Kinetic study on solute permeation at the interface of molecular aggregates by partial filling capillary electrophoresis

Moment analysis method using partial filling CE was developed for the kinetic study on solute permeation at the interface of spherical molecular aggregates. Moment equations for partial filling CE were developed by classifying CE systems into five categories according to the migration velocities of solute and molecular aggregate. The method was applied to the study on the dissolution of electrically neutral solutes into SDS micelles. Elution peaks were measured by partial filling CE while changing the concentration of SDS and the filling ratio of SDS micellar zone to the capillary (ϕ_M). Partition equilibrium constants (K_p) and rate constants of interfacial solute permeation of SDS micelles (k_in and k_out) were determined from the first absolute and second central moments of the elution peaks by using the moment equations. Their values were comparable irrespective of ϕ_M and were almost the same as those previously measured by complete filling CE. The positive correlation of K_p with the hydrophobicity of the solutes was explained in terms of the change in k_in and k_out. It was demonstrated that the moment analysis method using partial filling CE is effective for studying solute permeation kinetics at the interface of spherical molecular aggregates.     

New fabrication approach to develop a high birefringence photo-crosslinked film based on a sulfur-containing liquid crystalline molecule with large temperature dependence of birefringence

ABSTRACT

We present a new fabrication approach to achieve a high birefringence film by means of photopolymerization based on an alkylthio-containing rod-like liquid crystalline molecule exhibiting large temperature dependence of birefringence. We designed a new reactive mesogen having alkylthio linkages (BPM–S). It was found that BPM–S had a larger increment of birefringence with decreasing temperature, relative to commercially available alkoxy analog LC242. This result could be thought to be due to enhanced intermolecular attractive interaction for an alkylthio mesogen implied by the proximity of laterally neighboring molecules and cybotactic nematic tendency based on wide-angle X-ray measurement. The uniaxially-aligned photo-polymerized film for BPM–S showed higher birefringence than that for LC 242.     

Multibubble sonoluminescence enhancement by fluid flow

Forced fluid flow can cause the enhancement of multibubble sonoluminescence (SL) under suitable conditions. The effect of directional flow with a circulator is similar to that of rotating flow with a stirrer. The mechanism of the enhancement is that both flows prevent cavitation bubbles from coalescing and clustering, which are responsible for the quenching of SL. The intensity of sonochemiluminescence (SCL) in an aqueous luminol solution increases with flow speed at higher ultrasonic powers more significantly than that of SL in distilled water. However, in the range of low ultrasonic power, the intensities of SL and SCL decrease with flow speed. Therefore, an optimum flow speed exists in relation to ultrasonic power and frequency.     

Improved surface morphology of flow-modulated MOVPE grown AIN on sapphire using thin medium-temperature AIN buffer layer

High-temperature (HT) AIN films were grown on (0 0 0 1) sapphire by low-pressure flow-modulated (FM) metal organic vapor phase epitaxy (MOVPE) with and without inserting a thin medium-temperature (MT) AIN layer. To suppress parasitic reactions between the sources of trimethylaluminum (TMA) and ammonia (NH₃), TMA and NH₃ was introduced to the reactor of MOVPE by alternating supply way. Surface morphology and crystalline quality were characterized by a scanning electronic microscopy (SEM), atomic force microscopy (AFM) and X-ray rocking curve (XRC) measurements of (0 0 0 2) and (10-12) diffractions. The AFM and SEM measurements indicated that the thin MT-AIN layer had a strong influence on the surface morphology of the HT-AIN films. The surface morphology became quite smooth by inserting the thin MT-AIN layer and surface RMS roughness values were 0.84 nm and 13.4 nm for the HT-AIN films with and without inserting the thin MT-AIN buffer layer, respectively. By etching the samples in aqueous KOH solution, it was found that the polarity of AIN films was different, the HT-AIN film with the thin MT-AIN layer could not be etched, indicating that the film had an Al-polar surface; however, the film without the MT-AIN layer was etched, which was explained that that film had a N- or mixed-polar surface. The mechanism for the origin of the different polarity of HT-AIN with and without the thin MT-AIN layer was proposed and discussed in detail.     

