Molecular mobility in biodegradable poly( $ \varepsilon$ -caprolactone)/poly(hydroxyethyl acrylate) networks

Poly( e \varepsilon -caprolactone)/poly(hydroxyethyl acrylate) networks have been investigated by thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry (DSC). The introduction of hydrophilic units (HEA) in the system aiming at tailoring the hydrophilicity of the system results in a series of copolymer networks with microphase separation into hydrophobic/hydrophilic domains. Polycaprolactone (PCL) crystallization is prevented by the topological constraints HEA units imposed in such heterogeneous domains. Moreover, the mobility of the amorphous PCL chains is enhanced as revealed by the main relaxation process which becomes faster. The glass transition of PHEA-rich domains shifts to lower temperatures, as the total amount of PCL in the copolymer increases, due to the presence of PCL units within the same region. The behaviour of the copolymer networks swollen with different content of water has been investigated to analyze the interaction between water molecules and hydrophobic/hydrophilic domains and provide further insights into the molecular structure of the system.     

Dielectric relaxation spectrum of poly (ε-caprolactone) networks hydrophilized by copolymerization with 2-hydroxyethyl acrylate

The dielectric relaxation spectrum of polycaprolactone (PCL) networks hydrophilized with different amounts of 2-hydroxyethyl acrylate (HEA) is investigated. PCL is a semicrystalline polyester with a complex relaxation spectrum that includes the main α relaxation and two secondary modes (β, γ) at lower temperatures. The overlapping of the different relaxational modes was split by using several Havriliak-Negami functions. Crosslinking the material modifies the dynamics of the main relaxation process as reflected by the parameters that characterize the Vogel behavior of the process and the dynamic fragility. The incorporation of HEA units in the network results in a material with microphase separation: two α processes are detected, the one corresponding to the PCL chains and the new one associated to nanometric regions that contain different amount of both comonomers. The incorporation of the HEA units in the system involves the presence of a new β_sw relaxation due to the link of two side chains by water molecules through hydrogen bonding.     

Preparation and Properties of 2, 4-2-Isocyanic Acid Methyl Ester/Poly(ϵ-caprolactone)/Diethylene Glycol Hydrogels

The hydrophilic polyurethane (PU) hydrogels have become attractive in the biomedical field for drug delivery. In this work 2, 4-2-isocyanic acid methyl ester (TDI), poly(?-caprolactone) (PCL), and poly(ethylene glycol) (PEG) were used to prepare a prepolymer and then diethylene glycol (DEG) was used as a chain extender to prepare a novel hydrophilic polyurethane, TDI/PCL-PEG/DEG. The obtained PU hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM). By varying the ratio of PCL to PEG in the copolymer, modulations of hydrophilicity and drug release behavior were observed. FT-IR analysis confirmed the successful synthesis of the TDI/PCL-PEG/DEG hydrogels. The introduction of PEG into the PU hydrogels led to a porous structure. The water contact angle and swelling ratio results confirmed that the hydrophilicity increased with increasing amounts of the PEG segments. The introduction of PEG also increased the release rate of chloramphenicol, used as model drug, from the PU hydrogels.     

Structure of water in mesoporous organosilica by calorimetry and inelastic neutron scattering

In this paper, we describe the preparation of mesoporous organosilica samples with hydrophilic or hydrophobic organic functionality inside the silica channel. We synthesized mesoporous organosilica of identical pore sizes based on two different organic surface functionality namely hydrophobic (based on octyltriethoxysilane OTES) and hydrophilic (3-aminopropyltriethoxysilane ATES) and MCM-41 was used as a reference system. The structure of water/ice in those porous silica samples have been investigated over a range temperatures by differential scanning calorimetry (DSC) and inelastic neutron scattering (INS). INS study revealed that water confined in hydrophobic mesoporous organosilica shows vibrational behavior strongly different than bulk water. It consists of two states: water with strong and weak hydrogen bonds (with ratio 1:2.65, respectively), compared to ice-Ih. The corresponding O-O distances in these water states are 2.67 and 2.87 ?, which strongly differ compared to ice-Ih (2.76 ?). INS spectra for water in hydrophilic mesoporous organosilica ATES show behavior similar to bulk water, but with greater degree of disorder.     

