vortex points. The present article shows that it is possible to realize a global and efficient chaotic advection in the blinking vortex system with the help of the Thurston-Nielsen theory, which classifies periodic orbits for homeomorphisms in the plane into three types: periodic, reducible, and pseudo-Anosov (pA). It is mathematically shown that periodic orbits of pA type generate a complicated dynamics, which is called topological chaos. We show that the combination of the local chaotic mixing due to the topological chaos and the dipole-like return orbits realize an efficient and global particle mixing in the blinking vortex system.     

Synthesis of a protein biosynthesis inhibitor, 5′-tri-phosphoryladenylyl-(2′-5′)-adenosine

A protein biosynthesis inhibitor, 5′-triphosphoryladenylyl-(2′-5′)-adenylyl-(2′-5′)-adenosine was synthesized by polymerization of N⁶-benzoyl-3′-O-(o-nitrobenzyl)adenosine 5′-phosphate follwed by reaction with pyrophosphate using 1,1′-carbonyldiimidazole.     

Effect and Mechanism of a New Photodynamic Therapy with Glycoconjugated Fullerene

When irradiated, fullerene efficiently generates reactive oxygen species (ROS) and is an attractive photosensitizer for photodynamic therapy (PDT). Ideally, photosensitizers for PDT should be water-soluble and tumor-specific. Because cancer cells endocytose glucose more effectively than normal cells, the characteristics of fullerene as a photosensitizer were improved by combining it with glucose. The cytotoxicity of PDT was studied in several cancer cell lines cultured with C₆₀-(Glc)1 (d -glucose residue pendant fullerene) and C₆₀-(6Glc)1 (a maltohexaose residue pendant fullerene) subsequently irradiated with UVA₁. PDT alone induced significant cytotoxicity. In contrast, PDT with the glycoconjugated fullerene exhibited no significant cytotoxicity against normal fibroblasts, indicating that PDT with these compounds targeted cancer cells. To investigate whether the effects of PDT with glycoconjugated fullerene were because of the generation of singlet oxygen (¹O₂), NaN₃ was added to cancer cells during irradiation. NaN₃ extensively blocked PDT-induced apoptosis, suggesting that PDT-induced cell death was a result of the generation of ¹O₂. Finally, to investigate the effect of PDT in vivo, melanoma-bearing mice were injected intratumorally with C₆₀-(Glc)1 and irradiated with UVA₁. PDT with C₆₀-(Glc)1 suppressed tumor growth. These findings indicate that PDT with glycoconjugated fullerene exhibits tumor-specific cytotoxicity both in vivo and in vitro via the induction of ¹O₂.     

Identification of efferent flow in the superior vena cava and azygos vein confluence using cine phase-contrast MRI: speculation of the role of the azygos arch valves

Purpose

We aimed to evaluate flow patterns in the superior vena cava (SVC) and azygos vein confluence with cine phase-contrast magnetic resonance imaging with consideration for the role played by the azygos arch valves.

Materials and Methods

Two-dimensional cine phase-contrast magnetic resonance images of the SVC and azygos vein confluence were prospectively acquired in 10 healthy volunteers. Flow directions during the cardiac cycle were evaluated quantitatively using sequential flow profile graphs obtained from each orthogonal image and affirmed visually by two radiologists from the oblique sagittal cine images.

Results

Although the blood in the SVC and azygos vein confluence had an afferent flow during the systolic phase, a slight temporal efferent flow during the diastolic phase was quantitatively observed in all cases. Flow in the SVC can also be confirmed visually. The average velocity, average maximum afferent velocity during the systolic phase and average maximum efferent velocity during the diastolic phase of the SVC were 8.7±2.4, 19.9±3.7 and −1.0±3.2 cm/s, respectively; for the azygos vein confluence, these values were 2.2±1.5, 7.1±2.6 and −1.5±1.1 cm/s, respectively.

Conclusion

We verified that a slight temporal efferent flow exists in the SVC and azygos vein confluence during the diastolic phase, which suggests that the usual role of the azygos arch valves is to prevent this physiological retrograde flow.     

