SURFACE MODIFICATION OF MICROPOROUS POLYPROPYLENE MEMBRANES BY GRAFT POLYMERIZATION OF N,N-DIMETHYLAMINOETHYL METHACRYLATE

Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer concentration and pre-adsorbed amount of benzoyl peroxide on grafting degree were studied respectively. It was found that the appropriate graft temperature was 75℃, at which the grafting degree was the highest and the hydrolytic decomposition of DMAEMA the lowest. Scanning electron photomicrography and the average pore diameters of the modified membranes demonstrated that part of the micropores on the membrane surface was plugged by the grafted polyDMAEMA chains, especially at high grafting degree. Contact angle and water swelling experiments showed that a moderate grafting degree could improve the hydrophilicity of the membranes. In the range of I 1.3%o-12.0% grafting degree, the water swelling percentage reached its maximum (51.1%) and the contact angle reached its minimum (74 degrees). The bovine serum albumin (BSA) adsorption experiment indicated that the grafted polyDMAEMA had a dual effect on protein adsorption. At the first stage, the BSA adsorption decreased with increasing of DMAEMA grafting degree. As the interaction between BSA and polyDMAEMA on membrane surface increased, the BSA adsorption increased with increasing of DMAEMA grafting degree.     

SYNTHESIS AND OPTICAL-ELECTRONIC PROPERTIES OF POLY [METHYLTETRAPHENYLPHENYLSILYLENE-CO- BIS（METHYLPHENYLSILYL）ACETYLENE]

Poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)acetylene) (PSA) was synthesized by the cocondensation reaction of methyltetraphenylphenyldichlorosilane and bis(chloromethylphenylsilyl)acetylene with sodium in toluene. The PSA thus obtained was soluble in most organic solvents, and its molecular weight was smaller than that of poly[(disilanylene)acetylenes] with alkyl- or aryl-substitution because of the great steric congestion of tetraphenylphenyl groups. The optical and electronic properties of the polymer were investigated. The results show that PSA has strong UV absorption and fluorescence emission, the maximum UV absorption wavelength of PSA is 330 nm, which shows a considerable red-shift in comparison with that of poly(methylphenylsilylene-co-methylphenylsilylacetylene) (PSI) and alkylsubstituted poly[(disilanylene)acetylenes]. A strong photoluminescence band at 470 nm in THF and 432 nm in benzene can be observed in the visible region, respectively. Treatment of the films of PSA with I2 vapor afforded conducting films. The conductivity of PSA thin film doped with I2 was measured to be 0.35 Scm-1 in the air which is lower than that of poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)phenylene), but higher than that of σ-π polymers without tetraphenylphenyl groups. As an explanation, the tetraphenylphenyl group is a large π-electron-conjugated group; after being introduced to the Si atoms of the polysilanes, the interaction between π-electrons of the tetraphenylphenyl groups and the σ-electrons conjugated along the Si-Si bonds is increased strongly, and the σ-electrons can be conjugated more extensively along the main chain of the polysilanes.     

SYNTHESIS AND CHARACTERIZATION OF COPOLYMER OF 2,5-BIS[（4-METHOXYPHENYL）OXYCARBONYL]STYRENE AND STYRENE WITH HIGH MOLECULAR WEIGHT

The random copolymers of styrene and 2,5-bis[(4-methoxyphenyloxycarbonyl)styrene] (MPCS) with different copolymerization ratio were synthesized by conventional free radical polymerization. The copolymer having high molecular weight was experimentally elucidated using a combination of proton nuclear magnetic resonance spectroscopy and gel permeation chromatography. The liquid crystalline behavior of the copolymer was studied using differential scanning calorimetry, X-ray diffractometry and polarized optical microscopy. It was found that the liquid crystalline behavior was dependent on the content of styrene. Experimental results show that the copolymer could turn into a liquid crystalline phase at about 180℃ when the content of styrene was less than 20%. The mechanical properties of the copolymer were also studied. Preliminary results indicate that the tensile strength decreases while the tensile modulus increases as the content of MPCS is increased.     

Optical properties of Rhodamine B and Rhodamine 6G on silver surfaces

The transmission spectra of Rhodamine B and Rhodamine 6G dyes coated on silver island films for various thickness were recorded. A strong coupling between the silver particle plasma resonance and the dye molecules is observed. The absorption of dye molecules increases when the absorption band of individual dyes and silver particles overlaps. In higher silver film thicknesses, transmission increases. The theoretical calculation using Maxwell-Garnett theory and Wang and Kerker’s results qualitatively supports the observed phenomenon. A red shift in the absorption peak of dyes on silver surfaces in comparison to solution phase absorption peak indicates photobleaching.     

Increased on-column injection temperature for gas chromatography

A way of controlling the maximum allowable oven temperature during on-column injection by the column pressure drop is suggested. An arrangement using a restriction at the column outlet for adjustment of the column inlet pressure while maintaining the same column flow has been studied. Compared to non-restricted flow, substantially increased maximum oven temperatures were obtained during on-column injection. Injections at elevated temperatures resulted in an increased speed of analysis and decreased solute adsorption on the surface of the contaminated retention gap. The method is generally applicable to analysis of high boiling mixtures. In particular, with GC-AED, such an arrangement yields a higher sensitivity due to an increased solute interaction with the excitation plasma.     