Pulsed EPR Dipolar Spectroscopy under the Breakdown of the High-Field Approximation: The High-Spin Iron(III) Case

Pulsed EPR dipolar spectroscopy (PDS) offers several methods for measuring dipolar coupling and thus the distance between electron-spin centers. To date, PDS measurements to metal centers were limited to ions that adhere to the high-field approximation. Here, the PDS methodology is extended to cases where the high-field approximation breaks down on the example of the high-spin Fe³⁺/nitroxide spin-pair. First, the theory developed by Maryasov et al. (Appl. Magn. Reson. 2006 , 30, 683–702) was adapted to derive equations for the dipolar coupling constant, which revealed that the dipolar spectrum does not only depend on the length and orientation of the interspin distance vector with respect to the applied magnetic field but also on its orientation to the effective g-tensor of the Fe³⁺ ion. Then, it is shown on a model system and a heme protein that a PDS method called relaxation-induced dipolar modulation enhancement (RIDME) is well-suited to measuring such spectra and that the experimentally obtained dipolar spectra are in full agreement with the derived equations. Finally, a RIDME data analysis procedure was developed, which facilitates the determination of distance and angular distributions from the RIDME data. Thus, this study enables the application of PDS to for example, the highly relevant class of high-spin Fe³⁺ heme proteins.     

Preparation of free‐standing silicone particles in aqueous heterogeneous system

To prepare cross‐linked silicone (silicone rubber) particles in an aqueous medium, we investigated two synthesis methods involving a miniemulsion system. The first method was based on cationic ring‐opening polymerization of cyclic siloxane, which is a common synthetic route for linear silicone oil and uses octamethylcyclotetrasiloxane (D₄) as the monomer and dimeric D₄ (bis‐D₄) as the cross‐linker. Although this method produces silicone particles, the particles do not remain in the particulate state after drying because of low cross‐linking density. The polymerization mechanism of this method was also investigated, which proceeds under the ring‐opening reaction of D₄ in monomer droplets and upon polycondensation of hydrolyzed D₄, which occurs in the water phase (ie, outside the monomer droplets). This mechanism implied that introducing the cross‐linking structure into particles is difficult because of the low solubility of bis‐D₄ in water. To overcome these difficulties, we demonstrated a second method of preparing silicone particles based on the thiol‐Michael addition reaction between thiol‐terminated silicone oil and triacrylate in miniemulsion systems. Transmission electron microscopy images indicated that the silicone particles obtained in the particulate state upon drying and the aggregates of these particles showed elasticity.     

Velocity and metastable state population distributions of neodymium atoms produced by laser ablation

Laser-induced fluorescence spectroscopy has been employed to characterize the plume produced in nanosecond laser ablation of metallic neodymium. The kinetic-energy distributions of the neutral and ionized atoms in the plume under both vacuum and gas environments have been investigated. The population distribution of metastable levels in the ablated atoms was also derived. The results show that some metastable states are more heavily populated than predicted by a Boltzmann-type distribution. These investigations provide preliminary data for the design of a new type of resonance photo-ionization laser ion source as well as for high-resolution laser spectroscopy of refractory elements. PACS 52.38.Mf; 33.50.Dq; 42.62.Fi     

Selective permeation of CO2 through poly 2-(N,N-dimethyl)aminoethyl methacrylate membrane prepared by plasma-graft polymerization technique

A membrane having an amine moiety was prepared by plasma-grafting 2-(N,N-dimethyl)aminoethyl methacrylate (DAMA) onto a microporous polyethylene substrate. Permselectivity of the membrane for CO₂ over N₂ was achieved in both dry and water swollen conditions. When the CO₂ partial pressure in the feed gas was 0.047 atm, the selectivity of CO₂ over N₂ reached 130 for the highly swollen water containing membrane. This value was found to agree with that obtained with a mobile carrier membrane (supported liquid membrane) using DAMA as the carrier. The effects of several experimental conditions such as degree of grafting, feed partial pressure and temperature on the membrane performance were studied. It was suggested that the membrane acted as a fixed carrier membrane for CO₂ facilitated transport in under the dry condition and acted as a fixed reaction site membrane in the water swollen condition. The carrier transport mechanism is discussed for dry and aqueous membranes.     

Novel hierarchical classification and visualization method for multiobjective optimization of drug properties: application to structure-activity relationship analysis of cytochrome P450 metabolism

In the lead optimization process, medicinal chemists must consider various chemical properties of active compounds, including ADME/Tox properties, and find the best compromise among these. This study presents a novel data mining method for multiobjective optimization of chemical properties, which consists of the hierarchical classification and visualization of multidimensional data. A hierarchical classification tree model is generated by an extension of recursive partitioning that utilizes averaged information gains for multiple objective variables as a quality-of-split criterion. All the hierarchically structured data objects are represented using a large-scale data visualization technique. The technique is an extension of HeiankyoView, which displays data objects as colored icons and group nodes as rectangular borders. Each icon is divided into subregions with different colors, so that it can present multidimensional data according to brightness of the colors. The proposed method was applied to the structure-activity relationship analysis for cytochrome P450 (CYP) substrates. The substrate specificity of six CYP isoforms was successfully delineated: e.g., CYP2C9 substrates are anionic compounds, while CYP2D6 substrates are cationic; and CYP2E1 substrates are smaller compounds, while CYP3A4 substrates are larger compounds.