The Constituents of the Stem and Roots of Aristolochia foveolata

One new aristolactam glucoside: aristolactam-Ia-N-D-glucoside together with seventeen known compounds were isolated from the fresh stems and roots of Aristolochia foveolata. Their structures were determined by spectral and chemical methods. Among seven aristolochic acid derivatives, five were determined to be salt forms by IR and ¹H NMR methods.     

Fabrication of Mesoporous CoS2 Nanotube Arrays as the Counter Electrodes of Dye‐Sensitized Solar Cells

Mesoporous cobalt sulfide nanotube arrays on FTO‐coated glass were synthesized by combining three simple technologies: the selective etching of ZnO sacrificial templates, mesoporous Co₃O₄ formation from cobalt‐chelated chitosan, and ion‐exchange reaction (IER). The mesoporous Co₃O₄ nanotubes composed of the Co₃O₄ nanoparticles possess a high surface area and are taken advantage for further removal of templates and IER. The morphologies and crystal structures of the CoS₂ nanotube arrays were characterized by SEM, TEM, and XRD analyses. Their electrocatalytic properties were determined by electrochemical analyses including cyclic voltammetry measurements and Tafel polarization. The DSSCs assembled with a CoS₂ counter electrode achieved a power conversion efficiency of 6.13 %, which was comparable to that of the DSSC with the Pt counter electrode (6.04 %). This indicates that the mesoporous CoS₂ nanotube array can be a low‐cost and efficient alternative for the reduction of electrolytes in DSSCs.     

Facile synthesis of polymerized ionic liquids with high thermal stability

Twelve main-chain-type polymerized ionic liquids that have alkylimidazolium cation units were prepared using simple synthetic processes. The polymers were prepared using the self-polymerization of a single monomer; no polymerization initiators were required. The thermal stability and solvent miscibility of these polymers were studied. Results show that the combined anions greatly influence the solubility and thermal stability of the polymers. Among these polymers, poly-alkylimidazolium bis(trifluoromethylsulfonyl)imide polymers exhibited the highest thermal stability (>400 °C), which makes them candidates for many applications.     

New Spectral Techniques: Time-Resolved Fourier-Transform Spectroscopy and Two-Color Laser-Induced Grating Spectroscopy

Time-resolved Fourier-transform spectroscopy and two-color laser-induced grating spectroscopy are two new techniques recently employed in this laboratory. We recorded emission in the near infrared region during laser photolysis of HONO₂ with a step-scan Fourier-transform spectrometer and achieved temporal resolution in the microsecond range and spectral resolution of 0.1 cm¹. Rotationally resolved emission lines of the (0,0) band of the D ²∑⁺ →A ²∑ ⁺ transition of NO in the region 8900-9300 cnv^?1 with irregular relative intensities were observed when an ArF excimer laser was used to photodissociate HONO₂. The spectroscopic parameters of both D ²∑⁺ and A ²∑⁺ states agree with those previously reported. When a narrow-band ArF laser was used, selective rotational levels of the D state of NO were populated depending on the wavelength of the ArF laser. Our results indicate that absorption of a 193-nm photon by NO(υ″ = 1) is responsible for the observed emission. To test the technique of two-color laser-induced grating spectroscopy, we employed the B ³II_0U⁺-X ¹∑_g ⁺ system of I₂. Background-free spectra with transitions involving rotationally selected states were recorded. Various experimental schemes were employed with population gratings formed in either the B or X state. Signals due to different four-wave mixing schemes were distinguished by variation of relative timing between the grating beams and the probe beam.     

