Cross‐linked poly(aryl ether sulfone) membranes for direct methanol fuel cell applications

Partially sulfonated poly(aryl ether sulfone) (PESS) was synthesized and methacrylated via reaction with glycidyl methacrylate (PESSGMA) and cross‐linked via radical polymerization with styrene and vinyl‐phosphonic acid (VPA). The chemical structures of the synthesized pre‐polymers were characterized via FTIR and ¹H NMR spectroscopic methods and molecular weight was determined via GPC. Membranes of these polymers were prepared via solution casting method. The crosslinking of the PESS polymer reduced IEC, proton conductivity, swelling in water, and methanol permeability of the membranes while increasing the modulus and the glass transition temperature. However, the introduction of the VPA comonomer increased the proton conductivity while maintaining excellent resistance to methanol cross‐over, which was significantly higher as compared with both PESS and the commercial Nafion membranes. Membranes of PESSGMA copolymers incorporating VPA, exhibited proton conductivity values at 60 °C in the range of 16–32 mS cm⁻¹ and methanol permeability values in the range of 6.52 × 10⁻⁹ – 1.92 × 10⁻⁸ cm² s⁻¹. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 558–575     

Oxygen Barrier Properties of Waterborne Polyurethane/Silica Hybrids

The oxygen barrier properties of films obtained from waterborne polyurethane/silica hybrid dispersions were analyzed. Two different types of polyurethanes were used, based on poly(propylene glycol) and poly(1,4-butylene adipate). Three different strategies were followed in the preparation of the hybrid dispersions. In the first type of materials (series 1), the inorganic part came exclusively from the covalent incorporation of trifunctional silane groups into the polymeric chains. The other two series contained, in addition to the trifunctional silane groups, tetrafunctional silane groups either physically blended (series 2) or “in situ” generated (series 3). Materials of series 1 showed an increase of the oxygen permeability coefficient with the silane content. However, the other two types of materials presented just the opposite dependence. In this latter case, the systems containing “in situ” generated silica (series 3) presented higher permeability coefficient values, probably because of the steric hindrance imposed by the polyurethane that gave rise to silica networks containing silanol groups and free volume holes. Moreover, lower permeability coefficient values were obtained when larger size particles were added. This fact could mean that the polyurethane/silica interface effects were not totally hindered even when the organic/inorganic phases were covalently bonded.     

Evaluation of methoxy polyethylene glycol‐polylactide diblock copolymers as additive in hypromellose film coating

This paper deals with a new application of diblock methoxy polyethylene glycol‐polylactide block copolymers, a class of synthetic biomaterials largely studied in the pharmaceutical and biomedical fields owing to their favorable properties such as biocompatibility, biodegradability, low immunogenicity, and good mechanical properties. In this work, these materials were evaluated as additives for gastro‐soluble pharmaceutical coating aimed to reduce film stiffness and water permeability. Two copolymers with different polylactide chain lengths were synthesized and characterized in term of molecular weight and solid‐state properties. A series of free films with different hypromellose/copolymers ratio were prepared and characterized in terms of appearance, components miscibility, plasticity, and water vapor permeability. The obtained results demonstrate that copolymers effectively influence hypromellose film properties according to their concentration and molecular weight. Specifically, the addition of the copolymer with a molecular weight of 6.5 kDa in a ratio hypromellose:polymer 5:1, allowed to obtain films with good appearance, improved plasticization, and water permeability properties. For higher molecular weight, copolymer or different ratios was not possible to observe the improvement of all the properties at the same time. The results also make possible to define the critical features to improve in order to use block copolymers as additive in hypromellose film coating. The availability of new water‐soluble additives able to work as plasticizer and moisture sealer in polymeric films represents an important progress not only in the field of pharmaceutical coating but also in that of food coatings, as for example in the formulation of edible films. Copyright © 2013 John Wiley & Sons, Ltd.     

Laboratory Studies of Depressurization with a High Concentration of Surfactant in Low-Permeability Reservoirs

To solve the problem of high pressure of water injection in low permeability reservoirs, a high concentration of surfactant system was developed in this article. With the solubilization of oil in aqueous surfactant solution as a criterion, a formula was screened from anionic and nonionic-anionic surfactants, and the optimal depressurized system was obtained as follows, 13.3% surfactant HEX +2.23% n-propanol +4.47% n-butanol, the solubilization capability being up to 0.66 g/g. This system had good salt tolerance, and it exhibited water external microemulsion in the range of of 1 to 200 g/L NaCl. Core flooding results show that this high concentration of surfactant system formed water external microemulsion with the residual oil in the core, reducing the displacement pressure over 35%. Meanwhile, the effects of concentration and injection volume on depressurization were also investigated. It is indicated that a good depressurization effect was achieved after injecting 1 pore volume of the system with the salt concentration of 100 g/L.     

