Fe2+/Fe3+ based MOIFs + dye interaction study: Thermodynamic and kinetic analysis estimated through spectrophotometrically

Herein, the interaction study of organic dyes with newly reported metal organic ionic frameworks (MOIF) based on [Fe(CN)₆]^3-/[Fe(CN)₆]^4-/[Fe(CN)₅NO]^2- and cetylpyridinium cation, investigated through spectrophotometric method. Measurements were carried out at 303.15, 308.15 and 313.15 K where interaction found to be decreased with increase in temperatures. The 60–90% maximum interaction was noted for [Fe(CN)₅NO]^2- based MOIF with all chosen dyes at 303.15 K inferring the high interaction ability associated with dissymmetry of this MOIF due to presence of different ligands. The oxidation state and hydrophilicophobic domains of MOIFs have been found accountable for the stronger interaction where Fe²⁺ with high hydrophobicity was found more interacting as compared to Fe³⁺ with less hydrophobicity. The activation parameters ΔG⁰, ΔH⁰ have been found greater for MOIFs and methylene blue dye systems due to stronger interaction of their hydrophobic domains. The ΔS⁰ noted greater for [Fe(CN)₅NO]^2- based MOIF showing the impact of availability of interacting sites and distortion in symmetry. The isotherm analysis has inferred about the maximum uniform distribution of binding energy, favorability of interaction, interaction capacity and intensity, was associated with methylene blue and MOIFs systems. The positive slope (2.303/K) of a plot of log(A_o/A_t) vs t (time) inferred the first order kinetic of MOIF and chosen dyes.     

Improving the hydrophilicity of poly(vinylidene fluoride) porous membranes by electron beam initiated surface grafting of AA/SSS binary monomers

Poly(vinylidene fluoride) (PVDF) membranes were pre-irradiated by electron beam in vacuum, and then the hydrophilic sulfonate groups were introduced by the single step grafting method with binary monomer solution of acrylic acid (AA) and sodium 4-styrenesulfonate (SSS). The effect of binary monomer ratio and pH of reaction solution on the degree of grafting was investigated. The surface chemical change was characterized by Fourier transform infrared attenuated total reflection spectroscopy (FT-IR-ATR) and X-ray photoelectron spectroscopy (XPS). Morphological changes on the membrane surface were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface hydrophilicity of the modified membrane was characterized through water contact angle measurement. It was found that the water contact angle of the membrane surface decreased significantly when compared with the original one, indicating the improvement of the surface hydrophilicity.     

Interfacial Properties of Poly(Caprolactone) and Derivatives

Abstract

Monolayers of biodegradable polymers, poly(caprolactone) (PCL), poly(caprolactone) diol (PCL‐diol), and poly(caprolactone) triol (PCL‐triol) in the air/water interface were studied and characterized. The Langmuir–Blodgett technique was used for the monolayer transfer onto hydrophilic and hydrophobic solid substrates. The results obtained in both cases are dependent on the functional groups incorporated in the respective polymers. The surface energy (SE), and the polar and dispersion contributions, γ^p and γ^d, respectively, were obtained by wettability measurements. For polymeric spin‐casted thin films deposited over glass, the results also indicate an increment in the polymer hydrophilicity by hydroxyl groups insertion.     

Increasing surface hydrophilicity of titania thin films by doping

The hydrophilicity of RF sputtered thin films of: (a) pure TiO₂ and (b) TiO₂ doped with 0.3% Ce, 0.4% Nb, and 0.4% N (atomic percents) was investigated macroscopically by measurements of the contact angle between water and film surface. The results are discussed in terms of the connection of the hydrophilic and photocatalytic properties of the materials with their structure, morphology and optical characteristics. The 280 nm thick films were deposited on optical glass substrates at 250 °C. Film structure and surface morphology were investigated by X-ray diffraction and atomic force microscopy. The surface roughness was derived from atomic force microscopy and ellipsometric data. The contact angle of de-ionized water with film surface was monitored during photo-activation and after irradiating with near-UV light. The surface super-hidrophilicity of all the investigated samples decays, when samples are kept in darkness for 48 h after irradiation. The hydrophilic behavior of the doped TiO₂ thin films is discussed in terms of the effects of surface roughness, phase transformations enhanced by doping and charge carrier recombination.     

