Preparation of hydrophilic poly(vinylidene fluoride) membrane by in-situ grafting of N-vinyl pyrrolidone via a reactive vapor induced phase separation procedure

Increasing hydrophilicity of hydrophobic membrane is one of the strategies to improve its antifouling performance. Herein we report a procedure of reactive-vapor induced phase separation to prepare an N-vinyl pyrrolidone (NVP) modified poly(vinylidene fluoride) (PVDF) membrane to improve its hydrophilicity. PVDF solution containing NVP monomer was cast in ammonia water vapor atmosphere to prepare the modified membrane. During the process, PVDF was dehydrofluorinated by the reactive vapor of ammonia water to generate double bond of FC═CH, and then NVP was grafted. The degree of grafting modification and the microstructure evolution of the membrane were studied by adjusting the amount of NVP addition. A possible mechanism of membrane formation from crystallization gelling to non-crystallization gelling has been proposed to understand the morphology change from nodular sphere to bi-continuous microstructure with fibril matrix. It has been found that rising the degree of modification has changed the polymorph of PVDF from β to α crystalline phase, as well as turned the hydrophobic PVDF membrane into hydrophilic. Moreover, the modified membrane displayed obvious reduction in bovine serum albumin adsorption, suggesting improvement in anti-fouling performance. Therefore, our work provides an easy strategy to prepare hydrophilic PVDF membrane, which may have promising potential applications.     

Novel Azobenzene-Functionalized Polyelectrolytes of Different Substituted Head Groups 2: Control of Surface Wetting in Self-Assembled Multilayer Films

A novel set of light-responsive polyelectrolytes has been developed and studied, to control and tune surface wettability by introducing various types of substituted R head-groups of azo polyelectrolytes in self-assembled multilayer (SAMU) films. As part of a larger project to develop polymer surfaces where one can exert precise control over properties important to proteins and cells in contact, photo-reversibly, we describe here how one can tune quite reliably the contact angle of a biocompatible SAMU, containing a photo-reversible azo chromophore for eventual directed cell growth. The azo polyelectrolytes described here have different substituted R head-group pairs of shorter-ionized hydrophilic COOH and SO₃H, shorter non-ionized hydrophobic H and OC₂H₅, and larger non-ionized hydrophobic octyl C₈H₁₇ and C₈F₁₇, and were employed as polyanions to fabricate the SAMU onto silicon substrates by using the counter-charge polycation PDAC. The prepared SAMU films were primarily characterized by measurement of their contact angles with water. The surface wetting properties of the thin films were found to be dependent on the type of substituted R-groups of the azo polyelectrolytes through their degree of ionization, size, hydrophobicity/hydrophilicity, solubility, conformation, and inter-polymeric association and intra-polymeric aggregation. All these factors appeared to be inter-related, and influenced variations in hydrophobic/hydrophilic character to different extents of aggregates/non-aggregates in solution because of solvation effects of the azo polyanions, and were thus manifested when adsorbed as thin films via the SAMU deposition process. For example, one interesting observation is significantly higher contact angles of 79° for SAMU films of larger octyl R groups of PAPEA-C₈F₁₇ and PAPEA-C₈H₁₇ than for others with contact angles of 64° observed for non-polar R-groups of OC₂H₅ and H. Furthermore, lower contact angle values of 59° for SAMU films with polar R-groups of COOH and SO₃H relative to that of non-polar R-groups are in accordance with their expected order of the hydrophilicity or hydrophobicity. It is possible that the large octyl groups are more effective in shielding the ionic functional groups on the substrate surface, and contributed less to the water drop-molecule interactions with ionic groups of the PDAC and/or AA groups. In addition, higher hydrophobicity of the SAMU films may be due to the incorporation of bulky and hydrophobic groups in these polyelectrolytes, which can produce aggregates on the surfaces of the SAMU films. Through understanding and controlling the complex aggregation behavior of the different substituted R-groups of these azo polyelectrolytes, and hence their adsorption on substrates, it appears possible to finely tune the surface energy of these biocompatible films over a wide range, enhance the photo-switching capabilities of the SAMU films, and tailor other surface properties for the development and application of new devices in diverse areas of microfluidics, specialty coatings, sensors, and biomedical sciences.     

Tuning the Solid‐State Optical Properties of Tetracene Derivatives by Modification of the Alkyl Side‐Chains: Crystallochromy and the Highest Fluorescence Quantum Yield in Acenes Larger than Anthracene

In the solution state, there were no notable differences between the optical properties of a range of alkyl‐substituted tetracenes. However, in the solid state, their photophysical properties changed with respect to the length, shape, number, and substitution pattern of the alkyl side chains, as well as the distribution of two regioisomers. Remarkably, in the solid state, 1,4,7,10‐tetraisopropyltetracene exhibited the highest reported fluorescence quantum yield of any tetracene derivative (0.90). The changes in the optical characteristics of these tetracenes according to the arrangement of the tetracene rings and the color‐change mechanism in the solid state are discussed. Moreover, the world record in solid‐state fluorescence efficiency in acenes larger than anthracene is described. DOI 10.1002/tcr.201200003     

Modification of Poly(2, 6-dimethyl-1,4-phenylene Oxide): Phosphorylation Studies

Side chain bromination of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) was carried out by using N-bromosuccinimide followed by phosphorylation of the bromo derivative with triethyl phosphite. Optimum conditions for minimum gel formation have been established. The products have been characterized by 'H-NMR and IR studies. Thermal behavior was investigated by thermogravimetry and differential scanning calorimetry in an air nitrogen atmosphere. Phosphorylated PPO starts to lose weight at 200°C, but the char yield increases with an increase in the phosphorus content of the polymer.     

