Electrospray ionization multiple-stage tandem mass spectrometric analysis of diglycosyldiacylglycerol glycolipids from the bacteria Bacillus pumilus

Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MSn) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C-14-C-19 fatty acids, some of which were monounsaturated, Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type, The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations, The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MSn spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS2 spectra of[M + K](+) ions, it was established that all components have a C-15:0 fatty acid at the sn-2 position of the glycerol backbone and C-14-C-19 acids at the sn-1 position of the glycerol backbone. Copyright (C) 1999 John Wiley & Sons, Ltd.

Positive- and negative-ion matrix-assisted laser desorption/ionization mass spectrometry of saccharides

Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) of oligosaccharides and polysaccharides has been investigated in detail, It is demonstrated that cationized species of oligosaccharides, [M+Na](+) and [M+K](+), are dominant products under the MALDI condition, and negative ions of oligosaccharides are not formed to any significant extent in this process, The molecular masses of polysaccharides are similarly determined by positive- and negative-ion MALDI-MS with the help of column chromatography. The distinction between positive- and negative-ion MALDI mass spectra of oligo-and polysaccharides indicates that the MALDI processes for saccharides vary with molecular mass. The matrix plays a more important role in the ionization process for oligosaccharides, while in the desorption process for polysaccharides. (C) 1998 John Wiley & Sons, Ltd.

Paint-freeze method to form self-assembled alkanethiol/phospholipid bilayers on gold

A paint-freeze method for preparing self-assembled alkanethiol/phospholipid bilayers on a gold surface has been described (by cyclic voltammetry, a.c impedance, polarized FTIR-ATR) to be well-ordered and packed, stable, solvent-free bilayers. The lipid order parameter was 0.67, calculated from the dichroic ratio, consistent with a well-ordered lipid film in which the methylene groups have segmental flexibility and are disordered to a degree which is typical for a lipid bilayer in the liquid-crystalline phase. Such a supported membrane provides a useful way for studies in biophysics, physiology and electrochemistry.

Ion-conducting polymers based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CPs) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo(oxyethylene) side chains of the type -O(CH2CH2O)(n)CH3 were synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. Maximum conductivity close to 1.38 x 10(-4) S/cm was achieved at room temperature and at a [Li]/[EO] ratio (EO = ethylene oxide) of about 0.066. The temperature dependence of ionic conductivity suggested that the ion transport was controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moved to a higher salt concentration as the temperature increased, indicating that a larger number of charge carriers can be transferred through polymer chains, of which free volume is increased at higher temperature. IR results indicated that the ester in CPs might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Ionic conductivity of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with lithium salts to form amorphous polymer electrolytes. CP/salt complexes showed conductivity up to 10(-5)Scm(-1) at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Gas transport property of homo- and copolyimides from isomeric thiaphthalic dianhydride and oxydianiline

Gas transport properties of home- and copolyimides prepared from 3,3',4,4'- and 2,2',3,3'-thiaphthalic dianhydride (p-TDPA and m-TDPA, respectively) with 4,4-oxydianiline (ODA) were investigated. The fractional free volume of m-TDPA-ODA is larger than that of p-TDPA-ODA, and the chain segmental mobility of the former is lower than that of the latter. The permeability coefficients of m-TDPA-ODA to H-2, CO2, and O-2 are more increased by 48, 69 and 75%, at 30 degrees C and 10 atm, respectively, than those of p-TDPA-ODA; but the permselectivities of m-TDPA-ODA for H-2, CO2, and O-2 toward N-2 are more decreased by 33, 77, and 26%, respectively, than those of p-TDPA-ODA. The permeability coefficients and the diffusion coefficients of the copolyimides can be described by the following equations: log P = Phi(p) log P-p + Phi(m), log P-m and log D-a = D-a = Phi(p) log(D-alpha)(p) + Phi(m) log(D-a)(m), respectively. The variation of the permselectivity is controlled predominantly by diffusivity selectivity. These observations are interpreted in terms of variations in the fractional free volume of polyimides. (C) 1997 John Wiley & Sons, Inc.