EFFECT OF HYPERCROSSLINKED RESINS SURFACE CHEMISTRY ON THE ADSORPTION OF PHENOL FROM AQUEOUS SOLUTION

Two hypercrosslinked resins with similar physical characters but different surface chemistry were synthesized and used to remove phenol from aqueous solutions. The FTIR spectra, elemental analysis and the Boehm titration were used to characterize the chemical properties of the resins. The adsorption experiments were carried out using the bottle-point technique, and the effects of the surface chemistry on the adsorption were discussed. The adsorption data fit well with the Freundlich model, indicating the heterogeneity of the resins surface. It could be seen from the experimental results that the adsorption capacity increased with the increase in the total surface concentration of oxygen-containing groups. The pH dependence and the effects of ionic strength were also discussed. The kinetic adsorption data fit well with the pseudo-second order model, and the results showed that the surface oxygen-containing groups have little effect on the adsorption rate.     

MISCIBILITY, CRYSTALLIZATION AND MECHANICAL PROPERTIES OF PPC/PBS BLENDS

In this paper,melt blends of poly(propylene carbonate)(PPC)with poly(butylene succinate)(PBS)were characterized by dynamic mechanical analysis(DMA),differential scanning calorimetry(DSC),tensile testing,wide-angle X-ray diffraction(WAXD),polarized optical microscopy and thermogravimetric analysis(TGA).The results indicated that the glass transition temperature of PPC in the 90/10 PPC/PBS blend was decreased by about 11K comparing with that of pure PPC.The presence of 10% PBS was partially miscible with PPC.The 90/10 PPC/PBS blend had better impact ==========and tensile strength than those of the other PPC/PBS blends.The glass transition temperature of PPC in the 80/20,70/30,and 60/40 PPC/PBS blends was improved by about 4.9 K,4.2 K,and 13 K comparing with that of pure PPC,respectively;which indicated the immiscibility between PPC and PBS.The DSC results indicated that the crystallization of PBS became more difficult when the PPC content increased.The matrix of PPC hindered the crystallization process of PBS.While the content of PBS was above 20%,significant crystallization-induced phase separation was observed by polarized optical microscopy. It was found from the WAXD analysis that the crystal structure of PBS did not change,and the degree of crystallinity increased with increasing PBS content in the PPC/PBS blends.     

Covalent and electrostatic incorporation of amines into hypercrosslinked polymers for increased CO2 selectivity

Two methods of incorporating functional groups rich in nitrogen into low cost microporous hypercrosslinked polymers (HCPs) have been evaluated and the effects on the carbon dioxide CO₂/N₂ IAST selectivity were measured. Electrostatic incorporation of an ammonium salt into a sulfonic acid-containing HCP polymer afforded a static CO₂ uptake of 2.5 mmol g⁻¹ with a CO₂/N₂ IAST selectivity of 42:1 at 1 bar and 298 K. Using column breakthrough measurements with a 15:85 CO₂/N₂ mixture at 298 K and 1 bar, a selectivity of 17:1 was obtained. However, varying the counterion resulted in polymers with lower CO₂/N₂ selectivity values. Decoration of the parent polymer with CO₂-philic imidazole followed by electrostatic ammonium salt incorporation blocked some of the micropores reducing the selectivity which re-emphasizes the role and importance of pore width for CO₂/N₂ selectivity. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2513–2521     

Silver Fractal-Like Structures for Metal-Enhanced Fluorescence: Enhanced Fluorescence Intensities and Increased Probe Photostabilities

Substantial increases in fluorescence emission from fluorophore-protein–coated fractal-like silver structures have been observed. We review two methods for silver fractal structure preparation, which have been employed and studied. The first, a roughened silver electrode, typically yielded a 100-fold increase in fluorophore emission, and the second, silver fractal-like structures grown on glass between two silver electrodes, produced a 500-fold increase. In addition, significant increases in probe photostability were observed for probes coated on the silver fractal like structures. These results further serve to compliment our recent work on the effects of nobel metal particles with fluorophores, a relatively new phenomenon in fluorescence we have termed both metal-enhanced fluorescence [1] and radiative decay engineering [2,3]. These results are explained by the metallic surfaces modifying the radiative decay rate () of the fluorescent labels. We believe that this new silver-surface preparation, which results in ultrabright and photostable fluorophores, offers a new generic technology platform for increased fluorescence signal levels, with widespread potential applications to the analytical sciences, imaging, and medical diagnostics.     

2,2,6,6-Tetramethyl-4-Amino[d17]Piperidine-15N-1-OXYL as a Spin Label For Cell Surface Carbohydrates

Abstract

The first use of perdeuterated, ¹⁵N-Tempamine spin label to selectively monitor cell surface sialic acid of human erythrocyte membranes is reported. The molecular reasons for significantly increased sensitivity and significantly decreased scatter in the data over that of protonated, ¹⁴N-Tempamine are discussed. These advantages are illustrated by monitoring the effects of wheat-germ agglutinin on the motion of terminal sialic acid of membrane glycoconjugates.