Identification and characterization of component organic and glycosidic acids of crude resin glycoside fraction from Calystegia soldanella

Alkaline hydrolysis of the crude resin glycoside fraction of the leaves, stems, and roots of Calystegia soldanella ROEM. et SCHULT. (Convolvulaceae) gave four new glycosidic acids, named calysolic acids A, B, C, and D, along with one known glycosidic acid, soldanellic acid B, and three organic acids, 2S-methylbutyric, tiglic, and 2S,3S-nilic acids. The structures of the new glycosidic acids were characterized on the basis of spectroscopic data and chemical evidence.     

Synthesis of 3,3‐Dimethyl‐4‐chromanones: Improved Procedures Without Ring Opening

A procedure for the 3,3‐dimethylation of 4‐chromanones under basic conditions was improved; the by‐product from chromanone ring opening was isolated and its structure was determined.     

Rapid collection of iron hydroxide for determination of Th isotopes in seawater

This work introduces a novel method of recovery of iron hydroxide using a DIAION CR-20 chelating resin column to determine Th isotopes in seawater with a sector field (SF) inductively coupled plasma mass spectrometer (ICP-MS). Thorium isotopes in seawater were co-precipitated with iron hydroxide, and this precipitate was sent to chelating resin column. Ferric ions in the iron hydroxide were bonded to functional groups of the chelating resin directly, resulting in a pH increase of the effluent by release of hydroxide ion from the iron hydroxide. The co-precipitated thorium isotopes were quantitatively collected within the column, which indicated that thorium was retained on the iron hydroxide remaining on the chelating column. The chelating column quantitatively collected ²³²Th with iron hydroxide in seawater at flow rates of 20–25 mL min⁻¹. Based on this flow rate, a 5 L sample was processed within 3–4 h. The >20 h aging of iron hydroxide tends to reduce the recovery of ²³²Th. The rapid collection method was successfully applied to the determination of ²³⁰Th and ²³²Th in open-ocean seawater samples.     

Relationship between orbital energy gaps and excitation energies for long‐chain systems

The difference between the excitation energies and corresponding orbital energy gaps, the exciton binding energy, is investigated based on time‐dependent (TD) density functional theory (DFT) for long‐chain systems: all‐trans polyacetylenes and linear oligoacenes. The optimized geometries of these systems indicate that bond length alternations significantly depend on long‐range exchange interactions. In TDDFT formalism, the exciton binding energy comes from the two‐electron interactions between occupied and unoccupied orbitals through the Coulomb‐exchange‐correlation integral kernels. TDDFT calculations show that the exciton binding energy is significant when long‐range exchange interactions are involved. Spin‐flip (SF) TDDFT calculations are then carried out to clarify double‐excitation effects in these excitation energies. The calculated SF‐TDDFT results indicate that double‐excitation effects significantly contribute to the excitations of long‐chain systems. The discrepancies between the vertical ionization potential minus electron affinity (IP–EA) values and the HOMO–LUMO excitation energies are also evaluated for the infinitely long polyacetylene and oligoacene using the least‐square fits to estimate the exciton binding energy of infinitely long systems. It is found that long‐range exchange interactions are required to give the exciton binding energy of the infinitely long systems. Consequently, it is concluded that long‐range exchange interactions neglected in many DFT calculations play a crucial role in the exciton binding energies of long‐chain systems, while double‐excitation correlation effects are also significant to hold the energy balance of the excitations. © 2016 Wiley Periodicals, Inc.     

Evolution of standing mesochannels on porous anodic alumina substrates with designed conical holes

We report the formation of standing mesochannels simply by spin-coating a precursor solution onto a PAA (porous anodic alumina) substrate with designed conical holes, utilizing exactly the same precursors and reaction conditions that form two-dimensional (2D) hexagonal mesoporous SBA-15-type films. When the aspect ratios of the conical holes are lower, the sponge-like mesopores are generated within the conical holes. Such a formation of sponge-like mesostructures truly acts as a trigger for the evolution of perpendicularly oriented and tilted mesochannels. On the other hand, when the PAA substrates with high-aspect cones are used, the mesochannels are stacked like a doughnut within the conical holes, which leads to parallel orientations of the mesochannels in the continuous film region.     

High-density DNA alignment on an Au(111) surface starting from folded DNA

High-density uniform DNA alignment on a metal substrate is essential for creating sensitive DNA devices. We develop a self-sensing DNA alignment process starting from folded DNA to achieve high-density, uniform DNA alignment on an Au(111) surface. We demonstrate that folded DNA plays a critical role in avoiding DNA aggregation and distributing the DNA uniformly on an Au(111) surface at the greatest density and quality ever attained. We also verify that the distributed, folded DNA can be stimulated to align only when the appropriate buffer flow is applied. This selective self-sensing DNA alignment on an Au surface will be a key technology for creating dynamic DNA sensors and switches.     

Determination of Solvent‐Trapped Products Obtained by Photolysis of Aryl Azides in 2,2,2‐Trifluoroethanol

A series of nonfluorinated and fluorinated aryl azides with varied functionality patterns were irradiated in 2,2,2‐trifluoroethanol with either a high‐pressure or a low‐pressure mercury lamp. Interestingly, one of the major products in these reactions was the result of the recombination of anilino and alkyl radicals to form the corresponding hemiaminal compounds. The structure of the recombination products was assigned unambiguously after proton/deuterium exchange experiments followed by MS and MS/MS analysis.     

Size change of the wormlike micelles of pentaoxyethylene, hexaoxyethylene, and heptaoxyethylene dodecyl ethers with uptake of n-dodecane

Wormlike micelles of the surfactant penta-, hexa-, and heptaoxyethylene dodecyl ethers C12 E5, C12 E6, and C12 E7 were characterized by static light scattering (SLS) and dynamic light scattering (DLS) experiments to examine effects of uptake of n-dodecane on the micellar characteristics. The SLS results have been successfully analyzed by the light scattering theory for micelle solutions to yield the molar mass Mw(c) as a function of concentration c along with the cross-sectional diameter d of the micelle. The apparent hydrodynamic radius RH,app(c) determined by DLS as a function of c has also been successfully analyzed by the fuzzy cylinder theory which (-1). It has been found that the micellar length Lw increases with increasing surfactant mass concentration c and the values of d and lambda(-1) increase with increasing n-dodecane content wd, as in the case of various CiEj micelles containing n-alcohol. On the other hand, the values of Mw, Lw, and RH,app for all the micelles examined decrease with increasing wd contrary to the micelles containing n-alcohol. This finding may be attributed to the fact that the addition of n-dodecane into the micelles weakens hydrophilic interactions among polyoxyethylene chains of the surfactant molecules and water, making the micelles unstable, and then leading them to collapse into smaller micelles.     

The movement of a water droplet on a gradient surface prepared by photodegradation

A hydrophobic to hydrophilic gradient surface was prepared using the tuned photodegradation of an alkylsilane self-assembled monolayer (SAM) using irradiation of vacuum ultraviolet light (wavelength=172 nm). The water contact angle on the photodegraded SAM surface was adjusted using the intensity and time photoirradiation parameters. The formation of a gradient was confirmed by fluorescent labeling. The water drop moved from the hydrophobic to hydrophilic surface with a velocity that depended on the gradient. The higher the gradient, the faster the water moved. For the first time, we have prepared a gradient surface using photodegradation where the movement of a water drop was regulated by the degree of gradation. Considering that the photodegradation technique can be applied to various surfaces and to lithography, this technique will be useful for various material surfaces.