Synthesis and ionic conductivity studies of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type-O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with LiNO3 to form an amorphous polymer electrolyte. CP/salt complexes showed conductivity up to 10(-5) S/cm at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Rheological studies on the phase dissolution in a block copolymer

The microphase transition in a styrene-butadiene-styrene triblock copolymer was studied by rheometric mechanical spectroscopy. A high-temperature-melt rheological transition from the highly elastic, nonlinear viscous behavior typical of a multiphase structure to linear viscous behavior with insignificant elasticity typical of a single-phase structure was observed. The transition temperature is determined according to the discontinuity of the rheological properties across the transition region, which agrees well with the results obtained from the small angle X-ray scattering data and the expectation of the random phase approximation theory. Maybe for the first time, microphase dissolution was investigated theologically. The storage modulus (G') and the loss modulus (G '') increase with time during the process. An entanglement fluctuation model based on the segmental density fluctuations is presented to explain the rheological behavior in this dissolution process. (C) 1997 John Wiley & Sons.

Gas permeation properties of copolyimides from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride

A series of aromatic copolyimides was prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropane dianhydride (6FDA) with 3,3'-dimethyl-4,4'-methylene dianiline (DMMDA) by a chemical imidization. The gas permeability coefficients of the copolyimides to H-2, CO2, O-2, N-2 and CH4 were measured under 7 atm. pressure. The fractional free volume of 6FDA-DMMDA is larger than that of HQDPA-DMMDA, while the chain segmental mobility of 6FDA-DMMDA is lower than that of HQDPA-DMMDA. The gas permeability of 6FDA-DMMDA is much higher than that of HQDPA-DMMDA but the permselectivity of 6FDA-DMMDA for H-2, CO2, O-2, N-2 over CH4 is lower than that of HQDPA-DMMDA. The experimental values of the gas permeability coefficients of the copolyimides are in satisfactory agreement with the values estimated from the gas permeability coefficients of the constituent homopolyimides and their weight fractions.

Gas separation properties of aromatic polyetherimides from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride and 3,5-diaminobenzic acid or its esters

The gas transport properties of a series polyetherimides, which were prepared from 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (HQDPA) with 1,3-phenylenediamine or 3,5-diaminobenzic acid (DBA) or its esters are reported. The effects of carboxylic group (-COOH) and carboxylic ether groups (-COOR), at five positions of 1,3-phenylenediamine moiety, on H-2, CO2, O-2, and N-2 permeability, diffusivity, and solubility of the polyetherimides were investigated. The gas permeability, diffusion, and solubility coefficients of the polyetherimides containing COOR are bigger than those of HQDPA-PDA, but the ideal separation factors and ideal diffusivity selectivity factors are much smaller than that of HQDPA-PDA because COOR decreases chain segmental packing efficiency and increases chain segmental mobility. The permeability coefficients of HQDPA-DBA to H-2, CO2, and O-2 are bigger than those of HQDPA-PDA; the ideal separation factors for gas pairs H-2/N-2, CO2/N-2, and O-2/N-2 are also much bigger than those of HQDPA-PDA. Both the diffusion coefficients of CO2 and O-2 and the ideal diffusivity selectivity factors for CO2/N-2 and O-2/N-2 are bigger than those of HQDPA-PDA because COOH decreases both chain segmental packing efficiency and chain segmental mobility. The copolyimides, which were prepared from 3,5-diaminobenzic acid and 3,5-diaminobenzic esters, have both high permeability and high permselectivity. (C) 1997 John Wiley & Sons, Inc.

Local chain motions in a dilute solution of phenolphthalein poly(ether sulfone)

C-13 and H-1 relaxation times were measured as a function of temperature in two magnetic fields for dilute solutions of phenolphthalein poly(ether sulfone) (PES-C) in deuterated chloroform. The spin-lattice relaxation times were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (J. S. model). The phenyl group rotation is treated as a stochastic diffusion by the J. S. model. The restricted butterfly motion of the phenyl group attached to the cardo ring in PES-C is mentioned but is not discussed in detail in this work. Correlation times for the segmental motion are in the picosecond range which indicates the high flexibility of PES-C chains. The correlation time for the phenyl group internal rotation is similar to that of the segmental motion. The temperature dependence of these motions is weak. The apparent activation energy of the motions considered is less than 10 kJ/mol. The simulating results for PES are also reasonable considering the differences in structure compared with PES-C. The correlation times and the apparent activation energy obtained using the J. S. model for the main chain motion of PES-C are the same as those obtained using the damped orientational diffusion model and the conformational jump model.

