Tripolyphosphate-sensitive egg phosphatidylcholine liposomes incorporating hydrophobically modified poly(ethylene imine)

Liposomes, which release their contents in answer to tripolyphosphate (TPP, a penta-anion), were prepared by immobilizing hydrophobically modified poly(ethylene imine) (HmPEI) on the surface of egg phosphatidylcholine (egg PC) liposome. HmPEI was prepared by covalently attaching decanoyl chloride to PEI through a condensation reaction. According to the ¹H NMR spectrum, the number of decanoyl chloride per one molecule of PEI was about 21, and HmPEI was air/water interface-active. HmPEI could readily complex with TPP in HEPES buffer (30 mM, pH 7.0), confirmed by Fourier transformed infrared spectrophotometer spectroscopy. The complexation increased with increasing the concentration of HmPEI and TPP, investigated through the measurement of optical density and light scattering intensity. Liposomes incorporating HmPEI were prepared by a film hydration and sonication method. The liposomes were multi-lamellar vesicles, observed on transmission electron microscope. Liposomes free of HmPEI did not release calcien when they were mixed with TPP. Liposomes whose egg PC/HmPEI was relatively low (e.g., 20:1 and 20:2) released calcein but not extensively (less than 10%) when mixed with TPP. Liposomes whose egg PC/HmPEI was relatively high (e.g., 20:4 and 20:20) released calcein extensively. For example, when the liposomes with lager amount of HmPEI were mixed with TPP so that HmPEI/TPP weight ratio was 8:1, the release degree in 60 sec was more than 70%. HmPEI can complex with TPP through electrostatic interaction and the complexation was thought to cause perturbation in the liposomal membranes and trigger the release.     

磺化聚醚酰亚胺/聚醚砜共混型质子交换膜的制备及其性能

以磺化聚醚酰亚胺(SPEI)和聚醚砜(PES)为原料, 采用溶液共混法成功制备出了SPEI/PES共混型质子交换膜,并经热重分析、AFM、SEM等对膜的结构和性能进行了表征. 结果表明, 共混膜较纯SPEI膜具有更高的热稳定性和较低的溶胀性; 在室温环境下, 共混膜在干态和湿态时均具有优异的机械性能; 与纯SPEI膜相比, 共混膜的形态结构更为致密, 这将有利于降低甲醇的渗透性. 采用交流阻抗法和隔膜扩散法分别考察了膜的质子传导性和阻醇性能, 对于共混质量比为50/50的膜来说, 其质子传导率达到了5.5 mS·cm-1的水平, 能满足质子交换膜的需求, 但其甲醇渗透系数明显降低, 仅为市用Nafion 112膜的5%, 这表明该共混膜有望作为一种新型的直接甲醇燃料电池用质子交换膜.     

A new category of thermally stable poly(ether amide ether imide)s with increased solubility

Two new poly(ether amide ether imide)s (PEAEIs) were prepared from a new diamine (DA) containing ether, aliphatic, amide, naphthyl and pyridine functional groups that resulted flexible and thermally stable ultimate polymers. The DA was synthesized via two steps, starting from nucleophilic substitution reaction of 1,8‐diamino‐3,6‐dioxaoctane with 6‐chloronicotinoyl chloride in the presence of propylene oxide which, afforded dichloro‐diamide (DCDA) compound. In the second step for the preparation of DA, reaction of DCDA compound with 5‐amino‐1‐naphthol in the presence of K₂CO₃ was achieved. The new DA was then polycondensed with 2,2'‐bis‐(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride and pyromellitic dianhydride to produce PEAEIs. The precursor, monomer and obtained polymers were entirely characterized by FT‐IR and ¹H‐NMR spectroscopy and elemental analysis techniques. The physical properties of the polymers including solubility, thermal behavior, thermal stability, inherent viscosity, morphology and mechanical properties were studied. The new PEAEIs exhibited favorable balance of physical and thermal properties, and their solubility was improved without sacrificing their thermal stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Morphology control of sulfonated poly(ether ketone ketone) poly(ether imide) blends and their use in proton-exchange membranes

Polymer blends based on sulfonated poly(ether ketone ketone) (SPEKK) as the proton-conducting component and poly(ether imide) (PEI) as the second component were considered for proton-exchange membranes (PEMs). The PEI was added to improve the mechanical stability and lower the water swelling in the fuel cell environment. Membranes were cast from solution using N-methyl-2-pyrrolidone (NMP) and dimethylacetamide (DMAc). The ternary, polymer/polymer/solvent, phase diagram was determined to provide guidance on how to control the morphology during solvent casting of blend membranes.

