Molecular dynamics calculations of an amorphous interfacial system of poly(methyl methacrylate) (PMMA) and poly(tetrafluoroethylene) (PTFE) containing about 10,000 interaction sites were performed for 15 ns under constant pressure and constant temperature conditions. The time evolutions of the thickness, density and number of atomic pairs in the interfaces suggested that the interfaces reached their equilibrium states with an interfacial thickness of about 2 nm at 500 K. The molecular motion in the interface and bulk was compared using mean square displacement and torsional autocorrelation function. The separation at a PMMA/PTFE interface was mimicked using non-equilibrium molecular dynamics calculations by applying the potential energy to the MD cell in a direction perpendicular to the interface. Initially, the PTFE layer close to the interface was deformed, and before complete separation, some segments of the PTFE molecules extended from the bulk to the surface of the PMMA layer, which were attached by the intermolecular interaction. The remaining PTFE molecules were entangled in the bulk, which probably prevented the transfer of the PTFE molecules to the surfaces of the PMMA layers. On the other hand, the PMMA layer was only slightly deformed. This separation behavior can be explained by taking into account the intermolecular interaction, the barrier to the conformational changes of the backbones and the entanglement of the PTFE molecules in the bulk. 相似文献
The solubility of naphthalene was investigated in aqueous solutions of triblock copolymers poly(ethylene glycol)–poly(propylene glycol)–poly(ethylene glycol) (PEG–PPG–PEG) and (2-hydroxypropyl)cyclodextrins. The results with solutions of the individual solubilizers were as expected: the solubility enhancement was much higher with a micelle-forming copolymer than with the non-micellizing one and with (2-hydroxypropyl)--cyclodextrin (HPBCD) than with (2-hydroxypropyl)--cyclodextrin (HPACD). Although the formation of inclusion complexes between HPACD and PEG and between HPBCD and PPG is well established, the naphthalene solubility in mixed solutions does not significantly deviate from that predicted for a mixture of independent solubilizers. Thus the interactions between HPCD and PEG–PPG–PEG copolymers are not strong enough to disrupt micelles and aggregates formed by those copolymers. In fact, slight synergetic deviations were observed with the micellizing copolymer, indicating the existence of ternary naphthalene/HPCD/copolymer interactions. For pharmaceutical applications, it is important that the solubilization efficacy of PEG–PPG–PEG copolymers and that of cyclodextrins modified by the 2-hydroxypropyl group would not be compromised if these two types of solubilizers were co-administered. 相似文献
A series of triblock copolymers composed of poly(ethylene glycol) (PEG) and poly(β-amino ester urethane) (PAEU) was synthesized and characterized. Its aqueous solution can be used as a non-cytotoxic, biodegradable, and pH/temperature-sensitive hydrogel system. The copolymer solutions exhibited sol-to-gel and gel-to-sol transitions with increasing pH and temperature, respectively. The properties of this hydrogel system, such as its sol–gel transition diagram, mechanical properties, and degradation rate, can be controlled by modulating the PEG molecular weight, PAEU block length, copolymer concentration, or structure of the monomers. The presence of urethane groups and ionized tertiary amine groups in the copolymer solution at lightly acidic pH may lead to a strong interaction of the copolymer with formulated bioactive therapeutic agents, while the existence of the gel state under physiological conditions (37 °C, pH 7.4) may enable this copolymer hydrogel to be applicable as a drug/protein carrier. 相似文献
This paper presents a computational study on the formation of a molecular necklace formed by specific threading of cyclodextrins (CDs) on block copolymers. Structural as well as energetic principles for the selective complexation of - and -cyclodextrin with poly(ethylene oxide)–poly(propylene oxide) block copolymers (PEO–PPO) are elucidated considering a diblock copolymer of equimolecular composition (PEO)4–(PPO)4 as guest. A non-statistical distribution of CDs, i.e. -CDs primarily located on the PEO chain and -CDs on PPO blocks of the polymer, is based on a variety of structural features and energetic preferences considering both potential as well as solvation energies. This selectivity becomes already obvious considering 1:1 complexes between PEO and PPO monomers and the two CDs, but is increasingly evident when calculating higher order ensembles. Besides the host–guest interaction, docking between CDs themselves is an important, also non-statistical, prerequisite for the self-assembly of highly ordered tubes. The formation of intermolecular hydrogen bonds between adjacent CDs in a tubular aggregate gives an important contribution to the overall stability of the molecular necklace. The net effect, based on the preferential interaction between host and guest as well as between the host molecules themselves, results in the formation of a stable, highly ordered macromolecular, multicomponent aggregate. 相似文献
New hydrogels based on polyethylene glycol (PEG) and poly(vinyl alcohol) (PVA) of different degrees of hydrolysis were synthesized. To form the network the PEG was modified at their ends with acyl chloride groups to be used as the crosslinking agent. The compositions of the hydrogels were between 50% and 90% by weight of PEG and PVA of various degrees of hydrolysis were used. It was found that the degree of hydrolysis of the PVA and the PEG content influence the equilibrium water content of the hydrogel. The process of swelling of all the hydrogels prepared followed a second-order kinetics. 相似文献
The enzymatic hydrolysis by Humicola lanuginosa lipase (HLL) of spread insoluble monolayers of poly (α-hydroxy acid)s with various molecular weights and various lactic–glycolic
molar ratios was studied using a barostat surface balance. The interfacial hydrolysis under enzyme action leads to the progressive
fragmentation of the polymer molecules. The appearance at the interface of charged insoluble fragments was detected by measuring
the surface potential, while the solubilization of the small soluble fragments was detected by measuring the decrease in the
surface area. The data obtained were used to test the mode of fragmentation: either random or chain-end scission. The catalytic
specific activity of HLL was estimated in the framework of the random scission model and compared with the activities obtained
for the hydrolysis of simple molecules of di- and tri-glycerides organized as monolayers or emulsion.
