Cationic polymerization of p-methylstyrene initiated by acetyl perchlorate: An approach to living polymerization

The cationic polymerization of p-methylstyrene initiated by acetyl perchlorate at ?78°C led to long-lived (living-like) polymers with a narrow molecular weight distribution (M?_w/M?_n = 1.1–1.4) in methylene chloride containing a common ion salt (n-Bu₄NClO₄) or in a less polar solvent (CH₂Cl₂/toluene, 1/4v/v). Under these conditions, the number-average molecular weight (M?_n) of the polymers increased in proportion to monomer conversion and was regulated by the monomer-to-initiator ratio. When fresh feeds of the monomer were repeatedly added to a completely polymerized solution, the polymerization ensued at the same rate as before and the linear increase in M?_n with monomer conversion continued. The effects of solvent polarity and the common ion salt on the polymerization showed the suppression of the ionic dissociation of the propagating species, resulting in a “nondissociated species,” to be the key factor for the formation of the long-lived polymers.     

Effects of type and physical properties of oil phase on oil-in-water emulsion droplet formation in straight-through microchannel emulsification, experimental and CFD studies

Straight-through microchannel (MC) emulsification is a novel technique for formulating monodisperse emulsions using an array of micrometer-sized channels vertical to the surface of a silicon plate (a straight-through MC). We studied the effects of the type and physical properties of the dispersed oil phase and of the surfactant concentration on droplet formation from a straight-through MC by experiments and computational fluid dynamics (CFD) simulations. Monodisperse oil-in-water emulsions with coefficients of variation below 4% were formulated from an oblong straight-through MC using silicone oils, tetradecane, medium-chain triglyceride, soybean oil, and liquid paraffin as the oil phase. At oil viscosities (eta(d)) lower than a threshold value of 100 mPa s, the values of the resultant droplet diameter (d(ex)) gradually decreased with increasing eta(d), whereas they were not affected by the surfactant concentration. Conversely, at eta(d) higher than the threshold value, the d(ex) values significantly increased with increasing eta(d), and they were affected by the surfactant concentration. An analysis on the basis of droplet formation time and interfacial tension clarified that the trends in d(ex) at eta(d) above the threshold value would be caused by the significant decrease in the dynamic interfacial tension during droplet formation. We thus discovered that the dynamic interfacial tension is also a parameter affecting the d(ex) along with eta(d) in straight-through MC emulsification. CFD simulations using a three-dimensional (3D) model including a straight-through MC confirmed successful formation of micrometer-sized droplets for the above-mentioned oils. The experimental and CFD results for the resultant droplet size were compared using the dimensionless droplet diameter (d, droplet diameter/channel equivalent diameter). The d(CFD) values agreed well with the d(ex) values at eta(d) below the threshold value of 100 mPa s for all the experiment systems and at eta(d) above the threshold value for the experiment systems that did not contain a surfactant.     

Carbon-Fluorine Bondings of Fluorinated Fullerene and Graphite

Carbon-fluorine bondings of fluorinated fullerenes and fluorine-graphite intercalation compound C_xF were investigated in detail on the basis of XPS data and the potential model using the charge distribution calculated by semiempirical method. It has been confirmed by the present study that two peaks in the C_1s spectra observed for fluorinated fullerenes are assigned to carbon atoms bonded to fluorine atoms and those unbound to fluorine atoms, and the small difference in charges and Madelung potentials of fluorine atoms in different circumstances well explains the single peak in F_1s spectra of fluorinated fullerenes. In the calculated structures of 1,3-C₆₀F₂ and 1,2-C₆₀F_x (x = 2?6) used as the models of C_xF, three kinds of carbon-fluorine bondings were observed corresponding to nearly ionic, semicovalent and covalent C? F bondings. The calculated result supports that the bi-intercalation structure of stage 1 C_xF consists of nearly ionic and semi-covalent fluorines.     

Novel asymmetric through-hole array microfabricated on a silicon plate for formulating monodisperse emulsions

We have proposed a novel microchannel (MC) structure for formulating monodisperse emulsions. The emulsification device is a silicon array of microfabricated, asymmetric through-holes with a slit and a circular channel (an asymmetric straight-through MC). The asymmetric through-holes of a uniform size stably yielded monodisperse emulsions with average droplet diameters of 35-41 mum and coefficients of variation of less than 2% by forcing the to-be-dispersed phase into the continuous phase via the through-holes. Their asymmetry enabled the stable formation of monodisperse emulsion droplets by spontaneous transformation, even using a to-be-dispersed phase with a very low viscosity below 1 mPa s. Additionally, the asymmetric straight-through MC with a high-density through-hole layout has the potential for high-throughput formulation of monodisperse emulsions.     