For blends of SPEKK (ion-exchange capacity = 2 mequiv/g) with PEI as the minority component, the morphology consisted of dispersed particles of 0.5–6 μm. Larger particles were achieved by increasing the PEI content and/or lowering the casting temperature. High-temperature annealing after solution casting did not affect the morphology of blend membranes, due to the low mobility and compatibility of the two polymers.

The possible use of SPEKK/PEI blends in PEMs is discussed in terms of existing theories of ion transport in polymers.     

Synthesis and properties of poly(ether imide)s based on a benzonorbornane bis(ether anhydride)

A novel bis(ether anhydride) monomer, 3,6‐bis(3,4‐dicarboxyphenoxy)benzonorbornane dianhydride, was synthesized from the nitro displacement of 4‐nitrophthalonitrile with 3,6‐dihydroxybenzonorbornane in the presence of potassium carbonate, followed by the alkaline hydrolysis of the intermediate bis(ether dinitrile) and the cyclodehydration of the resulting bis(ether diacid). A series of poly(ether imide)s bearing pendant norbornane groups were prepared from the bis(ether anhydride) with various aromatic diamines via a conventional two‐stage process that included ring‐opening polyaddition to form the poly(amic acid)s followed by thermal imidization to the poly(ether imide)s. The inherent viscosities of the poly(amic acid) precursors were 0.81–1.81 dL/g. The poly(ether imide) with m‐phenylenediamine as a diamine showed good organosolubility. Most of the cast poly(ether imide) films have had high tensile strengths and moduli. The glass‐transition temperatures of these poly(ether imide)s, except for those from rigid p‐phenylenediamine and benzidine, were recorded between 211 and 246 °C by differential scanning calorimetry. The softening temperatures of all the poly(ether imide) films stayed within 210–330 °C according to thermomechanical analysis. No polymers showed significant decomposition before 500 °C in a nitrogen or air atmosphere. A comparative study of the properties with the corresponding poly(ether imide)s without pendant substituents was also made. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1712–1725, 2002     

Multiarm star nanocarriers containing a poly(ethylene imine) core and polylactide arms

Star polymers (SPs) containing a hyperbranched poly(ethylene imine) (PEI; number‐average molecular weight = 10,000) core and polylactide arms were synthesized via the ring‐opening polymerization of lactide. PEI was used as a multifunctional macroinitiator for the ring‐opening polymerization of lactide. Different lactide monomer/amino‐functional group (LA/NH_n; n = 1 or 2) ratios were used for preparing SPs with different molecular weights. SPs were able to encapsulate small guest molecules such as Rose Bengal; they also transported small, hydrophilic molecules from water to the organic phase. The transport capacity of all the nanocarriers depended on the LA/NH_n ratio used for synthesizing the SPs. Nanocarriers with a higher LA/NH_n ratio had higher transport capacities. The size of all the nanocarriers depended on the type of solvent. In chloroform, these nanoparticles had several sizes that were related to the self‐assembly of these nanocarriers, but in acetone, they were monodisperse, and their size was smaller than that in chloroform. Also, the transport of polar dyes from water to the chloroform phase was possible. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5740–5749, 2006     

Transition metal compatibilization of poly(vinylamine) and poly(ethylene imine)

Poly(vinylamine), PVA, complexes with cobalt chloride hexahydrate exhibit a 45 °C enhancement in the glass‐transition temperature per mol % of the d‐block metal cation. Poly(ethylene imine), PEI, complexes with CoCl₂(H₂O)₆ exhibit a 20 °C enhancement in T_g per mol % Co²⁺. Since the basicities of primary and secondary amines are comparable (i.e., pK_b,PVA ≈ 3.34 vs. pK_b,PEI ≈ 3.27) and the rates at which each polymeric ligand displaces waters of hydration in the coordination sphere of Co²⁺ are similar, transition metal compatibilization is operative in blends of both polymers with CoCl₂(H₂O)₆. These two polymers are immiscible in the absence of the inorganic component. Infrared spectroscopy suggests that nitrogen lone pairs in PVA and PEI coordinate to Co²⁺. The stress–strain response of a 75/25 blend of PVA and PEI with 2 mol % Co²⁺ reveals a decrease in elastic modulus from 4.4 × 10⁹ N/m² to 5.7 × 10⁷ N/m², a decrease in fracture stress from 3.7 × 10⁷ N/m² to 2.0 × 10⁶ N/m², and an increase in ultimate strain from 1.3 to 12% relative to the 75/25 immiscible polymer–polymer blend. A plausible explanation for this effect is based on the fact that cobalt chloride hexahydrate compatibilizes both polymers by forming a coordination bridge between nitrogen lone pairs in dissimilar chains. Hence, poly(ethylene imine), which is very weak with a T_g near −40 °C, is integrated into a homogeneous structure with poly(vinylamine) and the mechanical properties of the individual polymers are averaged in the compatibilized ternary complex. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 552–561, 2000     

