MECHANICAL RELAXATION TIME OF A TWO-COMPONENT EPOXY NETWORKLiClO_4 POLYMER ELECTROLYTE

The mechanical relaxation time of a two-component epoxy network-LiClO_4 system as a polymer electrolyte was investigated. The network is composed of diglycidyl ether of polyethylene glycol (DGEPEG) and triglycidyl ether of glycerol (TGEG), wherein LiCIO_4 was incorporated and acts as both the ionic carrier and the curing catalyst. As the relaxation time is informative to the segmental mobility, which is known to be essential for ionic conductivity, the average relaxation times of the specimens were determined through master curve construction. Experimental results showed that the salt concentration, molecular weight of PEG in DGEPEG and DGEPEG/TGEG ratio have profound effect on the relaxation time of the specimen. Among these factors , the former reinforces the network chains, leading to lengthen the relaxation time, whereas the latter two are in favour of the chain flexibility and show an opposite effect. The findings was rationalized in terms of the free volume concept.     

VISCOELASTICITY AND IONIC CONDUCTIVITY OF TWO-COMPONENT EPOXY NETWORK CONTAINING LITHIUM PERCHLORATE*

Polymeric solid electrolyte system composed of triglycidyl ether of glycerol (TGEG), diglycidyl ether of polyethylene glycol (DGEPEG)and LiClO_4 salt were synthesized. In this" system the electrolyte has a pecularity that not merely can the LiClO_4 provide ionic carriers, but also catalyze the crosslinking reaction without adding an usual curing agent. The effect of salt content and degree of crosslinking on the viscoelasticity and ionic conductivity were studied. Both WLF and VTF equations were used to treat the experimental data in order to elucidate the mechanism of ionic conduction. It was found that the ionic conductivity of the system is carded out through the segmental motion mechanism. However, the data must be treated with care. For example, in evaluating WLF parameters, the contribution concerned with ionic carrier generation with temperature to the conductivity must be differentiated from that concerned with segmental motion. Besides, the temperature range suitable to WLF equation must also be considered. For VTF equation, it might be inapplicable ff the temperature is too low and close to the glass transition temperature of the specimen. Further study is needed in order to have a quantitative information on the limitation of these equations.     

A SOLID NMR STUDY OF POLYETHERESTER-UREAS

The morphology of some polyetherester-ureas were studied by ~(13)C CP/MAS and ~1H wide-line NMR spectroscopy. It was found that the HDI and MDI based polymers have well crystallized hard segments, whereas the TDI and HMDI based ones have not. For HDI/MDI based polymers, the presented results suggest that the distribution of two kinds of hard segment units is mainly in a block form. The influences of the different hard segment and chain length on the mobility of the soft segment were also studied.     

SYNTHESIS AND CHARACTERIZATION OF A NEW COMBLIKE POLYMER BASED ON POLY (VINYL METHYL ETHER-ALT-MALEIC ANHYDRIDE) BACKBONE

A new comblike polymer host for polymer electrolyte was synthesized by reactingmonomethyl ether of poly (ethylene glycol) with poly (vinyl methyl ether alt-maleic anhydride)and endcapping the residual carboxylic acid with methanol. Butanone was selected as a solventfor the esterification in order to obtain a completely soluble product. The synthesis processwas traced through by IR. Compared with the model compounds, the presumed structure ofthis comblike polymer has been proved to be valid by ~(13)C NMR. The comb polymer is a whiterubbery solid. It can be dissolved in butanone and THF, and manifests good film formingability.     

PEO/LiClO4复合体系电解质膜的固体NMR研究

自1973年,Wright[1]等发现聚氧乙烯(PEO)/碱金属盐复合物具有离子导电性之后,人们对复合物的导电机理以及如何进一步提高复合物导电率等问题开展了大量研究.长期以来,人们普遍认为复合物中碱金属离子的传输是通过PEO非晶区的链段运动来实现的[2],因此探索新的物理或化学方法,通     

SYNTHESIS AND CHARACTERIZATION OF THERMOTROPIC COPOLYESTERS AND COPOLY (ESTER-AMIDE)S CONTAINING OXYETHYLENE-ETHER AS THE SPACER

Flexible oxyethylene-ether was introduced into the aromatic copolyesters and copoly(es-ter-amide)s to reduce the melting point of resulting polymers. The melting point was greatlyreduced to 200℃ or even lower in some cases, and the molecular weight was satisfactorilyhigh as reflected by inherent viscosity. The polymers exhibited high thermal stability and goodmechanical properties as determined by TGA and mechanical tests. The copolyester showedbetter crystallinity and liquid crystallinity than corresponding copoly(ester-amide)s with simi-lar monomer composition as reflected by POM observation and WAXD study. The meltingpoints for both copolyesters and copoly (ester-amide)s showed great dependence on the p-acetoxybenzoic acid (PAB) content in monomer composition and reached the lowest valuewhen PAB was 29 mol%.     

