Birefringence control by hydrogen bonding on compatible polymer pair composed of hydrogenated ring‐opening polymer and modified polystyrene

A new polymer blend composed of a hydrogenated ring‐opening polymer (HROP) with an ester group and hydroxyl functionalized polystyrene (HFP) produced the excellent transparent materials which enabled a precise birefringence control in keeping with the other physical properties for optical film use. The blend with a composition from 0.28 to 0.35 for the HFP weight fraction showed an extraordinary wavelength dispersion, transmitting through a zero birefringence point at the critical fraction of 0.45, while each polymer showed an ordinary wavelength dispersion. The observed excellent transparency even above those of the glass transition temperature was attributed to a depressed phase separation that resulted from strong hydrogen bond between the ester and hydroxyl groups. An IR analysis of the film demonstrated a remarkable red‐shift in the carbonyl peak with an increase of the hydroxylated polystyrene content, indicating a strong hydrogen bond between those groups. This new polymer blend provides a useful design to achieve practical demands for film use, both optical and mechanical under the fabrication conditions using the melt extrusion technique. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3132–3143     

Estimation of Activation Energy from the Survival Yields: Fragmentation Study of Leucine Enkephalin and Polyethers by Tandem Mass Spectrometry

A simple collision model for multiple collisions occurring in quadrupole type mass spectrometers was derived and tested with leucine enkaphalin a common mass spectrometric standard with well-characterized properties. Implementation of the collision model and Rice-Ramsperger-Kassel-Marcus (RRKM) algorithm into a spreadsheet software allowed a good fitting of the calculated data to the experimental survival yield (SY) versus collision energy curve. In addition, fitting also ensured to estimate the efficiencies of the kinetic to internal energy conversion for Leucine enkephalin in quadrupole-time-of-flight and triple quadrupole instruments. It was observed that the experimental SY versus collision energy curves for the leucine enkephalin can be described by the Rice-Ramsperger-Kassel (RRK) formalism by reducing the total degrees of freedom (DOF) to about one-fifth. Furthermore, this collision model with the RRK formalism was used to estimate the critical energy (E _o ) of lithiated polyethers, including polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetrahydrofurane (PTHF) with degrees of freedom similar to that of leucine enkephalin. Applying polyethers with similar DOF provided the elimination of the effect of DOF on the unimolecular reaction rate constant. The estimated value of E _o for PEG showed a relatively good agreement with the value calculated by high-level quantum chemical calculations reported in the literature. Interestingly, it was also found that the E _o values for the studied polyethers were similar.

Ligand size distribution of phenanthroline-functionalized polyethylene glycol-iron(II) complexes determined by electrospray ionization mass spectrometry and computer simulation

The complex formation in solution, and the gas-phase dissociation of a phenanthrolineterminated poly(ethylene glycol) with Fe²⁺ ions were investigated. The size distribution of poly(ethylene glycol)-α-monomethyl-ω-5-[1,10]phenanthroline (mPEG_phen) was determined by electrospray ionization mass spectrometry (ESI-MS). Based on the measured ligand size distribution of mPEG_phen by ESI-MS, the 1:3 complex formation (Fe²⁺/mPEG_Phen) was computer-simulated as a pure random assembly process. The simulated distribution fits excellently to that of the complex Fe(mPEG_phen)₃²⁺ determined from the ESI-MS intensities. In addition, the collision-induced dissociation (CID) of the Fe(mPEG_phen)₃²⁺ complex was also studied by tandem mass spectrometry (ESI-MS/MS) and by computer simulation, as well. The ESI-MS/MS intensity distribution of the Fe(mPEG_phen)₂²⁺ formed from Fe(mPEG_phen)₃²⁺ by the loss of an mPEG_phen ligand under CID conditions fits quite well to the calculated one.     

Mesogenicity of testosterone and estrone derivatives

Mesogenicity of 3β, 17β-bis(4-n-alkoxybenzoyloxy) androstene homologues (BABA) (carbon No. of alkoxy group, n, = 1-10) were studied by use of D.S.C. and a polarized microscopy. It was found that the n = 4-10 compounds of BABA have one cholesteric mesophase with high thermal stability enantiotropically, and that the n = 1-3 compounds decompose just above the melting point. Mesogenicities of BABA and several testosterone and estrone derivatives were also discussed from the perspective of chemical structure and shape. The presence of an intramolecular long-range dipole coupling in two alkoxybenzoyloxy chromophores is found in BABA from CD spectral studies.     