聚乙烯亚胺复合铜微粒的制备及表征

以溶液还原法对聚乙烯亚胺（PEI）和Cu2＋形成的配合物进行还原,制备了金属Cu微粒。扫描电镜对微粒的分析表明,低浓度Cu2＋配合物制备的微粒形态规则、分布均匀,粒径约0.98μm。红外光谱、X-衍射对微粒组成的分析表明,PEI键合地包覆Cu微粒,没有Cu的其他氧化物存在,PEI包覆量占微粒质量的14.6%,形成的复合...     

Poly(ethylene imine)s as Antimicrobial Agents with Selective Activity

We report the structure–activity relationship in the antimicrobial activity of linear and branched poly(ethylene imine)s (L‐ and B‐PEIs) with a range of molecular weights (MWs) (500–12 000). Both L‐ and B‐PEIs displayed enhanced activity against Staphylococcus aureus over Escherichia coli. Both B‐ and L‐PEIs did not cause any significant permeabilization of E. coli cytoplasmic membrane. L‐PEIs induced depolarization of S. aureus membrane although B‐PEIs did not. The low MW B‐PEIs caused little or no hemolysis while L‐PEIs are hemolytic. The low MW B‐PEIs are less cytotoxic to human HEp‐2 cells than other PEIs. However, they induced significant cell viability reduction after 24 h incubation. The results presented here highlight the interplay between polymer size and structure on activity.

     

Controlled sulfonation of poly(arylene ether sulfone)s and poly(arylene ether ketone)s with different molecular structures for polymer electrolyte membranes

Poly(arylene ether sulfone) copolymers derived from 9,9-bis(4-hydroxyphenyl)fluorene, bisphenol S and 4,4′-difluorodiphenylsulfone and poly(arylene ether ketone) copolymers derived from 4-phenoxybiphenyl, diphenyl ether and isophthaloyl chloride were prepared as precursor polymers for sulfonation reaction in which sulfonic groups are introduced quantitatively into specified positions. Sulfonation reaction for these two series of copolymers by concentrated sulfuric acid was successfully carried out to give sulfonated polymers with controlled positions and degree of sulfonation. Thermal stability, moisture absorption and proton conductivity for these two series of copolymers were measured and the results were compared to those of perfluorosulfonic acid polymers.     

Poly(ether imide)s with tailored end groups

Poly(ether imide) (PEI) from polycondensation of 2,2-bis[4-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride (BPADA) and m-phenylenediamine (mPD) is a type of high-temperature engineering thermoplastics that have high glass transition temperature and outstanding mechanical properties. Owing to its wide use in many fields including automotive, aircraft, and electronics, the research of PEI has surged in the last few decades. As science and technology continue to progress rapidly, there is a growing demand for PEIs with better properties. Although a few approaches have successfully improved the properties of PEI, it is recognized that these approaches require complex procedures and are uneconomical. Contrastingly, end-group modification of PEI is highly effective, simple, and economical. Over the last few years, our group has extensively studied the methods for improving the properties of PEI through end-group modification. The end-group moieties and polymer blocks introduce multiple hydrogen bonding, electrostatics, and microphase separation to PEI. In this article, we first classify the end groups based on their characteristics. Then, we compare their effects on the properties of PEIs, including thermal, rheological, mechanical, optical, flame-retardant, and morphological, and discuss the roots of these effects. The in-depth comparisons and discussion generate principles to guide the synthesis of PEIs with tailored properties by modifying the end groups. This timely article will provide insights into the synthesis of other novel high-temperature polymers and entice endeavors to develop novel end groups.     