SYNTHESIS AND CHARACTERIZATION OF NOVEL CHIRAL SMECTIC C(Sc*) PHASE SHISH-KEBAB TYPE LIQUID CRYSTALLINE BLOCK COPOLYMERS*

A new series of chiral shish-kebab type liquid crystal block copolymers that form the smecticC(Sc~*) phase was synthesized by solution polycondensation. The copolymers were characterized by GPC.DSC. TG, POM. X-ray diffraction and polarimeter. The copolymers 7 entered into liquid crystal phase whenthey were heated to their melting temperatures (T_m) and the copolymers 8 were in liquid crystal phase at roomtemperature with low viscosities. The smectic sanded texture or focal-conic texture were observed on POM.All the chiral block copolymers showed high optical activity. No racemization has happened. Temperature-variable X-ray diffraction study together with POM and polarimetric analysis realized that they are chiralsmectic C(Sc~*) phase. Thus we offer in this report the first example of shish-kebab type liquid crystal blockcopolymers that form a chiral smectic C(Sc~*) phase. The variation of melting and isotropization temperatureswith molecular structure was also discussed.     

A STUDY ON CONFORMATIONAL STRUCTURE OF MODEL COMPOUND OF NOVEL SIDE CHAIN LIQUID CRYSTALLINE POLYMER BY USING HIGH RESOLUTION SOLID STATE ~(13)C-NMR

~(13)C-NMR chemical shifts of model compound of a novel side chain liquid crystalline polymer, poly 2.5-his (4-alkoxybenzoyloxy) styrene , have been assigned in this study. Moreover, by using high-resolution solid-state CP/MAS (cross polarization/magic angle spinning) technique, the spectrum shows that in the crystalline state the ester linkage has a conformation nearly perpendicular to the either side of ring planes, and that the alkoxy groups are not fully in zigzag form. The possible conformational changes around the mesogens from the solid state to the mesophase are discussed.     

MNDO/GIAO PERTURBATION THEORY OF NMR SHIELDING CONSTANTS

By virtue of gauge-invariant atomic orbitals (GIAO), the basic approximations of MNDO method have been applied to the SCFMO theory of nuclear magnetic shielding constants. The derived equations are used to calculate NMR shielding constants. A simpler and more effective integration for 1-electron operators 1/r_m, L_m, and L_m/r_m is proposed. By proper selection of MNDO parameters and the 2-center approximation, a satisfactory agreement is obtained between the calculated and experimental ~(13)C shielding constants for a rèpresentative set of hydrocarbons.     

NMR研究HDI与水的加成产物N-100结构

用NMR研究了六次甲基二异氰酸酯与水的加成产物N－100的结构．结果表明：N－100中含有脲基、缩二脲基、双缩二脲基、三聚体异氰脲基、异氰酸酯和氨基等基团，是一种以氢原子为交联点、胺和异氰酸酯为端基的具有复杂网络结构的多异氰酸酯．一维核磁谱及二维化学位移相关谱不但分辨出4种羰基，还确定了氮上5种不同取代结构的分子链连接情况．通过建立理论模型，准确地定量描述了N－100的网络结构．     

SYNTHESIS,CHARACTERIZATION AND OPTICAL PROPERTIES OF THE COPOLYMERS OF C_(60) AND 1-PHENYL-1-PROPYNE*

While WCl_6-Ph_4Sn fails to polymerize 1-phenyl-1-propyne (PP) at room temperature, highmolecular weight (M_w up to 410×10~3) polymers are obtained in high yields (up to 80%) when thepolymerizations of PP are carried out in the presence of C_(60) using the W catalyst under the same conditions.The polymers are soluble in common organic solvents such as THF, chloroform, and toluene. Molecularstructures of the polymers are characterized by FT-IR, UV, NMR, GPC and XRD, and it is found that C_(60) iscopolymerized with PP. Thus C_(60) plays the dual roles of comonomer and cocatalyst in the polymerizationreaction. C_(60) contents of the copolymers can be easily changed by varying the C_(60) amounts in the feedmixtures. The copolymers effectively limit strong 532 nm laser pulses, whose limiting performance issuperior to that of parent C_(60).     

STUDY ON THE SEQUENCE STRUCTURE OF SBR BY 13C—NMR METHOD Ⅰ. ASSIGNMENT FOR UNSATURAT CARBONS SPECTRA*

The sequence structures of emulsion-processed SBR and solution-processed (by lithium catalyst) SBR were investigated by ~(13)C-NMR spectroscopy. Seventeen peaks within unsaturated carbon region were recorded under the adopted experimental conditions. Assignments for these peaks were made by empirical-parameter-evaluation method.     

