Vacuum ultraviolet-induced surface modification of cyclo-olefin polymer substrates for photochemical activation bonding

The surface of cyclo-olefin polymer (COP) was treated with vacuum ultraviolet (VUV) light at 172 nm wavelength to improve the wettability and adhesion properties. Through VUV treatment in air, the terminal groups of the COP surface were oxidized into oxygen functional groups, containing CO, CO, and COO components, making the COP surface hydrophilic. The extent of oxygenation was evaluated by XPS and FTIR-ATR spectra, and it was shown that the surface properties, hydrophilicity, and functionalization were dependent on both VUV irradiation distance and irradiation time, which have an effect on the concentration of oxygen functional groups. VUV-light treatment with a short irradiation distance was more effective in introducing oxygen functional groups.     

Surface modification of polymer latex particles by AGET ATRP of a styrene derivative bearing a lactose residue

Grafting of a styrene derivative bearing a lactose residue, i.e., N-2-4-(vinylbenzenesulfonamido)ethyl lactobionamide (VBSAELA), onto polymer latex particles was carried out in aqueous media by activator generated electron transfer atom transfer radical polymerization (AGET ATRP). The core polymer latex particles having α-chloroester groups as ATRP-initiating groups were prepared by miniemulsion polymerization of styrene and 2-chloropropionyloxyethyl methacrylate (CPEM) in the presence of a polymerizable surfactant, i.e., N,N-dimethyl-N-dodecyl-N-2-methacryloyloxyethylammonium bromide (C₁₂Br). AGET ATRP was initiated with tris[(2-pyridylmethyl)amine] copper (II) dichloride and l-ascorbic acid. Dynamic light scattering (DLS) revealed that the P(St-CPEM)-g-P(VBSAELA) particles possess graft layers of 10 nm in thickness on the core particles of 91 nm in diameter. Critical coagulation concentration measurement revealed that the dispersion stability of the particles in water increased due to hydrated P(VBSAELA) shell layers. Adsorption of bovine serum albumin (BSA) onto the particles was considerably suppressed by the hydrated shell layers.     

Synthesis of Au–Pd bimetallic nanoparticles under energetic irradiation fields

Bimetallic Au–Pd nanoparticles were synthesized under high-energy irradiation fields (1.17 and 1.33 MeV γ-rays, 9 MeV electrons, and 1.6 GeV C ions) from solutions containing Au³⁺ and Pd²⁺ and cationic surfactant (sodium dodecyl sulfate). Particles synthesized by the irradiation were observed using conventional transmission electron microscope (TEM) and annular dark-field scanning transmission electron microscopy (ADF-STEM). The particles synthesized by γ-rays and C ion irradiation exhibit core–shell structure with a Au-core and a Pd-shell. The dependence of the size distribution of nanoparticles on the dose rate is discussed.     

Helical metallohost-guest complexes via site-selective transmetalation of homotrinuclear complexes

We have designed a new type of bis(N2O2) chelate ligand that affords a C-shaped O6 site on the metalation of the N2O2 sites. UV-vis and 1H NMR titration clearly showed that the complexation between H4L and zinc(II) acetate affords 1:3 complex [LZn3]2+ via a highly cooperative process. Although the O6-recognition site of the dinuclear metallohost [LZn2] is filled with the additional Zn2+, the O6 site can bind a guest ion with concomitant release of the initially bound Zn2+. The novel recognition process "guest exchange" took place quantitatively when rare earth metals were used as a guest. In the case of alkaline earth metals, selectivity of Ca2+ > Sr2+ > Ba2+ > Mg2+ was observed. On the other hand, the transmetalation did not take place at all when alkali metals were used for the guest. Accordingly, the trinuclear complex [LZn3]2+ is excellent in discriminating charge of the guest ions. The metallohost-guest complexes thus obtained have a helical structure, and the radius d and winding angle theta of the helix depend on the size of the guest. The La3+ complex has the smallest theta (288 degrees), and the Sc3+ complex has the largest theta (345 degrees). Because the radius and winding angles of helices are tunable by changing the guest ion, the helical metallohost-guest complexes are regarded as a molecular spring or coil. Consequently, site-specific metal exchange of trinuclear complex [LZn3]2+ described here will be utilized for highly selective ion recognition, site-selective synthesis of (3d)2(4f) trimetallic complexes, and construction of "tunable" metallohelicenes.     

Effects of grafted polymer chains on lamellar membranes

We have investigated the effects of grafted polymer chains [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] on the bending modulus and the intermembrane interactions of lamellar membranes (C(12)E(5) water) by means of a neutron spin-echo and a small-angle x-ray scattering technique. In this study the hydrophilic chain takes the mushroom configuration on the membrane. The bending modulus of the polymer-grafted membranes increases in proportion to the square of the end to end distance of the polymer chain, which agrees well with the theoretical prediction of Hiergeist and Lipowsky [J. Phys. II 6, 1465 (1996)]. From the interlamellar interaction point of view, the mushroom layer is renormalized to the membrane thickness, which enhances the repulsive Helfrich interaction. When the size of the decorated polymer chain increases to the interlamellar distance, however, the mushroom is squeezed so as to optimize the interlamellar potential. Further increase of the grafted polymer size brings a lamellar-lamellar phase separation, where the grafted polymer chains are localized in the dilute lamellar phase and the concentrated lamellar phase forms the onionlike texture.     