Electronic structures of exohedral lanthanide-C60 clusters

We have studied the electronic structures of several gas phase exohedral lanthanide (Ln)-C(60) clusters, Ln(n)C(60) (Ln=Pr, Ho, Tb, Tm, Eu, and Yb) with n=1-4, by photoionization spectroscopy of the neutrals and photoelectron spectroscopy of their anions. Both of the spectroscopic analyses reveal that most of the Ln atoms preferably take +3 oxidation states, while Eu atoms alone assume +2 oxidation states, and that C(60) accepts up to twelve donated electrons in Ln(n)C(60). An additional photoionization examination of the oxygen atom mixing into the Ln(n)C(60) clusters demonstrated that each oxygen atom reduces two electrons from C(60). This result implies that the number of accepted electrons in C(60) can be varied by a suitable choice of the number of Ln atoms and O atoms.     

An efficient 1,3-dipolar cycloaddition between aromatic selenoaldehydes and nitrile oxides or nitrile imines: an easy access to selenium-containing five-membered heterocyclic ring system

1,3-Dipolar cycloaddition between aromatic selenoaldehydes, generated by thermal retro Diels-Alder reaction of anthracene cycloadducts, and nitrile oxides or nitrile imines proceeded efficiently to give the corresponding [3+2] cycloadducts as a single isomer in good yields, being 1,4,2-oxaselenazoles or 1,3,4-selenadiazoles, respectively.     

Structures and stabilities of 3d-transition metal-benzene organometallic clusters

In the gas phase, we have successfully synthesized organometallic clusters, M_n(benzene)_m (M=3d transition metal atoms), by using a laser vaporization method. The measurements of mass spectra and ionization energies (E_i) have revealed that the organometallic clusters can take two types of structures; layered sandwich structures (m = n + 1) and metal clusters saturatedly covered with benzenes. For early transition metals of Sc, Ti, and V, only the multiple decker sandwich structure clusters were preferentially produced, in which benzene and metal atoms are alternately piled up. For late transition metals of Co and Ni, the metal clusters saturatedly surrounded by benzenes were also produced as well as the sandwich clusters. Furthermore, the E_is of M₁(benzene)₂ (M = Sc-Ni) were systematically measured and their electronic properties will be discussed.     

CFD simulation and analysis of emulsion droplet formation from straight-through microchannels

We recently proposed a technique for preparing monodisperse emulsions with a coefficient of variation below 5% from a silicon array of micrometer-sized channels perpendicular to the plate surface, named a straight-through microchannel (MC). This study involved three-dimensional computational fluid dynamics (CFD) simulations to calculate the formation of an oil-in-water (O/W) emulsion droplet from straight-through MCs with circular and elliptic cross sections. The CFD results demonstrated that the oil phase that passed through the elliptic MCs exceeding a threshold aspect ratio between 3 and 3.5 was cut off spontaneously into a small droplet with a diameter of approximately 40 microm. Sufficient space for water at the channel exit had to be maintained for successful droplet formation. The formation and shrinkage of a neck inside the channel caused an increased pressure difference inside the channel and an increased velocity value near the neck. The pressure and velocity values at the neck drastically changed, and the neck was cut off instantaneously just before the completion of droplet formation. This process was triggered by a gradually increased pressure difference between the circular neck and inflating oil phase. The findings obtained in this paper provide useful numerical and visual information about the droplet formation phenomena from the straight-through MCs. The CFD results were verified by the experimental results, showing that the CFD approach can help design a suitable channel structure.     

Calculations of the electrostatic free energy contributions to the binding free energy of sulfonamides to carbonic anhydrase

The interactions between biologically important enzymes and drugs are of great interest. In order to address some aspects of these interactions we have initiated a program to investigate enzymedrug interactions. Specifically, the interactions between one of the isozymes of carbonic anhydrase and a family of drugs known as sulfonamides have been studied using computational methods. In particular the electrostatic free energy of binding of carbonic anhydrase II with acetazolamide, methazolamide,p-chlorobenzenesulfonamide,p-aminobenzenesulfonamide and three new compounds (MK1, MK2, and MK3) has been computed using finite-difference Poisson-Boltzmann (FDPB) [1] method and the semimacroscopic version [2, 3] of the protein dipole Langevin dipole (PDLD) method [4]. Both methods, FDPB and PDLD, give similar results for the electrostatic free energy of binding even though different charges and different treatments were used for the protein. The calculated electrostatic binding free energies are in reasonable agreement with the experimental data. The potential and the limitation of electrostatic models for studies of binding energies are discussed.