Self-assembled DNA-conjugated polymer for novel DNA chip.

We developed DNA-conjugated polymer for DNA chip fabrication. A 30 mer probe DNA and disulfide bridges were covalently attached to the polymer side chain. The DNA-conjugated polymer can be specifically adsorbed on a gold substrate surface by a self-assembly technique. The interaction between fully matched DNA and DNA-conjugated polymer was investigated by surface plasmon resonance (SPR) technique. The DNA-conjugated polymer-modified gold surface highly recognized fully matched DNA, rather than unmatched DNA. Therefore, DNA-conjugated polymer can be used for novel DNA chip fabrication.     

Influence of moisture on the viscoelastic relaxations in long aliphatic chain contained semiaromatic polyamide, (PA9‐T) fiber

The effect of moisture on the mechanical relaxation processes of semiaromatic semicrystalline polyamides synthesized by a long‐chain aliphatic diamine and terephthalic acid was investigated by dynamic viscoelastic analysis (DVA) and differential scanning calorimetry (DSC). Moreover, the implication of moisture with the amorphous and crystalline domains was also examined by temperature‐dependent wide‐angle X‐ray diffraction and Fourier transform infrared spectra. The characteristics of the relaxations such as α, β, γ, and the pronounced peak shoulder appeared at 25–100 °C in DVA tan δ curves were found to be strongly susceptible to the presence of moisture. With moisture evaporation, the peak shoulder of 25–100 °C and the β‐relaxation disappeared. The former is anticipated to originate from to the side group motion of hydrogen‐bonded water, whereas the later one is from the motions of the amide–water complex units. With the disappearance of the β‐relaxation, the γ‐relaxation appeared simultaneously in much lower temperatures and ultimately coupled with the δ‐relaxation. The γ‐relaxation is attributed to be associated with the molecular motion of the amide group and δ‐relaxation with for the motion of the methylene units. The existence of two types of water was identified in the polymer, namely, tightly bound and loosely bound. The tightly bound water is believed to be directly connected by hydrogen bonding with the strong polar groups and the loosely bound water weakly links with those connected water making hydrogen bridges. The moisture acts as a plasticizer in the polymer matrix, which causes quite a large depression in its glass transition temperature (T_g). WAXD and FTIR studies corroborated the existence of water solely in amorphous regions, i.e., no rapport of water with the crystalline parts. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2878–2891, 2003     

Synthesis of aromatic poly(thioether ketone)

Aromatic poly(thioether ketone)s were prepared by the direct polycondensation of aromatic dicarboxylic acids with aryl compounds containing ether or sulfide structures using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensation proceeded smoothly and produced aromatic poly(thioether ketone)s with inherent viscosities up to 0.73 dL/g. The synthesis of substituted aryl ketones by the reaction of substituted benzoic acids with aryl compounds in PMMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(thioether ketone)s showed a 10% weight loss in air and nitrogen at around 450 and 460°C, respectively. © 1992 John Wiley & Sons, Inc.     

Ethylene polymerization by chromium complexes with phosphorous‐bridged bisphenoxy ligand

Chromium catalysts combined with phosphorous‐bridged bisphenoxy ligands were found to be highly active for ethylene polymerization. The most efficient catalyst precursor among them, generated by combining bis[3‐tert‐butyl‐5‐methyl‐2‐hydroxyphenyl](phenyl)phosphine hydrochloride ( 1a ) and CrCl₃(THF)₃, was characterized. X‐ray analysis of (3‐tert‐butyl‐5‐methyl‐2‐phenoxy)(3‐tert‐butyl‐5‐methyl‐ 2‐hydroxyphenyl)(phenyl)phosphine bis(tetrahydrofuran)chromium dichloride ( 6 ), obtained by the reaction of 1a and CrCl₃(THF)₃ in the presence of NaH, revealed a unique structure in which one phenol moiety of the bisphenol did not coordinate to the chromium center. Complex 6 showed higher activities than those observed in the in situ catalyst system. Polyethylene of various molecular weights was obtained with differing activators. The highest activity (113.5 kg mmol (cat)^?1 h^?1) was observed when TIBA/TB was used as a cocatalyst. A medium molecular weight polymer with narrow molecular weight distribution (M_w = 128,700, M_w/M_n = 1.8) was obtained using a 6 ‐TIBA/B(C₆F₅)₃ system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3668–3676, 2007     

Synthesis of 5-heteroarylazulenes: first selective electrophilic substitution at the 5-position of azulene

1,3-Di-tert-butylazulene reacted with highly electrophilic trifluoromethanesulfonate of N-containing heterocycles to give 5-(dihydroheteroaryl)azulene derivatives in good yield and treatment of the 5-(dihydroheteroaryl)azulene derivatives with KOH afforded 5-(heteroaryl)azulenes in excellent yield.     

Continuous process for ATRP: Synthesis of homo and block copolymers

Continuous ATRP of MMA was carried out in a flow tubular reactor with varying flow rate, temperature, and [monomer]/[initiator] ratios. Changing the flow rate directly relates to the reaction time. This process produces polymer continuously with the conversion increasing with decreasing flow rate. The molecular weight (relating to the flow rate) increases linearly with conversion which is also observed when the [monomer]/[initiator] ratio was changed. The effect of altering the reaction temperature was studied and the apparent activation energy of the propagation reaction of MMA in this system was calculated to be ∼56.9 kJ mol⁻¹, close to the values reported previously. Preparation of diblock copolymers is also reported with varying comonomers and the conversion, and SEC results suggested that this continuous system is an excellent and facile way to have a continuous ATRP process.     

Strain analysis of Si by FEM and energy-filtering CBED.

Lattice strains around a platelet oxygen precipitate in Si wafer is studied by energy filtering convergent-beam electron diffraction (CBED) and calculations based on the finite element method (FEM). Local lattice strains are measured from CBD patterns obtained with a probe size less than 2 nm in a specimen thicker than 450 nm. Strains measured are compressive along a direction normal to a plate of the precipitation and tensile along a direction parallel to the plate. Two-dimensional stress fields near the precipitate are obtained with FEM computer analyses by fitting the measured strains. It appears that shear stresses are concentrated at the end of the precipitate edge and the maximum shear stress at an interface between the precipitate and the Si-matrix is 1.9 GPa. It is demonstrated that a combination of the energy filtering CBED and FEM is very useful for the study of local strains near interfaces in semiconductor devices, in particular for the study of stress fields that are too steep for application of the conventional CBED technique.