Further study of the viscoelastic phase separation of cyanate ester modified with poly(ether imide)

In this study, the viscoelastic phase separation process was studied further by time‐resolved light scattering, differential scanning calorimetry, and scanning electron microscopy in the system of poly(ether imide)‐modified bisphenol‐A dicyanate. It was observed that the evolution time of phase structure and relaxation time of diffusion flow of the bisphenol‐A dicyanate were similar with the phase diagram of curing conversion versus content of PEI. The results suggested that the viscoelastic phase separation was affected by the curing conversion of the system at the onset point of phase separation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 517–523, 2006     

Synthesis and characterization of aromatic poly(ether sulfone imide)s derived from sulfonyl bis(ether anhydride)s and aromatic diamines

Two sulfonyl group-containing bis(ether anhydride)s, 4,4′-[sulfonylbis(1,4-phenylene)dioxy]diphthalic anhydride ( IV ) and 4,4′-[sulfonylbis(2,6-dimethyl-1,4-phenylene)dioxy]diphthalic anhydride (Me- IV ), were prepared in three steps starting from the nucleophilic nitrodisplacement reaction of the bisphenolate ions of 4,4′-sulfonyldiphenol and 4,4′-sulfonylbis(2,6-dimethylphenol) with 4-nitrophthalonitrile in N,N-dimethylformamide (DMF). High-molar-mass aromatic poly(ether sulfone imide)s were synthesized via a conventional two-stage procedure from the bis(ether anhydride)s and various aromatic diamines. The inherent viscosities of the intermediate poly(ether sulfone amic acid)s were in the ranges of 0.30–0.47 dL/g for those from IV and 0.64–1.34 dL/g for those from Me- IV. After thermal imidization, the resulting two series of poly(ether sulfone imide)s had inherent viscosities of 0.25–0.49 and 0.39–1.19 dL/g, respectively. Most of the polyimides showed distinct glass transitions on their differential scanning calorimetry (DSC) curves, and their glass transition temperatures (T_g) were recorded between 223–253 and 252–288°C, respectively. The results of thermogravimetry (TG) revealed that all the poly(ether sulfone imide)s showed no significant weight loss before 400°C. The methyl-substituted polymers showed higher T_g's but lower initial decomposition temperatures and less solubility compared to the corresponding unsubstituted polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1649–1656, 1998     

Sulfonated poly(aryl ether ketone)s containing naphthalene moieties obtained by direct copolymerization as novel polymers for proton exchange membranes

A series of sulfonated poly(aryl ether ketone)s (SPAEKs) were prepared by aromatic nucleophilic polycondensation of 2,6‐dihydroxynaphthalene with 5,5′‐carbonyl‐bis(2‐fluorobenzenesulfonate) and 4,4′‐difluorobenzophenone. The structure and degree of sulfonation (DS) of the SPAEKs were characterized using ¹H NMR spectroscopy. The experimentally observed DS values were close to the expected values derived from the starting material ratios. The thermal stabilities of the SPAEKs were characterized by thermogravimetric analysis, which showed that in acid and sodium salt forms they were thermally stable in air up to about 240 and 380 °C, respectively. Transparent membranes cast from the directly polymerized SPAEKs exhibited good mechanical properties in both dry and hydrated states. The dependence of water uptake and of membrane swelling on the DS at different temperatures was studied. SPAEK membranes with a DS from 0.72 to 1.60 maintained adequate mechanical properties after immersion in water at 80 °C for 24 h. The proton conductivity of SPAEK membranes with different degrees of sulfonation was measured as a function of temperature. The proton conductivity of the SPAEK films increased with increased DS, and the highest room temperature conductivity (4.2 × 10^?2 S/cm) was recorded for a SPAEK membrane with a DS of 1.60, which further increased to 1.1 × 10^?1 S/cm at 80 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2866–2876, 2004     

聚乙烯胺类修饰萘酰亚胺衍生物的合成、DNA键合行为和活性研究

合成了二乙烯三胺、三乙烯四胺和四乙烯五胺等低分子量聚乙烯胺类修饰的萘酰亚胺衍生物.通过UV-Vis谱、荧光光谱、圆二色谱和热变性试验研究了合成化合物与小牛胸腺DNA的键合行为,同时通过四甲基偶氮唑蓝(MTT)染色法研究了化合物对Bel-7402(人肝癌细胞)、HL-60(白血病细胞)、A549(人肺癌细胞)和Hela(人宫颈癌细胞)等细胞株的体外抗肿瘤活性,化合物NI1对A549细胞显示良好的抑制活性,优于阳性对照顺铂.     