DMS AND ~(13)C NMR STUDIES ON THE COMPATIBILITY AND DYNAMICS OF LATEX BIDIRECTIONAL IPNS AND LATEX IPN OF PVAc/PBA

The compatibility and dynamics of latex bidirectional/nterpenetrating polymer networks (LBIPNs) and latex IPN(LIPN) of poly(vinyl acetate)(PVAc) and poly (butyl acrylate )(PBA) are investigated by means of dynamic mechanical spectroscopy (DMS) and nuclear magnetic resonance (NMR) techniques. The results of DMS show that the compatibility of the LBIPNs is much better than that of the corresponding LIPN and depends to, a large extent on the distribution of PVAc both in the core and in the shell. The results of NMR measurements indicate that the rotational correlation times of the side- groups of PBA in the LBIPN are longer than those in the LIPN. The relation between the ~(13)C linewidths of PBA and temperature is also discussed.     

SYNTHESIS AND SPECTRAL CHARACTERIZATION OF DIETHYL 2-[ARYL(4-ARYL-1,2,3-SELENADIAZOL-5-YL)METHYL]MALONATE

Synthesis and characterization of several diethyl 2-[aryl(4-aryl-1,2,3-selenadiazol-5-yl)methyl]malonates are reported.     

Production of monoclonal antibodies against hop-derived (Humulus lupulus L.) prenylflavonoids and the development of immunoassays

Monoclonal antibodies against the hop-derived prenylated chalcone xanthohumol (X) and the prenylated flavonoids isoxanthohumol (IX) and 8-prenylnaringenin (8-PN) were developed. Carboxylic acid haptens of X, IX and 8-PN were synthesized by linking a spacer to their C4′-OH group followed by subsequent coupling to bovine serum albumin (BSA) to form conjugates that were employed as immunogens in BALB/c mice to raise antibodies. The monoclonal antibodies that were secreted from the established hybridoma cell lines proved, in cross-reactivity studies, to possess highly specific binding capacities in an optimized competitive indirect ELISA. The immunoassays make use of immunogen-coated microtiterplates and a peroxidase-labeled anti-mouse IgG₁ secondary antibody with ABTS as a chromogenic substrate. For X the IC₅₀ value derived from the standard curve was 62.91 ng mL⁻¹, and for both IX and 8-PN 37.15 ng mL⁻¹. The assay was validated for the quantitative analysis of X, IX and 8-PN in urine and serum. A simple sample pretreatment procedure using a diethyl ether extraction was optimized and the recoveries and matrix effects were assessed. The validity of the established assay was tested and mean inter- and intra-assay variations in urine were 2.32% and 1.91%, respectively for X, 6.24% and 2.39%, respectively for IX and 7.18% and 0.74%, respectively for 8-PN. In serum, the mean inter- and intra-assay variations were 8.90% and 1.37%, respectively for X, 6.13% and 1.57%, respectively for IX and 6.13% and 2.43%, respectively for 8-PN. Furthermore, the method demonstrated excellent accuracy and significant correlation with measurements by an established and validated HPLC-MS method.     

Modified QuEChERS method for phenolic compounds determination in mustard greens (Brassica juncea) using UHPLC-MS/MS

A modified QuEChERS method (Quick, Easy, Cheap, Effective, Rugged, and Safe) for the determination of fifteen phenolic compounds in mustard greens (Brassica juncea) using ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) analysis was developed. The QuEChERS partitioning step and dispersive solid phase extraction (d-SPE) clean-up sorbents were investigated, aimed at phenolic compound extraction and pigment removal, respectively. QuEChERS acetate version combined with 25 mg of diatomaceous earth (DE) and 5.0 mg of graphitized carbon black (GCB) provided the best conditions for sample preparation of the target compounds. Under the optimized conditions, all phenolic compounds showed good linearity (r ≥ 0.99) over the concentration range of 0.1 to 8000 μg kg⁻¹, and the quantification limits were in the range of 0.06–230 μg kg⁻¹. The spectrophotometric analysis showed that the clean-up step promoted a significant removal of chlorophyll, which is the major pigment present in the sample. Furthermore, antioxidant activity analysis was also carried out after the clean-up step and, together with chromatographic data, showed that no significant retention of the phenolic compounds occurs in the clean-up step. Two mustard greens varieties – Southern Giant Curled (SGC) and Florida Broadleaf (FB) - were analyzed with the proposed method. Seven phenolic compounds (4-hydroxybenzoic, p-coumaric, ferulic and sinapic acids, naringenin, apigenin and kaempferol) were found in both varieties, the greatest abundance being for sinapic acid (1261.5 ± 23 μg kg⁻¹ in SGC and 1235.5 ± 26 μg kg⁻¹ in FB) and ferulic acid (2861 ± 24 μg kg⁻¹ in SGC and 3204.5 ± 45 μg kg⁻¹ in FB).