3D Arrangement of Magnetic Particles in Thin Polymer Films Assisted by Magnetically Patterned Exchange Bias Layer Systems

The possibility to arrange and embed magnetic micro- and nanoparticles in thin polymer film systems using flat magnetically patterned substrate templates is investigated. In contrast to self-organized particle rows forming by applying a homogeneous magnetic field, particles adapt to the magnetic field landscape of the substrate's magnetic pattern prior to polymer crosslinking. Crosslinking then fixes the particle positions in the polymer. The process is tested for composites of hydrophobic polydimethylsiloxane (PDMS) and maghemite nanoparticles as well as for hydrophilic polyvinyl alcohol (PVOH) and hydrophilic functionalized, superparamagnetic core–shell microspheres. The substrate template is an exchange bias layer system magnetically patterned into parallel-stripe domains with in-plane magnetizations and head-to-head/tail-to-tail remanent magnetization orientation in adjacent magnetic domains. A high occupancy percentage of magnetic beads on a domain wall as well as anisotropic actuation of the composite is achieved.     

Polypropylene modified with 2-hydroxyethyl acrylate-g-2-methacryloyloxyethyl phosphorycholine and its hemocompatibility

Polypropylene (PP) was modified with 2-hydroxyethyl acrylate (HEA) by solution radical grafting to introduce active hydroxyl groups on polypropylene backbone (PP-g-HEA). Then the biomimic monomer, 2-methacryloyloxyethyl phosphorycholine (MPC), was grafted onto the surface of PP-g-HEA film (PP-g-HEA-g-MPC) by redox graft polymerizations with ceric(IV) ammonium nitrate as an initiator. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) showed that the HEA and MPC were introduced onto PP molecular chains and the copolymer, PP-g-HEA-g-MPC were formed. The water contact angle measurements demonstrated that the final modified PP film exhibited a better hydrophilic surface compared to the neat PP film. The platelets adhesion on the neat PP, PP-g-HEA and PP-g-HEA-g-MPC film was examined by scanning electron microscopy (SEM). It was found that a large number of platelets were adhered and activated on the surface of neat PP and PP-g-HEA films, while the number of platelets on PP-g-HEA-g-MPC surface was decreased remarkably. The result revealed that the introduction of poly(MPC) onto the PP surface improved the hemocompatibility of PP substantially.     

Correlation of Diffusional Exponent with Structural Sequence of (N-Vinylpyrrolidone-alt-Acrylic Acid) Hydrogels: A Predictive Hydrogel Design Approach

Correlation of diffusional exponent of water into (N-Vinylpyrrolidone-alt-Acrylic acid) hydrogels with the structural sequence of hydrogel repeating units (i.e. hydrophilic and/or hydrophobic moieties) through a scaling law relationship has been investigated. The diffusional exponent (n) was found to depend linearly on Y/X² , where X equals to molar ratio of monomers in the feed (i.e. ([M₁ ]/[M₂ ])_feed) and Y equals to molar ratio of repeating units in the copolymer (i.e. ([M₁ ]/[M₂ ])_copolymer). Copolymers rich in hydrophilic acrylic acid (i.e. larger Y/X² ) were found to form more coiled polymeric chains as acrylic acid content increased due to H-bonding interactions, and hence results in lower diffusion coefficients and linear lowering of the n-value. On the other hand copolymers rich in partially hydrophobic N-vinylpyrrolidone (i.e. smaller Y/X²) formed more uncoiled polymeric chains as N-vinylpyrrolidone content increased due to larger amounts of positively charged protonated nitrogen atoms at pH 5.5 that tend to repel each other, which eventually lead to higher diffusion coefficients and a linear increase in n-value. These characteristic findings could be significant in sustained drug release studies, where the structural sequence of a hydrogel plays a dominant role in the release kinetics of a drug at certain positions and/or times.     

Mechanism and Kinetics of Drug Release from Poly(ϵ-Caprolactone) Based Extrudates Prepared By Hot-Melt Extrusion

In this study, different types of poly(?-caprolactone) (PCL)-based matrices were prepared by hot-melt extrusion. Methylene blue (MB) was used as a model drug, and various amounts and types of hydrophilic components (polyethylene glycol, PEG or polyethylene oxide, PEO) were added to the extrudates as release rate modifiers. The drug release mechanism and kinetics from these extrudates were investigated. Scanning electron microscopy (SEM) and micro-Fourier transform infrared spectroscopy (micro-FTIR) results revealed the dissolution of the hydrophilic components (PEG or PEO) during the drug release, and in-vitro release tests exhibited the tailorable release behavior of MB from the PCL/hydrophilic components. Based on the experimental results, it was speculated that the release kinetics of MB from the PCL/hydrophilic components was a combination of diffusion and dissolution models.     