Received: 9 August 1999 Accepted: 4 January 2000 相似文献
Shape-memory poly(p-dioxanone)–poly(e-caprolactone)/sepiolite(PPDO–PCL/OSEP) nanocomposites with different OSEP nanofiber loading were fabricated by chain-extending the PPDO-diol and PCL/OSEP precursors. The precursors and the composites were characterized by1 H NMR, FT-IR, GPC, SEM and TEM.The results demonstrate that a part of PCL segments grafted on the surface of OSEP and composites display a fine dispersion of OSEP fiber in nanoscale with low OSEP content. The shape memory effect(SME) was evaluated by DMA, the results reveal that the PPDO–PCL/OSEP nanocomposites exhibit desirable shape-memory performance. The reinforcement of composites by incorporation of trace OSEP nanofiber evokes an effective improvement in shape-memory recovery stress. 相似文献
Hydrophilic polymeric films based on blends of poly(acrylic acid) and poly(vinyl methyl ether) (PVME) were prepared by casting technique and were cross-linked by gamma-radiation. The films are soft and elastic in a dry state and form hydrogels upon immersion in water. Effect of absorbed dose on the gel fraction as well as on the swelling of the films in aqueous solutions of different pH is studied. It was found that addition of lower molecular weight PVME decreases the gelation dose, which is likely related to a decrease in glass transition temperature of the blends. In acidic media the films have low swelling degree because of suppression of carboxylic groups ionisation and formation of additional physical cross-links via interpolymer hydrogen bonding. 相似文献
The behavior of commercial poly(ethylene oxide)(PEO)–poly(propylene oxide)(PPO)–PEO triblock copolymers at the water/air
interface and in microscopic foam films is studied. In aqueous solution these amphiphilic nonionic substances exhibit a surfactant-like
aggregation and adsorption behavior. Even below the critical micelle concentration (cmc) the surface concentration is so high
that the PEO chains are squeezed and protrude into the solution in order to accommodate to the situation at the interface.
As evidenced by measurements of the ellipticity of light reflected from the free surface of the solution a PEO brush is created
at the fluid interface. The microscopic foam film is used as a tool for investigating the normal interaction between two PEO
brushes facing each other. Stable foam films are obtained at concentrations below the cmc and steric repulsion predominates
(in 0.1 M NaCl). A brush-to-brush contact is established only at higher capillary pressures and the disjoining pressure isotherm
follows de Gennes' scaling prediction. At lower pressure a softer steric repulsion occurs. It is governed by the bulk copolymer
concentration and hence is fundamentally different from the brush-to-brush repellency. On the whole PEO–PPO–PEO copolymers
behave as nonionic surfactants, but the large size of their molecules exemplifies the excluded-volume features.
Received: 13 July 1999/Accepted: 27 July 1999 相似文献
The structure and flow behaviour of a micellar “cubic” phase is studied, using small-angle X-ray scattering (SAXS) and constant
stress rheometry on a poly(oxyphenylethylene)–poly(oxyethylene) diblock copolymer in water. The predominant structure is a
face-centred cubic (fcc) array of spherical micelles, which under shear undergoes layer sliding to give a scattering pattern
from stacked hexagonal close-packed layers. A detailed analysis of the SAXS data indicates the presence of a fraction of grains
with a structure distorted from a fcc phase. The additional reflections that characterize this structure can be indexed to
a rhombohedral unit cell, space group R3ˉm, with the same volume as the fcc unit cell. The rhombohedral unit cell corresponds to a cubic cell that has been “stretched”
along a [111] direction, and it is suggested that such a structure results from the gradient in shear velocity in the Couette
cell employed. Shearing at high shear rates leads to a “smearing out” of the reflections, but upon cessation of shear under
these conditions a highly oriented SAXS pattern is obtained, which confirms the persistence of rhombohedral ordering. The
shear-induced changes in orientation are correlated to a plateau observed in the stress plotted against shear rate, such a
plateau being a sign of inhomogeneous flow.
