Structure and properties of the mesophase of syndiotactic polystyrene. II. Effect of stepwise extraction on the preparation of the mesophase

In this study, a novel stepwise extraction method has been examined. The guest molecules housed between the helices of the clathrate δ form of syndiotactic polystyrene can be removed completely with this method. A systematic study of the preparation of a solvent‐free mesophase (emptied clathrate) membrane, its helical and residual solvent contents, and its structural transformations has been performed. In this first attempt, an enhancement in the TTGG helical content has been observed in the extracted membrane, and a conceptual mechanism is proposed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 269–273, 2003     

Structure and properties of the mesophase of syndiotactic polystyrene—III. Selective sorption of the mesophase of syndiotactic polystyrene

Syndiotactic polystyrene (sPS) has various crystalline forms such as α, β, γ, and δ forms, and a mesophase depending on the preparation method. In this study, we focused on the mesophase with the molecular cavity of sPS, which is obtained by step‐wise extraction of the guest molecules from the sPS δ form. To prepare the mesophase containing different shapes and sizes of the cavity, two kinds of the sPS δ form membrane cast from either toluene or chloroform solution were first prepared and then the guest molecules were removed by a step‐wise extraction method using acetone and methanol. We could succeed in the preparation of two kinds of mesophase with different shapes and sizes of the molecular cavity. Either toluene or chloroform vapor sorption to the sPS mesophase membranes was examined at 25 °C. Sorption analysis indicates that the mesophase with large molecular cavities can mainly sorb large molecules; on the other hand, the mesophase with small cavities can sorb only the small molecules, and is unable to sorb a large amount of large molecule because the cavity was too small to sorb the large molecules. Therefore, the sPS mesophase membrane has sorption selectivity based on the size of the molecular cavity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 238–245, 2004     

Analysis of rabbit tear proteins by high-pressure liquid chromatography/electrospray ionization mass spectrometry

The aim of this study was to develop a fast and reliable analytical procedure for the display of the protein components of tears that can be used to differentiate the status of the ocular surface. Using this new procedure, we analyzed the tear protein components following a corneal wound in the rabbit. Calibrated 10-microL glass, fire-polished capillary micropipettes were used to collect tears from New Zealand White rabbits prior to and daily for 9 days following a unilateral 6-mm diameter centrally placed anterior keratectomy. Tear proteins were eluted by a reversed-phase high-performance liquid chromatography (RP-HPLC) column and the tear protein profile was monitored by electrospray ionization (ESI) mass spectrometry positive total ion current (TIC) chromatography. Tear proteins were reliably separated into 17 peaks, each of which contained one or a number of protein components. The molecular weight of each protein component was determined by on-line ESI. Major tear protein components, lactoferrin, lysozyme (minimally detectable in rabbit tears), albumin, lipocalin, lipophilin and beta2-microglobulin, were tentatively identified by this method. Based on the mass spectrometric data, beta2-microglobulin was found to be glycosylated with N-acetylhexosamine. ESI-positive TIC chromatograms and mass spectra revealed comparative differences in the tear protein spectra after corneal wounding. One day after wounding, rabbit lysozyme with a molecular weight of 14,717 Da was found to be 8-fold higher in the tears of wounded eyes when compared with tears from unwounded eyes. It dropped back to normal 3 days after wounding. The expression of an unidentified tear protein with the molecular weight of 16,060 Da was also elevated after corneal wounding and returned to normal level by day 5. In this study, LC/ESI-MS was developed as a fast, reproducible and simple method for the identification and analysis of many of the protein components of the tears. Importantly, this technique also allows quantification of each component resolved in the chromatogram. This method is very suitable for mapping peptides and proteins (<80 kDa) in tears.     

Effect of s-, p-, d-, and f-block elements on the structure and properties of ammonium dihydrogen phosphate crystals

The influence of the s-, p-, d-, and f-block elements (Cs, Sb, Pd, and Ce) doping on the properties of ammonium dihydrogen phosphate (ADP) crystals has been described. Incorporation of small quantity of dopants into the crystalline matrix is well confirmed by energy dispersive X-ray spectroscopy (EDS) and inductively coupled plasma (ICP) techniques. The reduction in the intensity observed in powder X-ray diffraction (XRD) of doped specimens and slight shifts in vibrational frequencies confirm the lattice stress. Surface morphological changes due to doping of metals are observed by scanning electron microscopy (SEM). The differential scanning calorimetry (DSC) curves show only a slight variation in endothermic peak temperatures. The sharpness of the DSC peaks shows the good degree of crystallinity of the material. The cell parameters have been determined using single crystal XRD analysis of pure ADP and ADP:Cs/ADP:Sb/ADP:Pd/ADP:Ce specimens. The influence of metals on the second harmonic generation (SHG) efficiency is also investigated.     