Preparation and properties of morphology controlled poly(2-hydroxyethyl methacrylate)/poly(N-vinyl pyrrolidone) double networks for biomedical use

Poly(2-hydroxyethyl methacrylate)/poly(N-vinyl pyrrolidone) (PHEMA/PVP) double networks (DN) were prepared using a sequential method by incorporating a second network of crosslinked PVP into PHEMA. We found that the distributions of the two networks can be regulated just by modulating the morphology of the first network, thus giving expected high water content of these gels. Fourier transform infrared (FTIR) spectroscopy and scanning electronic microscopy (SEM) were used to confirm the structure of the DN. The incorporation of more hydrophilic PVP enhanced swelling ability of these gels. Because of improved hydrophilicity, the PHEMA/PVP DN exhibited higher loading capability for water-soluble substance than that of pure PHEMA, while showed a slower release rate than corresponding HEMA/NVP copolymer hydrogel. It is suggested that the DN gels are potential biomaterials for wound dressing, medical implants and other drug delivery systems.     

Designing and Characterization of Poly(L-Lactide)/Poly(ϵ-Caprolactone) Multiblock Copolymers

A series of poly(L-lactide)/poly(?-caprolactone) (PLA/PCL) biodegradable multiblock copolymers was synthesized by a two-step process and characterized. Ring-opening polymerization was used to prepare a series of HO-PLA-PCL-PLA-OH copolymers initiated by hydroxyl-terminated PCL. Then the triblock copolymers and 1,6-hexamethylene diisocyanate (HDI) were reacted with different copolymer/HDI weight ratios. Consequently, a series of PLA/PCL multiblock copolymers with designed molecular chain structure was obtained. Gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, and ¹H NMR were used to characterize these copolymers and the results showed that the designed PLA/PCL copolymers had been synthesized. Dynamic mechanical analysis (DMA) was applied to characterize their thermal properties. Stress–strain curves showed that a PLA/PCL copolymer with adjustable mechanical properties had been achieved.     

AFM studies on Langmuir-Blodgett films of cholesterol

The Langmuir monolayer of cholesterol at the air-water interface exhibits a condensed phase in which the cholesterol molecules are aligned normal to the water surface. We have transferred the monolayer from water surface to different substrates by Langmuir-Blodgett (LB) technique and have studied their assembly by atomic force microscope (AFM). Our studies reveal that the aggregation of cholesterol molecules on hydrophobic surfaces leads to interesting structures. The cholesterol molecules assemble into a uniform film, elongated domains and uniformly distributed torus-shaped domains (doughnuts) for one, two and four cycles of deposition, respectively. Beyond four cycles, the molecules adsorb and desorb by an equal amount resulting in no further deposition. The formation of uniformly distributed doughnuts can be attributed to the hydrophobic interaction and reorganization of the molecules due to successive adsorption and desorption during deposition cycles. Our studies on hydrophilic surfaces show that cholesterol cannot form more than one layer of deposition.PACS: 68.47.Pe Langmuir-Blodgett films on solids; polymers on surfaces; biological molecules on surfaces - 68.37.Ps Atomic force microscopy (AFM) - 68.43.Mn Adsorption/desorption kinetics     

Hydrophobic/hydrophilic solvation: inferences from Monte Carlo simulations and experiments

In this study Monte Carlo simulations are used to determine the solvation properties of model hydrophobic (xenon and hard sphere) and hydrophilic (dimethyl ether) solutes in SPC/E water. Various contributions to the experimental solvation entropy, including the solvent reorganization entropy, have been determined. The main conclusion drawn, which is in accord with solubility data, is that poor solubility correlates with poor solute-water interaction. At room temperature, energy dominates the aqueous solubility of both hydrophobic and hydrophilic solutes, rather than entropy. However, at higher temperatures the solubility can pass through a minimum, and then entropy becomes dominant. Another interesting finding is the presence of larger than expected cavities in water. Two different simulation results support this finding. This unexpected hollow structure in water explains why a hard sphere solute is more soluble in water than in a comparable hard sphere or Lennard-Jones solvent. Hydrogen bonding causes water to aggregate into clusters that produce a few large cavities rather than many smaller cavities. The propensity for clustering also explains why water gives the illusion of being a low density liquid. Sufficient theoretical apparatus is developed to connect theoretical solvation properties to those measured by simulation and experiment. Finally, based on gas solubility, an intuitive hydrophobic/hydrophilic scale is developed.     

