Spectral Anomalies in the Fraunhofer Diffraction Pattern

We study the spectral characteristics theoretically and experimentally in the Fraunhofer diffraction pattern formed by the diffraction of a spatially coherent, polychromatic light through a slit. It is found that the spectrum in some diffraction directions close to the singular direction is redshifted, compared to the spectrum of the incident polychromatic light, and blueshifted in other directions, and splits into two lines at the singular direction. We show that the experimental results are consistent with the theoretical expectations.     

A Large Conformational Change of a Bridged b-Cyclodextrin Dimer in Aqueous Solution

As artificial enzymes, the binding constants of cyclodextrins (CDs) and their substrates are expected to be high1. For this purpose, many kinds of bridged cyclodextrin dimers2 whose two cyclodextrins are linked by various spacers have been constructed. It was of interest to make the dimers, whose binding constants would exceed 108dm3/mol3. Up to date, the bridged cyclodextrin dimers have been extensively studied as enzyme models and as molecular receptors4-6. Recently, we synthesized a brid…     

Diisobutylaluminium hydride (DIBAL-H) as a molecular scalpel: a new mechanistic proposal for a spiroketal rearrangement

Taking advantage of our knowledge of the capacity of DIBAL-H to de-O-alkylate, we propose an alternative mechanism for a spiroketal rearrangement described by E. Suàrez. We also show that this proposal can account for the formation of the secondary product, whose original structure we propose to correct.     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004     

Completely biodegradable composites of poly(propylene carbonate) and short,lignocellulose fiber Hildegardia populifolia

The composites of biodegradable poly(propylene carbonate) (PPC) reinforced with short Hildegardia populifolia natural fiber were prepared by melt mixing followed by compression molding. The mechanical properties, thermal properties, and morphologies of the composites were studied via static and dynamic mechanical measurements, thermogravimetric analysis, and scanning electron microscopy (SEM) techniques, respectively. Static tensile tests showed that the stiffness and tensile strength of the composites increased with an increasing fiber content. However, the elongation at break and the energy to break decreased dramatically with the addition of short fiber. The relationship between the experimental results and the compatibility or interaction between the PPC matrix and fiber was correlated. SEM observations indicated good interfacial contact between the short fiber and PPC matrix. Thermogravimetric analysis revealed that the introduction of short Hildegardia populifolia fiber led to a slightly improved thermooxidative stability of PPC. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 666–675, 2004     

Exploitation of introducing of catalytic centers into layer galleries of layered silicates and related epoxy nanocomposites. I. Epoxy nanocomposites derived from montmorillonite modified with catalytic surfactant‐bearing carboxyl groups

Montmorillonite (MMT) was modified with the acidified cocamidopropyl betaine (CAB) and the resulting organo‐montmorillonite (O‐MMT) was dispersed in an epoxy/methyl tetrahydrophthalic anhydride system to form epoxy nanocomposites. The intercalation and exfoliation behavior of the epoxy nanocomposites were examined by X‐ray diffraction and transmission electron microscopy. The curing behavior and thermal property were investigated by in situ Fourier transform infrared spectroscopy and DSC, respectively. The results showed that MMT could be highly intercalated by acidified CAB, and O‐MMT could be easily dispersed in epoxy resin to form intercalated/exfoliated epoxy nanocomposites. When the O‐MMT loading was lower than 8 phr (relative to 100 phr resin), exfoliated nanocomposites were achieved. The glass‐transition temperatures (T_g's) of the exfoliated nanocomposite were 20 °C higher than that of the neat resin. At higher O‐MMT loading, partial exfoliation was achieved, and those samples possessed moderately higher T_g's as compared with the neat resin. O‐MMT showed an obviously catalytic nature toward the curing of epoxy resin. The curing rate of the epoxy compound increased with O‐MMT loading. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1192–1198, 2004     

Reversible nonlinear conduction in high‐density polyethylene/acetylene carbon black composites at various ambient temperatures

The reversible nonlinear conduction (RNC) in of high‐density polyethylene/acetylene carbon black composites with different degrees of crosslinking was studied above room temperature and below the melting point of high‐density polyethylene (HDPE). The experimental current density‐electric field strength curves can be overlapped onto a master curve, suggesting that the microscopic mechanisms for the appearance of RNC exist regardless of the ambient temperature and the crosslinking degree of the HDPE matrix. The relationship between the crossover current density and the linear conductivity can be explained in the framework of the dynamic random‐resistor‐network model. According to these results, two electron‐tunneling models are suggested to interpret the microscopic conduction behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1212–1217, 2004     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004     

A Quantum Chemical Study on Recognition of Nitro-phenols by Calix[n]arenes

A PM3 calculation in vacuum of the inclusion complexation ofo-, m-, p-nitro-phenol with calix[n]arenes is performedsuccessfully. The pathways for inclusion process are describedand the most probable structures of the 1:1 complex are soughtthrough a potential energy scan. The energy differences betweenthe inclusion complexes and the hosts, by calculation, show thatthe most stable complexation is calix[4]-p-nitro phenol andcalix[6]-m-nitro phenol.     

Behavior of cellulose in NaOH/Urea aqueous solution characterized by light scattering and viscometry

Cellulose was dissolved in 6 wt % NaOH/4 wt % urea aqueous solution, which was proven by a ¹³C NMR spectrum to be a direct solvent of cellulose rather than a derivative aqueous solution system. Dilute solution behavior of cellulose in a NaOH/urea aqueous solution system was examined by laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 6 wt % NaOH/4 wt % urea aqueous solution at 25 °C was [η] = 2.45 × 10^?2 weight‐average molecular weight (M_w)^0.815 (mL g^?1) in the M_w region from 3.2 × 10⁴ to 12.9 × 10⁴. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were 6.0 nm, 350 nm^?1, and 20.9, respectively, which agreed with the Yamakawa–Fujii theory of the wormlike chain. The results indicated that the cellulose molecules exist as semiflexible chains in the aqueous solution and were more extended than in cadoxen. This work provided a novel, simple, and nonpollution solvent system that can be used to investigate the dilute solution properties and molecular weight of cellulose. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 347–353, 2004