Expanded poly(tetrafluoroethylene) membrane surface modification using acetylene/nitrogen plasma treatment

In this article, expanded poly(tetrafluoroethylene) (e-PTFE) membrane surface modification was carried out using acetylene/nitrogen plasma treatment (p-e-PTFE). The variation in surface morphology of the p-e-PTFE membranes was confirmed by FTIR-ATR, scanning electron microscopy (SEM), and contact angle measurements. It was found that the surface hydrophilicity increased with increasing nitrogen content in the feed gas mixture, RF power, and plasma treatment time. The surface pore size decreased with increasing RF power and plasma treatment time. The water contact angles of the modified e-PTFE membrane decreased from 125.8° to 34.1° through the acetylene/nitrogen plasma treatment.     

Tailoring the wettability of patterned silicon surfaces with dual-scale pillars: From hydrophilicity to superhydrophobicity

Wettability tailoring of patterned silicon surface has great potential in fields producing integrated circuits, solar cells, sensors, detectors, and micro/nano electromechanical systems. The present paper presents a convenient yet effective method of combining reactive ion etching and catalyzed etching to prepare silicon surface with micro-nano dual-scale pillars. The experimental results indicate that the hydrophilic surface transformed to a superhydrophobic surface when micro-nano dual-scale pillars were formed. The surface preserved superhydrophobicity even when the geometric parameters of the micropillars were changed. Overhangs of water drops on steep micro-nano dual-scale pillars result in superhydrophobicity. This method offers a new way for tailoring the wettability of patterned silicon surfaces.     

Surface roughness analysis of hydrophilic SiO2/TiO2/glass nano bilayers by the level crossing approach

The effect of etching time on the statistical properties of hydrophilic surfaces of SiO₂/TiO₂/glass nano bilayers has been studied using atomic force microscopy (AFM) and a stochastic approach based on a level crossing analysis. We have created rough surfaces of the hydrophilic SiO₂/TiO₂ nano bilayer system by using 26% potassium hydroxide (KOH) solution. Measuring the average apparent contact angle allowed us to assess the degree of hydrophilicity, and the optimum condition was determined to be 10 min etching time. A level crossing analysis based on AFM images provided deeper insight into the microscopic details of the surface topography. With different etching times, it has been shown that the average frequency of visiting a height with positive slope behaves in a Gaussian manner for heights near the mean value and obeys a power law for heights far away from the mean value. Finally, by applying the generalized total number of crossings with positive slope, it was found that the both high heights and deep valleys of the surface have a great effect on the hydrophilic degree of the SiO₂/TiO₂/glass nano bilayer investigated system.     

聚丙交酯及其共聚物的研究进展

聚丙交酯（PLA）是一种非常重要的生物医用材料,由于它在体内可降解、无毒、安全,在临床上得到了广泛的应用.为了适应更多、更广的医学应用,要求对聚丙交酯的降解速度、力学性能等进行调节控制,或者要求改善PLA的亲水性、生物相容性、细胞亲和性等等,为此合成了一系列PLA的共聚物,并对其性能进行了研究.本文对上述领域的研究进展进行了综述,结合了作者常年来在PLA共聚物的合成与性能方面的研究,分成四大类进行阐述：（1）丙交酯与其它内酯类的共聚;（2）丙交酯与聚乙二醇类大分子的共聚;（3）丙交酯与带有功能基团单体的共聚;（4）丙交酯与其它天然材料的共聚,并简要地叙述其在医学领域应用的前景.     

A study on the degradation property of a hydrophilic polycarbonate film treated by inductively coupled plasma using CO2 as reactive gas

In this study, we report investigations on surface modification of polycarbonate (PC) films for hydrophilicity and degradability under acid/base environmental conditions. The aims of our study were to modify a PC surface by the inductively coupled plasma (ICP) using CO₂ as precursor gas and to confirm the improved hydrophilic and degradable properties. X-ray photoelectron spectroscopy and contact angle measurement were carried out to characterize the chemical binding state and to observe the specific chemical change on the surface, respectively. After the plasma treatment and degradability test, scanning electron microscopy (SEM) was also employed to observe the surface morphologies. The results showed that the CO₂-plasma treatment can be a possible method to improve the hydrophilicity and degradability of the PC surface.     

Effect of hydrophilicity of polymer particles on their glass transition temperatures in the emulsion state

The glass transition temperatures (Tg) of three kinds of poly(methyl methacrylate)-based copolymer emulsions having wide polymer compositions, which were prepared by emulsifier-free emulsion copolymerizations of methyl methacryalate with ethyl acrylate, n-buthyl methacrylate and methacrylic acid, were measured with a power compensation-type highly sensitive differential scanning calorimeter. The Tg values of the copolymers in their emulsion state (Tg _E) were always lower than those in their dry states (Tg _D), and the difference between Tg _E and Tg _D increased with an increase in copolymer hydrophilicities.Part CCLIII of the series Studies on Suspension and Emulsion