Masked imidazolyl-dipyrromethanes in the synthesis of imidazole-substituted porphyrins

Imidazole-substituted metalloporphyrins are valuable for studies of self-assembly and for applications where water solubility is required. Rational syntheses of porphyrins bearing one or two imidazol-2-yl or imidazol-4-yl groups at the meso positions have been developed. The syntheses employ dipyrromethanes, 1-acyldipyrromethanes, and 1,9-diacyldipyrromethanes bearing an imidazole group at the 5-position. The polar, reactive imidazole unit was successfully masked by use of (1) the 2-(trimethylsilyl)ethoxymethyl (SEM) group at the imidazole pyrrolic nitrogen, and (2) a dialkylboron motif bound to the pyrrole of the dipyrromethane and coordinated to the imidazole imino nitrogen. The nonpolar nature of such doubly masked imidazolyl-dipyrromethanes facilitated handling. Selected masked dipyrromethanes were characterized by 11B and 15N NMR spectroscopy. Five distinct methods were examined to obtain trans-A2B2-, trans-AB2C-, and trans-AB-porphyrins. Each porphyrin contained one or two SEM-protected imidazole units. The SEM group could be removed with TBAF or HCl. Two zinc(II) porphyrins and a palladium(II) porphyrin bearing a single imidazole moiety were prepared and subjected to alkylation (with ethyl iodide, 1,3-propane sultone, or 1,4-butane sultone) to give water-soluble imidazolium- porphyrins. This work establishes the foundation for the rational synthesis of a variety of porphyrins containing imidazole units.     

Absolute configurations of endoperoxides determined by vibrational circular dichroism (VCD)

Diastereomeric mixture on the peroxide portion of an endoperoxide acetylmajapolene A (1) was efficiently separated by HPLC on a chiral column, submitting to vibrational circular dichroism (VCD) investigation. The ab initio theoretical VCD and IR calculations of 1a and 1b were performed by density functional theory (DFT) using the B3PW91/6-31G(d,p) level of theory. Focusing on an isolated characteristic peroxide vibrational band, absolute configurations of 1a and 1b were unambiguously determined as (1R,4R,7S,10S) and (1S,4S,7S,10S), respectively. This is the first VCD application to endoperoxides which exist abundantly in nature.     

Synthetic chlorins bearing auxochromes at the 3- and 13-positions

Synthetic chlorins bearing diverse auxochromes at the 3- and 13-positions of the macrocycle are valuable targets given their resemblance to chlorophylls a and b, which bear 3-vinyl and 13-keto groups. A de novo route has been exploited to construct nine zinc chlorins bearing substituents at the 3- and 13-positions and two benchmark zinc chlorins lacking such substituents. The chlorins are sterically uncongested and bear (1) a geminal dimethyl group in the reduced pyrroline ring, (2) a H, an acetyl, a triisopropylsilylethynyl (TIPS-ethynyl), or a vinyl at the 3-position, (3) a H, an acetyl, or TIPS-ethynyl at the 13-position, and (4) a H or a mesityl at the 10-position. The synthesis of the 13-substituted chlorins relied on p-TsOH x H2O-catalyzed condensation of an 8,9-dibromo-1-formyldipyrromethane (eastern half) and 2,3,4,5-tetrahydro-1,3,3-trimethyldipyrrin (western half), followed by metal-mediated oxidative cyclization, affording the 13-bromochlorin. Similar use of a bromo- or TIPS-ethynyl-substituted western half provided access to 3-substituted chlorins. A 3-bromo, 13-bromo, or 3,13-dibromochlorin was further transformed by Pd-coupling to introduce the vinyl group (via tributylvinyltin), TIPS-ethynyl group (via TIPS-acetylene), or acetyl group (via tributyl(1-ethoxyvinyl)tin, followed by acidic hydrolysis). In the 10-mesityl-substituted zinc chlorins, the series of substituents, 3-vinyl, 13-TIPS-ethynyl, 3-TIPS-ethynyl, 13-acetyl, 3,13-bis(TIPS-ethynyl), 3-TIPS-ethynyl-13-acetyl, or 3,13-diacetyl, progressively causes (1) a redshift in the absorption maximum of the B band (405-436 nm) and the Q(y) band (606-662 nm), (2) a relative increase in the intensity of the Q(y) band (I(B)/I(Q) = 4.2-1.5), and (3) an increase in the fluorescence quantum yield phi(f) (0.059-0.29). The zinc chlorins bearing a 3-TIPS-ethynyl-13-acetyl or a 3,13-diacetyl group exhibit a number of spectral properties resembling those of chlorophyll a or its zinc analogue. Taken together, this study provides access to finely tuned chlorins for spectroscopic studies and diverse applications.     

Stabilization of a channeled spectropolarimeter by self-calibration

A novel method to stabilize a channeled spectropolarimeter is described. The fluctuating retardations of the high-order retarders used in the spectropolarimeter are calibrated in parallel to the measurement of the wavenumber-dependent state of polarization (SOP) of light. Both the calibration of the retarders and the measurement of the SOP can be made simultaneously using a single light to be measured, and hence the resultant wavenumber-dependent SOP is almost immune to fluctuation of the retardations. The effectiveness of this method is experimentally demonstrated with retardation fluctuations induced by a temperature change up to 40 degrees C.     

Shock-Induced Phase Transitions in Systems of Hard Spheres with Attractive Interactions

Shock-induced phase transitions are studied by adopting the recently-developed theoretical framework, which is applicable for shock waves in three phases (gas, liquid, and solid), based on the system of hard spheres with mutual attractive interactions. The Rankine-Hugoniot conditions derived from the system of Euler equations with caloric and thermal equations of state are studied, and the admissibility (stability) of a shock wave is analyzed. Two typical scenarios of the shock-induced phase transitions from gas phase to solid phase are found. A scenario of shock-induced phase transitions involving three phases simultaneously near the triple point is also found.