Glass transition,crystallization, and morphology relationships in miscible poly(aryl ether ketones) and poly(ether imide) blends

The relationships among glass transition, crystallization, melting, and crystal morphology of poly(aryl ether ketone) (PAEK)/poly(other imide) (PEI) blends was studied by thermal, optical and small-angle x-ray scattering (SAXS) methods. Two types of PAEK were chosen for this work: poly(aryl ether ether ketone), PEEK, and poly(aryl ether ketone ketone), PEKK, which have distinctly different crystallization rates. Both PAEKs show complete miscibility with PEI in the amorphous phase. As PAEK crystallizes, the noncrystallizable PEI component is rejected from the crystalline region, resulting in a broad amorphous population, which was indicated by the broadening and the increase of T_g over that of the purely amorphous mixture. The presence of the PEI component significantly decreases the bulk crystallization and crystal growth rate of PAEK, but the equilibrium melting temperature and crystal surface free energies are not affected. The morphology of the PEI segregation was investigated by SAXS measurements. The results indicated that the inter(lamellar-bundle) PEI trapping morphology was dominant in the PEEK/PEI blends under rapid crystallization conditions, whereas the interspherulitic morphology was dominant in the slow crystallizing PEKK/PEI blends. These morphologies were qualitatively explained by the expression δ=D/G, where G was the crystal growth rate and D was the mutual diffusion coefficient. © 1993 John Wiley & Sons, Inc.     

Synergistic mechanical behaviour and improved processability of poly(ether imide) by blending with poly(trimethylene terephthalate)

Fully miscible poly(ether imide) (PEI)/poly(trimethylene terephthalate) (PTT) blends were obtained by melt mixing in an extruder followed by injection moulding. The viscosity of PEI, represented by the pressure at the extruder output, almost halved upon the addition of only 10% PTT, allowing the use of PEI in applications where either complex parts or thin sections must be moulded. The modulus of elasticity showed a synergistic behaviour which was absolute (modulus higher than that of any of the two components) in the blend with 10% PTT. This was attributed mainly to the decrease in specific volume upon blending. The additional absolute synergism in the yield stress of PEI‐rich blends and their ductile nature depict a set of properties that make these new materials attractive in a number of new applications. Copyright ­© 2003 John Wiley & Sons, Ltd.     

Recovery as a measure of oriented crystalline structure in poly(ether ester)s based on poly(ethylene oxide) and poly(ethylene terephthalate) used as shape memory polymers

Poly(ether ester)s consisting of poly(ethylene oxide) and poly(ethylene terephthalate) segments, EOET copolymers, could be used as shape memory polymers (SMP). Crystalline structural characters of the copolymers during the memory process were investigated by dynamic mechanical analysis, differential scanning calorimeter, wide-angle X-ray diffraction, polarizing microscopy, and recovery measurements. PEO crystals in stretched EOET copolymer preferentially oriented along fiber axis or stretch direction. During stretching, the structure of the copolymer undertake a transformation from spherulite to fiber, resulting in a crystalline morphology similar to shish-kebab, and recovery properties of stretched EOET samples were dependent on as-described crystalline structural characters that can be influenced by draw ratio. Driving forces for contraction come from the oriented chains, and only oriented or extended chains can be contributive to the recovery of deformation; these extended chains involve both crystalline and amorphous segments. The recovery process in shape memory behavior was noticed to be deorientation of oriented chains due to thermodynamic entropy effect, and was divided into three stages. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 101–112, 1999     

Micellization and Thermogelation of Poly(ether urethane)s Comprising Poly(ethylene glycol) and Poly(propylene glycol)

A series of multiblock poly(ether urethane)s comprising poly(ethylene glycol) (PEG), and poly(propylene glycol) (PPG) segments were synthesized. Their aqueous solutions exhibited thermogelling behavior at critical gelation concentrations (CGC) ranging from 8 to 12 wt%. The composition and structural information of the copolymers were studied by GPC and ¹H NMR. The critical micellization concentration (CMC) and thermodynamic parameters for micelle formation were determined at different temperatures. The temperature response of the copolymer solutions were studied and found to be associated with the composition of the copolymers.     

Poly(ether imide)s derived from phthalazinone‐containing dianhydrides

An unsymmetrical and noncoplanar heterocyclic dianhydride was synthesized from a bisphenol‐like phthalazinone, 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, and a series of novel poly(ether imide)s based on it, with intrinsic viscosities of 0.67–1.42 dL/g, were obtained by one‐step solution polymerization in m‐cresol at 200 °C for 20 h. The polymers were readily soluble in N‐methyl‐2‐pyrrolidinone and m‐cresol. The poly(ether imide)s derived from 4,4′‐oxydianiline and 4,4′‐methylenedianiline were also very soluble in chloroform, 1,1′,2,2′‐tetrachloroethane, and N,N‐dimethylacetamide. The glass‐transition temperatures were 289–326 °C, as determined by differential scanning calorimetry. All the degradation temperatures for 5% weight loss occurred above 482 °C in nitrogen. The tensile strength of thin films of some of the polymers varied from 103.1 to 121.4 MPa. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6089–6097, 2004