Direct analysis in real time mass spectrometry (DART‐MS) of highly non‐polar low molecular weight polyisobutylenes

Low molecular weight polyisobutylenes (PIB) with chlorine, olefin and succinic acid end‐groups were studied using direct analysis in real time mass spectrometry (DART‐MS). To facilitate the adduct ion formation under DART conditions, NH₄Cl as an auxiliary reagent was deposited onto the PIB surface. It was found that chlorinated adduct ions of olefin and chlorine telechelic PIBs, i.e. [M + Cl]^? up to m/z 1100, and the deprotonated polyisobutylene succinic acid [M? H]^? were formed as observed in the negative ion mode. In the positive ion mode formation of [M + NH₄]⁺, adduct ions were detected. In the tandem mass (MS/MS) spectra of [M + Cl]^?, product ions were absent, suggesting a simple dissociation of the precursor [M + Cl]^? into a Cl^? ion and a neutral M without fragmentation of the PIB backbones. However, structurally important product ions were produced from the corresponding [M + NH₄]⁺ ions, allowing us to obtain valuable information on the arm‐length distributions of the PIBs containing aromatic initiator moiety. In addition, a model was developed to interpret the oligomer distributions and the number average molecular weights observed in DART‐MS for PIBs and other polymers of low molecular weight. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of a novel constrained α-amino acid with quinoxaline side chain: 7-amino-6,7-dihydro-8H-cyclopenta[g]quinoxaline-7-carboxylic acid

A novel constrained 7-amino-6,7-dihydro-8H-cyclopenta[g]quinoxaline-7-carboxylic acid derivative was prepared starting from 4,5-dimethyl-o-phenylenediamine.     

Combined EPMA and AES depth profiling of a multilayer Ti-Al-O-N coating

In order to compare thin-film electron probe microanalysis (EPMA) and Auger electron spectroscopy (AES) regarding reliability in quantifying chemical compositions of Ti-Al-O-N coatings with depth, a multilayer was prepared on a silicon wafer by using reactive ionized cluster beam deposition technique. Within a total thickness of about 25 nm the composition of the multilayer varied step by step from Ti-Al-O-N at the bottom to Al-O at the top. AES and, as an innovation, EPMA crater edge profiling was applied to measure the composition with depth. For quantification special thin-film EPMA techniques based on Monte Carlo simulations were applied. The chemical binding states of Al and Ti with depth were analysed using a high resolution energy analyser (MAC 3) for the AES investigations working in the direct mode. According to the deposition procedure the concentration profiles of the components varied with depth for both AES and EPMA measurements. AES provided a better depth resolution than EPMA. To get a true calibration of the depth scale an in-situ measurement method like an optical interferometry will be required. Assuming that the relative sensitivity factors are available AES depth profiling delivers concentration profiles with good accuracy. The new EPMA application provided quantitative depth profiles concerning concentration and coverage. For EPMA crater edge profiling the coating needs to be deposited on a foreign substrate because depth distributions of elements being present in both the layer and the substrate cannot be resolved.The combination of AES-depth profiling with EPMA crater edge profiling techniques is a powerful tool to analyse heterostructures quantitatively.     

Gas chromatographic determination of lower fatty acids in gaseous samples via conventional in situ derivatization of the strontium salts catalysed by poly(crow ether)

Poly(crown ether)-catalysed derivatization of lower fatty acids with p-bromophenacyl bromide or pentafluorobenzyl bromide has been used for their determination in gaseous samples by gas chromatography (employing either flame-ionization or electron-capture detection). Stontium hydroxide was employed as a base for the derivatization, taking advantage of the fact that a column packed with strontium hydroxide-coated glass beads is very suitable for preconcentration of the fatty acids from ambient air. In situ derivatization of lower fatty acids, preconcentrated on the glass beads as their strontium salts, proceeded nearly quantitatively in acetonitrile. Traces of lower fatty acids in artificial sample gases could be determined successfully using this conventional derivatization followd by direct injection of the reaction mixture into a gas chromatograph.     

Upper Bound on the Diameter of a Domination Dot-Critical Graph

A vertex of a graph is called critical if its deletion decreases the domination number, and an edge is called dot-critical if its contraction decreases the domination number. A graph is said to be dot-critical if all of its edges are dot-critical. In this paper, we show that if G is a connected dot-critical graph with domination number k??? 3 and diameter d and if G has no critical vertices, then d??? 2k?3.