Analytical estimation of liquid film thickness in two-phase annular flow using electrical resistance measurement

This paper presents an analytical solution to estimate the liquid film thickness in two-phase annular flow through a circular pipe using electrical resistance tomography. Gas–liquid flow with circular gas core surrounded by a liquid film is considered. Conformal mapping is employed to obtain the analytic solution for annular flow with an eccentric circular gas core. The liquid film thickness for an arbitrary annular flow is estimated by comparing the resistance values for concentric and eccentric annular flows. The film thickness estimation has a good performance when the normalized distance between the gas core center and the flow center is less than 0.2 and the void fraction is greater than 0.4, the estimated error of the normalized thickness is less than 0.04.     

Multilayer transfer printing on microreservoir-patterned substrate employing hydrophilic composite mold for selective immobilization of biomolecules

In this study, we introduce a hydrophilic composite mold with elasticity and moderate water permeability, suitable for transferring water-soluble polar molecules such as polyelectrolyte multilayer. This composite mold is constructed from two UV-curable polymers-Norland Optical Adhesives (NOA) 63, a urethane-related polymer, and poly(ethylene glycol) diacrylate (PEGDA). The mixture of inherently hard NOA 63 and hydrogel precursor, PEGDA, resulted in an optically transparent mold with some degree of elasticity and enhanced water permeability upon UV polymerization. Employing the NOA 63-PEGDA composite mold, a polyelectrolyte multilayer comprising alternate thin layers of poly(acrylic acid) (PAA) and poly(acrylamide) (PAAm) was transfer-printed onto arrays of microreservoir-patterned substrate to selectively prevent unwanted adsorption of biomolecules on the protruding surface. Antibody was immobilized selectively inside the microreservoirs where multilayer was not transferred, and a specific antibody binding reaction was detected inside the microreservoirs. Furthermore, the potential of this composite mold as a convenient tool for constructing a biosensor for detecting Escherichia coli (E. coli) O157:H7 was explored.     

Grid-based Thomas-Fermi-Amaldi equation with the molecular cusp condition

First, the Thomas-Fermi-Amaldi (TFA) equation was formulated with a newly derived condition to remove the singularities at the nuclei, which coincided with the molecular cusp condition. Next, the collocation method was applied to the TFA equation using the grid-based density functional theory. In this paper, the electron densities and the radial probabilities for specific atoms (He, Be, Ne, Mg, Ar, Ca) were found to agree with those from the Thomas-Fermi-Dirac (TFD) method. Total energies for specific atoms (He, Ne, Ar, Kr, Xe, Rn) and molecules (H2,CH4) were also found to be close to those from the Hartree-Fock method using the Pople basis set 6-311G relative to the TFD method. In addition, the computational expense to determine the electron density and its corresponding energy for a large scale structure, such as a carbon nanotube, is shown to be much more efficient compared to the conventional Hartree-Fock method using the 6-31G Pople basis set.     

A study of the radical-radical reaction dynamics of O(3P)+t-C4H9 --> OH+iso-C4H8

The radical-radical reaction dynamics of ground-state atomic oxygen [O(3P)] with t-butyl radicals (t-C4H9) in the gas phase were investigated using high-resolution laser spectroscopy in a crossed-beam configuration, together with ab initio theoretical calculations. The radical reactants, O(3P) and t-C4H9, were produced by the photodissociation of NO2 and the supersonic flash pyrolysis of the precursor, azo-t-butane, respectively. A new exothermic channel, O(3P)+t-C4H9 --> OH+iso-C4H8, was identified and the nascent rovibrational distributions of the OH (X 2Pi: upsilon" = 0,1,2) products were examined. The population analyses for the two spin-orbit states of F1(2Pi32) and F2(2Pi12) showed that the upsilon" = 0 level is described by a bimodal feature composed of low- and high-N" rotational components, whereas the upsilon" = 1 and 2 levels exhibit unimodal distributions. No noticeable spin-orbit or Lambda-doublet propensities were observed in any vibrational state. The partitioning ratio of the vibrational populations (Pupsilon") with respect to the low-N" components of the upsilon" = 0 level was estimated to be P0:P1:P2 = 1:1.17+/-0.24:1.40+/-0.11, indicating that the nascent internal distributions are highly excited. On the basis of the comparison of the experimental results with the statistical theory, the reaction mechanism at the molecular level can be described in terms of two competing dynamic pathways: the major, direct abstraction process leading to the inversion of the vibrational populations, and the minor, short-lived addition-complex process responsible for the hot rotational distributions. After considering the reaction exothermicity, the barrier height, and the number of intermediates along the addition reaction pathways on the lowest doublet potential energy surface, the formation of CH3COCH3(acetone)+CH3 was predicted to be dominant in the addition mechanism.     