Fabrication and characterization of core-shell photonic crystals via a dipping process

High-quality polystyrene (PS) colloidal photonic crystals in large area were fabricated in 24 h via a capillary-enhanced process. Then, the photonic crystals with core-shell structure were obtained by incorporating silica nanoparticles into the interstitial space of opal template via a dipping process. The filling ratio (V_silica) of interstitial space could be manipulated by dipping colloidal crystals into suspensions with different concentrations of silica nanoparticles, which in turn renders the obtained core-shell photonic crystals. The absorptive peak of opal without dipping process is at 445 nm as measured by UV–vis spectrometry. The filling ratios of 0.130, 0.167 and 0.253 can be calculated according to the modified Bragg's Law, which corresponds to the absorptive peaks for core-shell opals at 453, 463 and 469 nm obtained from suspensions with silica nanoparticles of 0.017, 0.122, and 0.244 wt%, respectively. Therefore, by using this dipping process, the characteristic absorption wavelength for photonic crystal will be varied easily, efficiently and cost effectively than that by traditional methods for constructing opal from monodispersed colloids of different diameters.     

Synthesis,characterization, and properties of novel epoxy resins and cyanate esters

We synthesized a novel epoxy (dopotep) and cyanate ester (dopotcy) based on a phosphorus‐containing triphenol (dopotriol). The proposed structures were confirmed by IR, mass spectra, NMR spectra, and epoxy‐equivalent‐weight titration. The synthesized dopotep or dopotcy was copolymerized with diglycidyl ether of bisphenol A (DGEBA), 6′,6‐bis(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazineyl)methane (F‐a), or dicyanate ester of bisphenol A (BADCY). Thus, copolymers based on DGEBA/dopotep/diphenylmethane (ddm), F‐a/dopotep, BADCY/dopotcy, and DGEBA/dopotcy were developed. The thermal properties, dielectric properties, and flame retardancy of these copolymers were investigated. The curing kinetics of dopotep/ddm and dopotep/diamino diphenylsulfone were studied with differential scanning calorimetry. The microstructure of DGEBA/dopotcy was studied with IR. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3487–3502, 2006     

Kinetic models for solution imidization of polyamic acid containing naphthalene‐pendant group

The kinetics and mechanisms of the solution imidization of polyamic acid resulting from a diamine, bis(4‐aminophenoxy‐3,5‐dimethylphenyl)naphthylmethane, and a dianhydride, 3,3′4,4′‐diphenylsulfonetetracarboxylic dianhydride, were studied at three various temperatures (145, 165, and 180 °C). The results were confirmed by means of ¹H NMR and gel permeation chromatography (GPC). Kinetic parameters were obtained by an isothermal study, and the results were quite close to second‐order kinetics for the homogeneous solution imidization. In addition, Carother's equation, Mark–Houwink theory, and GPC were used to explain the molecular weight of the imidization processes. The apparent activation energy (E_a) was 104 KJ/mol, and the pre‐exponential factor (k₀) was 3.48 × 10¹⁴. The proposed kinetic mechanism is in good agreement with the kinetic models. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4139–4151, 2001     

Non-commutative Łukasiewicz propositional logic

The non-commutative counterpart of the well-known Łukasiewicz propositional logic is developed, in strong connection with the algebraic theory of psMV-algebras. An extension by a new unary logical connective is also considered and a stronger completeness result is proved for this system.     

A new probe of pore geometry: diffusive MASS NMR

NMR methods are widely used to probe the structure and fluid dynamics of porous materials, as they are uniquely suited to these studies since NMR records the correlation of changing local magnetic fields over a time scale of ns to seconds. The local magnetic fields are established by local variations in the bulk magnetic susceptibility of the sample (and so are directly tied to the sample's local structure). The fluctuation in field that a spin sees is due to molecular transport (including molecular diffusion) through these local fields, and so reports on the length scales of structures and impediments to transport. We have developed a new set of methods DIFFUSIVE-MASS to provide a means of systematically varying the effective time scale of the measurement and thus the effective length scale. This new handle permits a detailed, microscopic picture of the structure and dynamics. Diffusive MASS NMR methods will permit a systematic set of methods and analysis for characterizing the chemistry, structure and fluid dynamics of the mobile phase in porous materials. The approach will be applicable to any diamagnetic material. In particular, the industry of oil discovery depends on understanding heterogeneous porous media.