Received: 8 September 2000 Accepted: 29 November 2000 相似文献
Aqueous polyurethane dispersions (PUDs) with poly(dimethylsiloxane) (PDMS), or mixed poly(dimethylsiloxane)/poly(ethylene glycol) (PDMS/PEG) as the soft segment were synthesized, and made into thin films for characterization with differential scanning calorimetry (DSC), thermogarvimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), size exclusion chromatography (SEC) and transmission electron microscopy (TEM). Seven thin film composite (TFC) membranes prepared on PUDs and PVDF substrates were evaluated by the separation of air as well as hydrocarbon–nitrogen mixtures. A promising membrane was then selected for further investigation of the morphological structure and permselectivities, using pure gases and binary mixtures of ethylene, ethane, propylene and propane with nitrogen at ambient temperature. It was found that PDMS/PEG-based PU membrane was typically solubility-selective for condensable hydrocarbons, and nitrogen permeance was marginally enhanced in hydrocarbon–nitrogen mixtures. It appears that the copolymer membrane with both urethane and PEG segments can effectively tolerate the swelling caused by the condensable gases. As a result, the selectivities of propylene and propane to nitrogen were substantially improved, e.g., in a mixture containing 28% propylene and 72% nitrogen, the selectivity of propylene to nitrogen reached 29.2 with a propylene permeance of 34.4 gas permeation unit (GPU). 相似文献
The swelling and shrinking kinetics of thermosensitive gels based on N-isopropylacrylamide (NiPAAm) and N-n-propylacrylamide (NnPAAm) were studied. Four gels cylindrical in shape were prepared by two different methods: γ-ray irradiation
to aqueous solutions of poly(NiPAAm) (PNiPAAm) or poly(NnPAAm) (PNnPAAm) and redox polymerization of NiPAAm or NnPAAm monomer
using N,N′-methylenebisacrylamide as a crosslinker. There were a few differences in the swelling kinetics among these gels. However,
a marked difference was observed in the shrinking processes, the rate of which was faster in the order of radiation-crosslinked
PNiPAAm gel > radiation-crosslinked PNnPAAm gel > chemically crosslinked PNnPAAm gel > chemically crosslinked PNiPAAm gel.
This difference was discussed in terms of the microscopic structure of the gels, which was studied by light scattering techniques.
It was found that the static inhomogeneities frozen in the chemically and radiation-crosslinked gels play a key role in their
shrinking kinetics. 相似文献
Ionic liquids extend the Hofmeister series and create a wide range of new possibilities for processes involving salt effects on both soluble and crosslinked systems. This work reports on some mixtures of water with NaCl or an ionic liquid, either 1-ethyl-3-methylimidazolium tosylate or 1-hexyl-3-methylimidazolium chloride, which are better solvents for linear poly(N-vinylimidazole) (L-PVI) than water, i.e., that exhibit a salting-in effect. The intensity of the salt effects was measured on the basis of the polymer solubility, the decrease in polymer–solvent interaction parameter (measured by light scattering), and the increase of coil size (measured through the intrinsic viscosity). It was thus found that the intensity of the salting-in effect of either NaCl or 1-hexyl-3-methylimidazolium chloride on L-PVI is different (larger for the ionic liquid), which denotes that salt effects are not under anion control, and the mechanisms operating in the linear and crosslinked polymers are different. These results are discussed after accounting for the role of ion–polymer interactions. 相似文献
Poly(3,4-ethylenedioxythiophene) (PEDOT) was electropolymerised on aluminium substrates. The Al/Al oxide/PEDOT junction was
studied by electrochemical impedance spectroscopy, comparing the impedance response of the polymer film in oxidised, neutral
and reduced form. The p- and n-doping behaviour of the PEDOT films was studied by in situ external reflection Fourier transform
infrared spectroscopy during stepwise potential cycling of the films. The Al surface underneath the polymer was analysed with
X-ray photoelectron spectroscopy. The impedance spectra indicate that an insulating layer between the metal and the polymer
grows thicker during doping of the polymer film. The other techniques used suggest that this interfacial layer consists mainly
of Al oxides and fluorides. Neither the conductivity nor the dopability of the polymer is notably affected by the growing
of this insulating interfacial layer, which makes the concept of PEDOT electropolymerised on Al promising from an organic
electronics applications point of view. 相似文献