基于自洽场理论两亲高分子自组装的研究

运用扩展的自洽场和密度泛函理论(SCF/DFT),研究ABC蝌蚪形两亲高分子在稀溶剂中的自组装形态,其中蝌蚪形两亲高分子由线形嵌段共聚物链AB嫁接到球形纳米颗粒C上构成.与以往研究的线形ABC两亲高分子相比,蝌蚪形两亲高分子的自组装形态有着很大的不同.在粒子亲溶剂,嵌段共聚物疏溶剂时,各组分间弱分凝条件下,蝌蚪形两亲高分子自组装成胶球状形貌;在强分凝条件下,随着嵌段共聚物疏溶剂性的增强,两亲高分子的自组织态由胶球状转变成四角、三角状形貌,其中嵌段B主要分布在各角上.通过改变各组分间的相互作用,在嵌段A亲溶剂,嵌段B和粒子疏溶剂时,粒子呈平行棒状或小方块状分布在胶球中.     

Monte Carlo simulations of an amphiphilic polymer at a hydrophobic/hydrophilic interface

Monte Carlo simulations have been carried out for an off-lattice model of an amphiphilic polymer at a hydrophobic/hydrophilic interface. The model system consists of a polynorbornene backbone with poly(ethylene oxide) (PEO) grafts modelled atomistically at an idealized interface between hydrophobic and hydrophilic regions, which are represented by external potentials. Results are presented for the distribution of PEO chain ends, and the density of PEO segments perpendicular to the surface. The latter is used to provide predictions for neutron reflectivity profiles normal to the surface as a function of the lateral confinement of the PEO grafts. At low surface coverage the simulation results are found to be in good agreement with experimental neutron scattering results from similar polymers studied at the water/air interface.     

Immobilization of poly(?-caprolactone)-poly(ethylene oxide)-poly(?-caprolactone) triblock copolymer on poly(lactide-co-glycolide) surface and dual biofunctional effects

Poly(?-caprolactone)-poly(ethylene oxide)-poly(?-caprolactone) (PCL-PEG-PCL) triblock copolymer was covalently immobilized onto poly(lactide-co-glycolide) (PLGA) surface with the precursor of photopolymerizable and biodegradable PCL-PEG-PCL diacrylates. Argon plasma technique was exploited to obtain hydrophilic PLGA surface (HPLGA). The surface properties were characterized by Water contact angle and X-ray photoelectron spectroscopy (XPS) techniques. PCL-PEG-PCL surface modified hydrophobic PLGA and hydrophilic PLGA results in different surface physicochemical properties. PCL-PEG-PCL modified hydrophobic PLGA surface (PLGA-PCL-PEG-PCL) demonstrates excellent inhibition of platelet adhesion and activation; while PCL-PEG-PCL modified hydrophilic PLGA surface (HPLGA-PCL-PEG-PCL) results in good cytocompatibility. The possible mechanism was discussed and the driven force was ascribed to the different assembly behavior of PCL-PEG-PCL on PLGA surface dependant on the hydrophilic/hydrophobic property of PLGA. This simple and effective surface engineering method is also suitable for the other biomaterials such as polyurethane (PU), silicon rubber and poly(ethylene terephthalate) (PET) to obtain the enhanced biocompatibility.     

Tunable wettability of carbon nanotube/poly (?-caprolactone) hybrid films

We have realized a stable superhydrophobic surface, a thermally tunable superhydrophobic surface, and a thermally tunable hydrophobic surface by combining the crystalline/amorphous phase transition of the poly(?-caprolactone) (PCL) with the optimized surface roughness of the carbon nanotube/PCL hybrid films. The water droplet mobilities and wettabilities were reversibly thermally switched on the tunable superhydrophobic and the hydrophobic surfaces, respectively. These responsive surfaces have potential applications in microfluidic devices and microreactors and for liquid transportation.     