The effect of tourmaline on cell membrane of nitrosomonas europaea and biodegradation of micropollutant

As a kind of ammonia‐oxidizing bacteria, Nitrosomonas europaea (N. europaea) was chosen as a research model to study the alteration of cell membrane in the presence of tourmaline and biodegradation of acetochlor. atomic force microscopy images reveal that the presence of tourmaline substantially changes the structure of the outer membrane of the cell responsible for the cell permeability. SEM images show that the introduction of tourmaline makes the cell lose its ability to resist lysozyme owing to the damages. The fluorescence polarization has shown a significant decrease in membrane fluidity and the increase of permeability of cell membrane. Ca²⁺ and Mg²⁺ was measured using inductively coupled plasma mass spectrometry and was found in the supernatant from the cells treated by tourmaline. Tourmaline can improve the efficiency of biodegradation of acetochlor for N. europaea. It is proposed that the cell permeability is slightly increased, and the absorbability of nutrition from the medium becomes easier. As a result, N. europaea grows faster in the presence of tourmaline than the native cells. Copyright © 2014 John Wiley & Sons, Ltd.     

低渗温热腹腔灌注化疗治疗恶性腹腔积液的临床研究

目的 评价低渗温热腹腔灌注化疗治疗恶性腹腔积液的疗效及不良反应。方法 行腹腔穿刺置单腔中心静脉导管,外接引流袋,记录腹水引流量,当日排放腹水1 500ml 后,予加热至43~45℃注射用双蒸馏水1 000ml 行腹腔灌注,次日重复放液1 500ml,再予加热至43~45℃注射用双蒸馏水1 000ml 行腹腔灌注,并于灌注后腹腔注入顺铂60mg、氟尿嘧啶500mg 并封管,治疗期间常规给予简单水化、对症止吐等治疗。结果 31 例恶性腹腔积液患者共完成低渗温热腹腔灌注化疗42 周期,完全缓解7例,部分缓解15,稳定5 例,进展4 例,完全缓解+ 部分缓解占70.97%。中位进展时间（TTP）3.6个月（2～9 个月）, 中位生存期（MST）5.6 个月。毒副反应以消化道反应为主。结论 低渗温热腹腔灌注化疗治疗恶性腹腔积,在延长患者的生存期、提高生活质量方面效果较好,临床上可推荐应用。     

meso‐Ester and Carboxylic Acid Substituted BODIPYs with Far‐Red and Near‐Infrared Emission for Bioimaging Applications

A series of meso‐ester‐substituted BODIPY derivatives 1–6 are synthesized and characterized. In particular, dyes functionalized with oligo(ethylene glycol) ether styryl or naphthalene vinylene groups at the α positions of the BODIPY core ( 3 – 6 ) become partially soluble in water, and their absorptions and emissions are located in the far‐red or near‐infrared region. Three synthetic approaches are attempted to access the meso‐carboxylic acid (COOH)‐substituted BODIPYs 7 and 8 from the meso‐ester‐substituted BODIPYs. Two feasible synthetic routes are developed successfully, including one short route with only three steps. The meso‐COOH‐substituted BODIPY 7 is completely soluble in pure water, and its fluorescence maximum reaches around 650 nm with a fluorescence quantum yield of up to 15 %. Time‐dependent density functional theory calculations are conducted to understand the structure–optical properties relationship, and it is revealed that the Stokes shift is dependent mainly on the geometric change from the ground state to the first excited singlet state. Furthermore, cell staining tests demonstrate that the meso‐ester‐substituted BODIPYs ( 1 and 3 – 6 ) and one of the meso‐COOH‐substituted BODIPYs ( 8 ) are very membrane‐permeable. These features make these meso‐ester‐ and meso‐COOH‐substituted BODIPY dyes attractive for bioimaging and biolabeling applications in living cells.     

Water permeability in MXene membranes: Process matters

Recent studies have shown impressive transport behaviors of water and ions within lamellar MXene membranes,which endows great promise in developing advanced separation application based high performance MXene membranes.However,most of the researches focused on modification of MXene nanoflakes and optimizing interlayer distance,leaving the impact of membrane fabrication process marginal.In this work,we studied the water flux of membranes made by vacuum filtration using delaminated MXene nanoflakes as the building-blocks.Our results show that the water permeability is extremely sensitive to the process,especially at the drying process,loading and deposit rate of nanoflakes(the feeding concentration).We find that the voids from less ordered stack rather than in-plane defects and interlayer galleries contribute to the large water permeability.The voids can be effectively avoided via deposition of MXene nanoflakes at a slow rate.Manipulating the stack of MXene nanoflakes during vacuum filtration and drying are critical for development of MXene membranes with desired performance for water permeation.