Development of the Pictet-Spengler reaction catalyzed by AuCl3/AgOTf

Mild and efficient AuCl3/AgOTf-catalyzed Pictet-Spengler reactions were developed to afford in good yields a variety of tetrahydroisoquinoline and tetrahydro-beta-carboline ring systems, which constitute important motifs in biologically active natural and synthetic organic compounds.     

Binary mixing of micelles using Pluronics for a nano-sized drug delivery system

Pluronics with different structural compositions and properties are used for several applications, including drug delivery systems. We developed a binary mixing system with two Pluronics, L121/P123, as a nano-sized drug delivery carrier. The lamellar-forming Pluronic L121 (0.1 wt%) was incorporated with Pluronic P123 to produce nano-sized dispersions (in case of 0.1 and 0.5 wt% P123) with high stability due to Pluronic P123 and high solubilization capacity due to Pluronic L121. The binary systems were spherical and less than 200-nm diameter, with high thermodynamic stability (at least 2 weeks) in aqueous solution. The CMC of the binary system was located in the middle of the CMC of each polymer. In particular, the solubilization capacity of the binary system (0.1/0.1 wt%) was higher than mono-systems of P123. The main advantage of binary systems is overcoming limitations of mono systems to allow tailored mixing of block copolymers with different physicochemical characteristics. These nano-sized systems may have potential as anticancer drug delivery systems with simple preparation method, high stability, and high loading capacity.     

Block Copolymer Micelles with Near Infrared Metal Phthalocyanine Dyes for Laser Induced Writing

A route has been developed to disperse metal‐containing phthalocyanine dyes in a non‐polar medium based on amphiphilic block copolymer micelles of poly[styrene‐block‐(4‐vinylpyridine)] (PS‐b‐P4VP) and poly[styrene‐block‐(acrylic acid)] (PS‐b‐PAA) copolymers. Polar P4VP and PAA efficiently encapsulate cobalt(II ), manganese(II ), and nickel(II ) phthalocyanine dyes by axial coordination of nitrogen and µ‐oxo bridged dimerization with the transition metals, respectively. Good dispersion of the dyes is confirmed by the linear enhancement of Q‐bands in UV–vis absorption spectra with dye concentration. A thin monolayered PS‐b‐P4VP micelle film that contained a nickel(II ) phthalocyanine dye which efficiently adsorbs a laser beam on a localized area to generate a local heat higher than the glass transition temperatures of both blocks. One‐dimensional laser writing on the dye‐containing film allows the fabrication of a few submicrometer wide line patterns in which the self‐assembled nanostructure of the block copolymer is modified by the directional heat arising from laser scanning.

     

Monitoring Transformations of Catalytic Active States in Photocathodes Based on MoSx Layers on CuInS2 Using In Operando Raman Spectroscopy

The electrochemical activation of CuInS₂/MoS_x for photoelectrochemical (PEC) H₂ production was revealed for the first time through in operando Raman spectroscopy. During the activation process, the initial metallic MoS_x phase was transformed to semiconducting MoS_x, which facilitates charge carrier transfer between CuInS₂ and MoS_x. Ex situ X-ray photoelectron spectroscopy and Raman spectroscopy suggest the existence of MoO₃ after the activation process. However, apart from contradicting these results, in operando Raman spectroscopy revealed some of the intermediate steps of the activation process.