Selective interaction water-hydrophilic/hydrophobic impurities observed by four-photon Brillouin spectroscopy

The four-photon scattering spectra of water in the aqueous solution/suspension of various hydrophilic/hydrophobic impurities in the range ±3 cm^?1 (±90 GHz) have been observed. We have found the strong dependence of the Brillouin resonance frequency upon the connectivity of the impurities and water molecules. The Brillouin shift is attributed to the local restructuring of the hydrogen bond network in water inside the interface layer that is sensitive to the hydrophilic/hydrophobic properties. In fact, it results in variations in the isothermal compressibility and sound velocity.     

Small angle neutron scattering study on the aggregation behaviour of PEO-PPO-PEO copolymers in the presence of a hydrophobic diol

Small angle neutron scattering (SANS) measurements on aqueous solutions of four polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymers (commercially known as Pluronic®)F88, P85, F127 and P123 in the presence of hydrophobic C14Diol (also known as Surfynol® 104) reveal information on micellization, micellar size and micellar transitions. While most hydrophilic F88 (with least PPO/PEO ratio) remained unimers in water at 30°C, other copolymers formed micellar solutions. Surfynol® 104 is sparingly soluble in water to only about ～0.1 wt%, but on addition to pluronic solution, it gets incorporated in the micellar region of block copolymer which leads to increase in aggregation number and transformation of spherical to ellipsoidal micelles. The added diol-induced micellization in F88, though hydrophilic copolymers F88 and F127 did not show any appreciable micellar growth or shape changes as observed for P85 and P123 (which are comparatively more hydrophobic). The SANS results on copolymer pairs with same molecular weight PPO but different % PEO (viz. F88 and P85, F127 and P123) and with same molecular weight PEO but different PPO (F88 and F127) reveal that the copolymer with large PPO/PEO ratio facilitate micellar transition in the presence of diol. An increase in temperature and presence of added electrolyte (sodium chloride) in the solution further enhances these effects. The micellar parameters for these systems were found out using available software and are reported.     

单甲氧基聚乙二醇-聚(己内酯-co-丙交酯)嵌段共聚物的NMR表征

利用溶液¹³C NMR和HMBC实验对AB型两亲性嵌段共聚物单甲氧基聚乙二醇－聚（己内酯-co-丙交酯）[MeOPEG-P(Cap-co-LL)]的嵌段结构以及聚（己内酯-co-丙交酯）[P(Cap-co-LL)]嵌段中Cap和LL的无规结构进行了表征. 研究发现,P(Cap-co-LL)中Cap、LL的组成对P(Cap-co-LL)的无规度、Cap和LL的酯交换程度以及不同组分的平均链长均有影响. 对LL中立体结构不同所产生的酯交换也进行了表征.     

A well-defined biodegradable 1,2,3-triazolium-functionalized PEG-<Emphasis Type="Italic">b</Emphasis>-PCL block copolymer: facile synthesis and its compatibilization for PLA/PCL blends

A novel biodegradable 1,2,3-triazolium-functionalized PEG-b-PCL copolymer (TAPEC) was synthesized by the “click” coupling of methoxypolyethylene glycol azide and α-propargyl-ω-hydroxyl-poly(ε-caprolactone), followed by the quaternization of the 1,2,3-triazole moiety with iodomethane. All the intermediates and TAPEC were characterized by ¹H NMR, FT-IR, and gel permeation chromatography (GPC). Taking advantage of the characteristics of ionic liquid and block copolymer, this ion-containing diblock copolymer is expected to be used as a novel compatibilizer in mixed biopolyester for regulating the interface and crystallization behaviors. Hence, the TAPEC was evaluated as a compatibilizer and an interface emulsifier in the blends of polylactic acid (PLA) and poly(ε-caprolactone) (PCL). Non-isothermal crystallization experimental results showed that the TAPEC with the higher amount of ε-caprolactone units induces a plasticization and nucleate effect that increased the crystallization ability of the PLA phase; meanwhile, in the PCL phase, the agminated ionic cluster acting as a nucleating agent significantly increased the crystalline of PCL.