We recently discovered that poly(aspartate) (PAA) hydrolase‐1 from Pedobacter sp. KP‐2 has a unique property of specifically cleaving the amide bond between β‐aspartate units in thermally synthesized PAA (tPAA). In the present study, the enzymatic synthesis of poly(α‐ethyl β‐aspartate) (β‐PAA) was performed by taking advantage of the substrate specificity of PAA hydrolase‐1. No polymerization of diethyl L ‐aspartate by native PAA hydrolase‐1 occurred because of the low dispersibility of the enzyme in organic solvent. Poly(ethylene glycol) (PEG) modification of the enzyme improved its dispersibility and enabled it to polymerize the monomer substrate. MALDI‐TOF MS analysis showed that the synthesized polymer was observed in the range of m/z = 750–2 500. This analysis also revealed that the polymer was composed of ethyl aspartate units, containing either an ethyl ester or a free carboxyl end group at its carboxyl terminus. 1H NMR analysis demonstrated that the synthesized polymer consisted of only β‐amide linkages. Thus, the present results indicate that PAA hydrolase‐1 modified with PEG is useful for the synthesis of β‐PAA due to its unique substrate specificity and good dispersibility in organic solvent.
Phase behavior and structure formation was studied using optical interferometry, nephelometry, and refractometry in the polymer–solvent–nonsolvent system for DMF solutions of two poly(amic acids): based on 3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride and meta-phenylenediamine (PAA-1) and pyromellitic acid dianhydride and 4,4′-oxydianiline (PAA-2). Distilled water and its mixtures with DMF were used as a nonsolvent. According to the results of the study, isothermal cross sections of the phase state diagram in the threecomponent system were plotted, the position of the critical point, the spinodal, and the conodes were determined, the movement of the figurative points in the system was traced depending on the nonsolvent composition. 相似文献
We describe herein, the electrochemical properties of an hydroporphyrin of Ni(II) substituted by two pyrrole groups in organic media (THF and CH2Cl2). In the anodic region it has been shown that the electrochemical behaviour of this complex investigated by cyclic voltammetry and coulometry coupled with UV–visible spectroscopy is strongly dependent on the nature of the solvent.Furthermore, the electrochemical oxidation of the pyrrrole groups has led to the first example of an electrogenerated polypyrrole–metallochlorin film. The resulting modified electrodes exhibit the same electrochemical properties as the monomer free in solution. Preliminary experiments have also demonstrated the possibility to study electrochemically this polymeric film in CH3CN contrary to the Ni(II) chlorin, which is insoluble in this medium. 相似文献
Pore structure variation as a function of pH was investigated for the pore-filled pH-sensitive poly(acrylic acid)-poly(vinylidene fluoride) membranes. The pore radius reduced drastically as the poly(acrylic acid) gel incorporated inside the nascent substrate, which is from 113 nm of nascent substrate to as low as 7.0 nm of pore-filled membranes at pH acidic. For the membranes, the pore radii at pH neutral estimated by the extend Nernst–Planck equation (2.76–4.20 nm) and by the Spiegler–Kedem model with the steric-hindrance pore model (3.4–4.1 nm) are close to each other and comparable with that calculated from the poly(acrylic acid) gel correlation length (1.79–2.93 nm). The calculated pore density at pH neutral (49–258 × 1014 m−2) is much higher than that at pH acidic (2.8–39.8 × 1014 m−2). The results are interpreted in terms of the gel structure in the pore-filled membranes. 相似文献
We have applied the PFG NMR technique to investigate the translational mobility in the PVP-PEG system as a function of composition
and temperature at the stages of PVP-PEG complex formation, its swelling, and dissolution in excess of liquid PEG. It has
been found that the variations of the spin-echo attenuation with PEG content, water amount, and temperature reflect the different
stages. The first two stages are characterized by a distribution of the self-diffusion coefficients of PEG involved in the
network. The dissolution shows two diffusion coefficients; the fast one is attributed to PEG molecules, the slow one to the
associates of PEG and PVP. The temperature dependencies can be described by an Arrhenius law with an activation energy depending
on the composition of the blend. The concentration dependence of the PEG self-diffusion coefficients in the blend occurred
to be independent of the molecular weight of PVP. The results are discussed in terms of the Mackie-Meares model.
Received: 23 August 2000 Accepted: 19 October 2000 相似文献