NMR Spectra of polyimides: Interpretation and local chain motion study

Three kinds of high-performance polyimides 1 (poly(ketone-imide) PKI), 2 (poly(ether-imide) PEI) and 3 (poly(oxy-imide) POI) were studied using nuclear magnetic resonance (NMR). The NMR spectra of the polyimides were assigned according to the comprehensive consideration of the substitution effect of different substituting groups, viz. distortionless enhancement by polarization transfer (DEPT), no nuclear Overhauser effect (NNE), analysis of relaxation time, and two-dimensional correlated spectroscopy (COSY) techniques. The structural units of these three polyimides were determined. Carbon-13 and proton relaxation times for PEI and PKI were interpreted in terms of segmental motion characterized by the sharp cutoff model of Jones and Stockmayer (JS model) and anisotropic group rotation such as phenyl group rotation and methyl group rotation. Correlation times for the main-chain motion are in the tens of picosecond range which indicates the high flexibility of polyimide chains. Correlation times for phenyl group and methyl group rotations are more than 1 order of magnitude lower and approximately 1 order of magnitude higher than that of the main chain, respectively.

LOCAL MAIN-CHAIN DYNAMICS OF PHENOLPHTHALEIN POLYETHERSULFONE

Local main chain dynamics of dissolved phenolphthalein polyethersulfone (PES-C) in solution with chloroform-d(1) were examined through C-13 NMR relaxation measurements. Spin-lattice relaxation times and NOE (nuclear Overhauser effects) factors were measured as a function of temperature. The relaxation data were interpreted in terms of main chain segmental motion by using the damped orientational diffusion model (DAMP) and the conformation jump model (VJGM) derived by Valeur, Jarry, Geny, and Monnerie. The simulation method used is N-SIMPLEX, which gives, in this study, a result of the object function less than 10(-4). Correlation times were obtained for the main chain motion of PES-C with these models and the results indicate that the main chain of PES-C are flexible. The comparison between PES-C and 1,2-polybutadiene is proposed. The distribution of the correlation time for the main chain motion by using VJGM model is discussed. The temperature dependence of correlation times for PES-C indicating the dynamical rigidity of its chains is obtained.

IONIC-CONDUCTIVITY AND DYNAMIC MECHANICAL RELAXATION OF A 2-COMPONENT EPOXY NETWORK-LICLO4 ELECTROLYTE SYSTEM

The correlation between mechanical relaxation and ionic conductivity was investigated in a two-component epoxy network-LiClO4 electrolyte system. The network was composed of diglycidyl ether of polyethylene glycol (DGEPEG) and triglycidyl ether of glycerol (TGEG). The effects of salt concentration, molecular weight of PEG in DGEPEG and the proportion of DGEPEG (1000) in DGEPEG/TGEG ratio on the ionic conductivity and the mechanical relaxation of the system were studied. It was found that, among the three influential factors, the former reinforces the network chains, reduces the free volume fraction and thus increases the relaxation time of the segmental motion, which in turn lowers the ionic conductivity of the specimen. Conversely, the latter two increase the free volume and thus the chain flexibility, showing an opposite effect. From the iso-free-volume plot of the shift factor log at and reduced ionic conductivity, it is noted that the plot can be used to examine the temperature dependence of segmental mobility and seems to be useful to judge whether the incorporated salt has been dissociated completely. Besides, the ionic conductivity and relaxation time at constant reference temperature are linearly correlated with each other in all the three cases. This result gives an additional experimental confirmation of the coordinated motion model of the ionic hopping with the moving polymer chain segment, which is generally used to explain the ionic conduction in non-glassy amorphous polymer electrolytes.

TENSILE PROPERTIES OF BLENDS OF POLY(ETHER SULFONE) WITH A POLY(ETHER IMIDE)

Blends of poly(ether sulphone) (PES) with a poly(ether imide) (PEI) in various proportions were prepared by the coprecipitation method. Mechanical properties and morphology of the blends were studied using tensile tests and scanning electron microscopy (SEM). The tensile moduli exhibit positive deviations from simple additivity. Marked positive deviations were also observed for ultimate strength. These results suggest that the PEI/PES blends are mechanically compatible. SEM study revealed that the blends are not homogeneous and the polymers are immiscible on the segmental level. However, the dispersions of the blends are rather fine. The interfaces between the two phases are excellently bonded; PEI and PES appear to interact well.