Differential scanning calorimetry analysis of crystal structure transformation in spray-dried particles consisting of ammonium nitrate,potassium nitrate,and a polymer

Ammonium nitrate (AN) is an affordable oxidant; however, it undergoes crystal structure transformations accompanied by a change in volume at comparatively low temperatures (approx. 30, 80, and 125 °C) and exhibits high hygroscopicity. Both these properties are particularly problematic for the industrial application of AN. In a previous study, we prepared spray-dried particles comprising three components: AN, potassium nitrate (PN) as a phase stabilizer, and a polymer (e.g., polyvinyl alcohol, carboxymethylcellulose salt, and styrene-butadiene latex), which was confirmed to provide effective moisture proofing. In the present study, the crystal transformation behavior of AN/PN/Polymer particles is investigated by observing their thermal behavior by differential scanning calorimetry. The results reveal that phase-stabilized AN can be successfully prepared by the addition of PN. In addition, an intriguing possibility was identified in that carboxymethylcellulose ammonium salt and polyvinyl alcohol, which were both added as polymer components for moisture proofing, also acted as phase stabilizers for AN crystal transformation.     

Novel Disaccharides Containing 3-Deoxy-D-Manno-2-Octulosonic Acid (KDO) and Lipid a Subunit Analogs

Abstract

3-Deoxy-D-manno-2-octulosonic acid (KDO)₁ is a prominent constituent of bacterial lipopolysaccharides (LPS),₂ and recently it has been demonstrated _3,4 that the KDO part in the core region of LPS is α-ketosidically linked to 0-6′ of the o-glucosamine-disaccharide backbone of lipid A. Although the portion, including KDO, has been suggested_5,6 to be necessary for expression of antitumor and interleukin 1 (IL 1)-induction activities of LPS, the disticnt biological roles of KDO in LPS are still obscure.     

Synthesis of new chitosan derivatives and combination with biodegradable polymer

New chitosan derivatives are synthesized by the reductive N‐alkylation reaction of chitosan with various aldehydes, such as 2,4‐dihydroxybenzaldehyde, cholesteryl 4‐formylbenzoate, and N‐dehydroabietyl‐4‐formylbenzamide. The palladium‐adsorption ability of the newly synthesized derivatives is found to be as good as that of chitosan. A blend of chitosan and other biodegradable polymers is also found to exhibit palladium‐adsorption ability. In comparison to the starting chitosan, the chitosan derivative having dehydroabietyl‐type side chains exhibited an improved solubility in methanol. The chitosan derivatives are successfully applied as plastic coating materials for electroless plating. Copyright © 2003 John Wiley & Sons, Ltd.     

Porphyrin derivatives act as vinylene monomers in TEMPO‐mediated radical copolymerization with styrene

In this article, we offer clear evidence for the radical copolymerizability of porphyrin rings in 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO)‐mediated radical copolymerizations with styrene. The radical copolymerizations of styrene with 5,10,15,20‐tetrakis(pentafluorophenyl)porphyrin (H₂TFPP) was conducted using 1‐phenyl‐1‐(2,2,6,6‐tetramethyl‐1‐piperidinyloxy)ethane as an initiator. The refractive index (RI) traces for the size‐exclusion chromatography of the resulting copolymers were unimodal with narrow molecular weight distributions. The RI traces shifted toward higher molecular weight regions as the polymerization progressed, and the number‐average molecular weights were close to those calculated on the basis of the feed compositions and monomer conversions. These features were in good agreement with a TEMPO‐mediated mechanism. The traces recorded by the ultraviolet‐visible (UV‐vis) detector (430 nm) were identical to those obtained by the RI detector, indicating a statistical copolymerization of styrene with H₂TFPP. This also indicated that H₂TFPP acted as a monomer and not as a terminator or a chain‐transfer agent under the conditions used. A benzyl radical addition to H₂TFPP was conducted as a model reaction for the copolymerization using tributyltin hydride as a chain‐transfer agent, affording a reduced porphyrin, 2‐benzyl‐5,10,15,20‐tetrakis(pentafluorophenyl)chlorin 1 , via radical addition to the β‐pyrrole position. The UV‐vis spectrum of 1 was fairly similar to that of poly(styrene‐co‐H₂TFPP), indicating that H₂TFPP polymerized at its β‐pyrrole position in the TEMPO‐mediated radical polymerization. TEMPO‐mediated radical copolymerizations of styrene with several porphyrin derivatives were also demonstrated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Copper-Catalyzed Electrophilic Amidation of Organotrifluoroborates with Use of N-Methoxyamides

A copper-catalyzed electrophilic amidation of aryltrifluoroborates with use of N-methoxyamides is reported. The reaction shows high functional group compatibility derived from two distinct features: 1) the high stability of the N-methoxyamides and 2) the nonbasic mild conditions in the presence of LiCl. The developed method can also be applied to the synthesis of enamides, which are widely distributed in natural products. Preliminary mechanistic studies suggest that the initial step is the transmetalation of the aryltrifluoroborate by the assistance of LiCl, and the resulting aryl copper intermediate provides the anilide through non-S_N2 oxidative addition to the N-methoxyamide and subsequent reductive elimination.