Surface‐Tension‐Confined Microfluidics and Their Applications

This article is a brief overview of the emerging microfluidic systems called surface‐tension‐confined microfluidic (STCM) devices. STCM devices utilize surface energy that can control the movement of fluid droplets. Unlike conventional poly(dimethylsiloxane)‐based microfluidics which confine the movement of fluids by three‐dimensional (3D) microchannels, STCM systems provide two‐dimensional (2D) platforms for microfluidics. A variety of STCM devices have been prepared by various micro‐/nanofabrication strategies. Advantages of STCM devices over conventional microfluidics are significant reduction of energy consumption during device operation, facile introduction of fluids onto 2D microchannels without the use of a micropump, increased flow rate in a special type of STCM device, among others. Thus, STCM devices can be excellent alternatives for certain areas in microfluidics. In this Minireview, fabrication methods, operating modes, and applications of STCM devices are introduced.     

三嵌段两亲性聚乳酸共聚物的合成及其PVDF共混膜的制备

利用原子转移自由基聚合法(ATRP)合成三嵌段两亲性聚乳酸共聚物聚乙烯吡咯烷酮-聚乳酸-聚乙烯吡咯烷酮(PVP-b-PLA b-PVP),然后将其与聚偏氟乙烯(PVDF)进行其混,制备PVP-b-PLA-b-PVP/PVDF共混膜.结果表明:PVDF膜表面致密,膜断面中指状大孔和海绵状孔同时存在,而共混膜表面多孔,指状大孔贯穿整个断面;与PVDF膜相比,共混膜的孔隙率和孔径增大,水通量提高了158.87％,接触角下降了16.70％,抗污染指标下降了64.7％.     

Surfactant-Free Multiple Pickering Emulsions Stabilized by Combining Hydrophobic and Hydrophilic Nanoparticles

A series of W/O/W or O/W/O emulsion stabilized solely by two different types of solid nanoparticles were prepared by a two-step method. We explored the option of particular emulsifiers for the multiple Pickering emulsions, and a variety of nanoparticles (silica, iron oxide, and clay) only differing in their wettability was used. The primary W/O emulsion was obtained by the hydrophobic nanoparticles, and then the hydrophilic nanoparticles were used as emulsifier in the secondary emulsification to prepare the W/O/W emulsion. In a similar way, the primary O/W emulsion of the O/W/O emulsion was stabilized by the hydrophilic nanoparticles, while the secondary emulsification to prepare the O/W/O emulsion was effected with the hydrophobic nanoparticles. The resultant multiple Pickering emulsion was stable to coalescence for more than 3 months, except the W/O/W emulsions of which the secondary emulsion stabilized by clay nanoparticles became a simple O/W emulsion in a day after preparation. Moreover, the temperature and pH sensitive poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAm-co-MAA)) microgels were introduced as an emulsifier for the secondary emulsification to obtain the stimulus-responsive multiple W/O/W emulsion. Such microgel-stabilized multiple emulsions could realize the efficient controlled release of water-soluble dye, Rhodamine B (RB) on demand in a multiple-emulsion delivery system.      

Single‐electron transfer‐living radical polymerization of oligo(ethylene oxide) methyl ether methacrylate in the absence and presence of air

The efficient Cu(0) wire‐catalyzed single‐electron transfer‐living radical polymerization (SET‐LRP) of oligo(ethylene oxide) methyl ether methacrylate (OEOMA) in DMSO and binary mixtures of DMSO with H₂O is reported. Addition of 10–80% H₂O to DMSO resulted in an increase in the apparent rate constant of propagation ( ), corresponding to an increase in the polarity and extent of disproportionation. At higher H₂O content, decreases, and in H₂O is slightly lower than that in DMSO. This unexpected behavior was attributed to the physical inaccessibility of Cu(0) wire catalyst to the hydrophobic reactive centers of OEOMA and initiator which self‐assemble in H₂O into micellar aggregates and vesicles. This hypothesis was confirmed by the faster polymerization in H₂O than in DMSO during catalysis with Cu(0) nanoparticles generated by disproportionation of CuBr. SET‐LRP of OEOMA can be performed in protic and dipolar aprotic solvents in air by the addition of hydrazine hydrate. The polymerization exhibited no induction period and identical as in the degassed experiment, and led to polymers with narrow molecular weigh distribution. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3110–3122     

表面官能团化增强碳纳米笼超级电容器性能

以具有多级孔结构、高比表面积、良好导电性等特征的碳纳米笼（CNCs）为前体,采用硝酸氧化法在CNCs表面引入含氧官能团。以CNCs为超级电容器电极材料,在相同电流密度下,官能团化样品的比电容显著高于纯CNCs;在1A·g^-1下比电容最高可达到255F·g^-1,比纯CNCs的188F·g^-1增加了34%,这表明表面含氧官能团化能够显著提高CNCs的超级电容器比电容。在100A·g^-1的大电流密度下,硝酸氧化后CNCs的比电容保持在111~167F·g^-1,表明具有良好的耐大电流充放电性能。在10A·g^-1的电流密度下循环10000圈后,CNC-6M样品的比电容由196F·g^-1下降到176F·g^-1,样品的比电容仍保留90%,具有良好的循环稳定性。表面含氧官能团化CNCs所表现出的这种优异的超级电容器性能归因于CNCs的多尺度分级孔结构、高比表面积、良好的导电性、表面亲水性含氧官能团化带来的浸润性提高和引入的赝电容。