Synthesis and Stereodynamics of N-Formyl-1,2,3- Selenadiazolopyridines

Abstract

The 4,6-diaryl-6,7-dihydro-[1,2,3]selenadiazolo[5,4-c]pyridine-5(4H)-carbalde hydes were synthesized from 2,6-diarylpiperidin-4-ones and characterized using infrared, ¹H, ¹³C Nuclear Magnetic Resonance (NMR), and mass spectroscopic techniques. On the NMR time scale, the compounds exist in syn and anti isomeric forms. Separate signals were obtained for isomers in the NMR spectra. The compounds’ stereodynamic nature was studied based on the intensity and position of NMR signals.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

A simple spectrophotometric method for the determination of zirconium in U–Zr alloy samples in presence of fluoride ions

Journal of Radioanalytical and Nuclear Chemistry - A spectrophotometric method, circumventing interference from F− ions, during estimation of Zr in U-Zr alloy fuel, has been developed....     

Influence of substrate temperature on microcrystalline structure and optical properties of ZnTe thin films

ZnTe thin films were deposited onto well‐cleaned glass substrates kept at different temperatures (Ts = 303, 373 and 423 K), by vacuum evaporation method under the pressure of 10^–5 Torr. The thickness of the film was measured by quartz crystal monitor and verified by the multiple beam interferometer method. The structural characterization was made using X‐ray diffractometer with filtered CuKα radiation. The grain sizes of the microcrystallines in films increases with increase in substrate temperature. The strain (ε), grain size (D) and dislocation density (δ) was calculated and results are discussed based on substrate temperature. Optical behaviour of the film was analyzed from transmittance spectra in the visible region (400–800 nm). The optical transition in ZnTe films is direct and allowed type. The optical band gap energy shows an inverse dependence on substrate temperature and thickness. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Solution structure and conformational dynamics of deoxyxylonucleic acids (dXNA): an orthogonal nucleic acid candidate

Orthogonal nucleic acids are chemically modified nucleic acid polymers that are unable to transfer information with natural nucleic acids and thus can be used in synthetic biology to store and transfer genetic information independently. Recently, it was proposed that xylose-DNA (dXNA) can be considered to be a potential candidate for an orthogonal system. Herein, we present the structure in solution and conformational analysis of two self-complementary, fully modified dXNA oligonucleotides, as determined by CD and NMR spectroscopy. These studies are the initial experimental proof of the structural orthogonality of dXNAs. In aqueous solution, dXNA duplexes predominantly form a linear ladderlike (type-1) structure. This is the first example of a furanose nucleic acid that adopts a ladderlike structure. In the presence of salt, an equilibrium exists between two types of duplex form. The corresponding nucleoside triphosphates (dXNTPs) were synthesized and evaluated for their ability to be incorporated into a growing DNA chain by using several natural and mutant DNA polymerases. Despite the structural orthogonality of dXNA, DNA polymerase β mutant is able to incorporate the dXNTPs, showing DNA-dependent dXNA polymerase activity.     

Synthesis and Characterization of Organosoluble Polyimides Containing Pyridyl Moiety with Ether Linkages

Two novel diamine monomers, bis(4‐amino‐3,5‐dimethylphenyl)‐3‐pyridyl methane and bis(4‐aminophenoxy‐3,5‐dimethylphenyl)‐3‐pyridyl methane were synthesized. A series of pyridine containing aromatic polyimides derived from the diamines were synthesized through a typical two‐step polymerization method. Most of the polymers show good solubility in NMP, DMAc, DMF, DMSO and CHCl₃ at room temperature. These polyimides exhibit T_g in the range of 249–317°C and 10% wt loss (T₁₀) takes place in the range of 474–564°C in N₂ and 469–558°C in air. The polymers have tensile strength in the range of 88–96 MPa, elongation at break in the range of 8.5–12.5% and tensile modulus in the range of 1.5–2.1 GPa. These polyimides also have low dielectric constant (3.26–3.64 at 1 KHz and 3.24–3.61 at 10 KHz) and low moisture absorption (0.42–0.89%).     

Solvent‐Free Nucleophilic Addition of N‐Alkylhydroxylamines to Substituted Nitroolefins: Formation of Nitrones by a Tandem process

Nucleophilic addition of 1‐methyl‐2‐arylethylhydroxylamine to substituted β‐nitrostyrene under solvent‐free conditions has led to unexpected nitrones via a tandem process involving 1,4‐addition and elimination.