Three-layer flow membrane system on a microchip for investigation of molecular transport

A stable three-layer flow system, water/organic solvent/water, has been successfully applied for the first time in a microchannel to get rapid transport through an organic liquid membrane. In the continuous laminar flow region, the analyte (methyl red) was rapidly extracted across the microchannel from the donor to the acceptor phase through the organic solvent phase (cyclohexane). Thermal lens microscopy was used to monitor the process. The thickness of the organic phase, sandwiched by the two aqueous phases, was approximately 64 microm, and it was considered as a thin liquid organic membrane. Permeability studies showed the effects of molecular diffusion, layer thickness, and organic solvent-water partition coefficient on the molecular transport. In the microchip, complete equilibration was achieved in several seconds, in contrast to a conventionally used apparatus, where it takes tens of minutes. The thickness of the organic and aqueous boundary layers was defined as equal to the microchannel dimensions, and the organic solvent-water partition coefficient was determined on a microchip using the liquid/liquid extraction system. Experimental data on molecular transport across the organic membrane were in agreement with the calculated permeability based on the three-compartment water/organic solvent/water model. This kind of experiment can be performed only in a microspace, and the system can be considered as a potential biological membrane for future in vitro study of drug transport.     

Liquid membrane operations in a microfluidic device for selective separation of metal ions

A three-phase flow, water/n-heptane/water, was constructed in a microchannel (100-microm width, 25-microm depth) on a glass microchip (3 cm x 7 cm) and was used as a liquid membrane for separation of metal ions. Surface modification of the microchannel by octadecylsilane groups induced spontaneous phase separation of the three-phase flow in the microfluidic device, which allows control of interfacial contact time and off-chip analysis using conventional analytical apparatus. Prior to the selective transport of a metal ion through the liquid membrane in the microchannel, the forward and backward extraction of yttrium and zinc ions was investigated in a two-phase flow on a microfluidic device using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (commercial name, PC-88A) as an extractant. The extraction conditions (contact time of the two phases, pH, extractant concentration) in the microfluidic device were examined. These investigations demonstrated that the conventional methodology for solvent extraction of metal ions is applicable to solvent extraction in a microchannel. Finally, we employed the three-phase flow in the microchannel as a liquid membrane and observed the selective transport of Y ion through the liquid membrane. In the present study, we succeeded, for the first time, in the selective separation of a targeted metal ion from an aqueous feed solution to a receiving phase within a few seconds by employing a liquid membrane formed in a microfluidic device.     

中空纤维反渗透复合膜的制备及分离性能研究

通过间苯二胺水溶液和均苯三甲酰氯的正己烷溶液的界面缩聚反应,以聚砜中空纤维超滤膜为基膜,制备了聚芳香酰胺反渗透复合膜.用扫描电镜对复合膜的表面及断面进行表征,探索了复合膜在不同操作条件以及进液性质下的分离性能.研究结果表明:中空纤维反渗透复合膜具有良好的耐压密性和稳定性,在0.7MPa下具有良好的分离性能.此复合膜对NaCl、KCl、CaCl2、MgCl2、MgSO4、Na2SO4等无机盐水溶液的脱盐率不低于93.5%,通量大于21L/(m2·h);对天津市大港、小站两地的苦成水具有优异的淡化性能;对天津市自来水中的盐分也有良好的去除率.     

Inner Surface Design of Functional Microchannels for Microscale Flow Control

Fluidic flow behaviors in microfluidics are dominated by the interfaces created between the fluids and the inner surface walls of microchannels. Microchannel inner surface designs, including the surface chemical modification, and the construction of micro‐/nanostructures, are good examples of manipulating those interfaces between liquids and surfaces through tuning the chemical and physical properties of the inner walls of the microchannel. Therefore, the microchannel inner surface design plays critical roles in regulating microflows to enhance the capabilities of microfluidic systems for various applications. Most recently, the rapid progresses in micro‐/nanofabrication technologies and fundamental materials have also made it possible to integrate increasingly complex chemical and physical surface modification strategies with the preparation of microchannels in microfluidics. Besides, a wave of researches focusing on the ideas of using liquids as dynamic surface materials is identified, and the unique characteristics endowed with liquid–liquid interfaces have revealed that the interesting phenomena can extend the scope of interfacial interactions determining microflow behaviors. This review extensively discusses the microchannel inner surface designs for microflow control, especially evaluates them from the perspectives of the interfaces resulting from the inner surface designs. In addition, prospective opportunities for the development of surface designs of microchannels, and their applications are provided with the potential to attract scientific interest in areas related to the rapid development and applications of various microchannel systems.     

Surface modification method of microchannels for gas-liquid two-phase flow in microchips

A capillarity restricted modification method for microchannel surfaces was developed for gas--liquid microchemical operations in microchips. In this method, a microstructure combining shallow and deep microchannels and the principle of capillarity were utilized for chemical modification of a restricted area of a microchannel. A hydrophobic--hydrophilic patterning in microchannels was prepared as an example for guiding gas and liquid flows along the respective microchannels. Validity of the patterning was confirmed by measuring aqueous flow leak pressure from the hydrophilic microchannel to the hydrophobic one. The leak pressure of 7.7-1.1 kPa agreed well with that predicted theoretically from the Young-Laplace equation for the microchannel depth of 8.6-39 microm. In an experiment to demonstrate usefulness and effectiveness of the method, an air bubble was first introduced into the hydrophilic microchannel and purged from the hydrophobic-hydrophilic patterned microchannels. Next, the patterning structure was applied to remove dissolved oxygen by contacting the aqueous flow with a nitrogen flow. The concentration of dissolved oxygen decreased with contact time, and its time course agreed well with numerical simulation. These demonstrations showed that the proposed patterning method can be used in general microfluidic gas-liquid operations.     

Simultaneous emulsification and interfacial polycondensation for the preparation of colloidal suspensions of nanocapsules

Sub-micrometric particles having an oil core and a polymer shell (nanocapsules) have been prepared by combining in a single stage the emulsification process and an interfacial polymerization reaction. The spontaneous emulsification produced very fast a dispersion of oil droplets of 100–400 nm mean diameter at the surface of which the subsequent polycondensation reaction took place. The process has been optimized with respect to the choice of α-tocopherol as the oil and made robust regarding the presence of monomers in the aqueous and oil phases and their conversion into polymers. The major cause of troubles was the large concentration of diol or diamine monomers in the aqueous phase that made the oil droplets unstable with respect to aggregation immediately after their formation. Once the emulsifier has adsorbed and the polymerization has completed, the final suspensions of nanocapsules were quite stable over long periods. A secondary population of micrometric particles that coexisted with the nanocapsules was present in several cases, which was unfavourable regarding their application as a drug delivery system for cosmetic applications.     

Flow behavior in surface-modified microchannels with polymer nanosheets

The paper describes water flow behavior in surface-modified microchannels. We prepared straight-type microchannels which had rectangular cross sections with four different combinations of microchannel surface wettability; cleaned glass substrates served as hydrophilic microchannel walls and the microchannel walls coated with polymer Langmuir–Blodgett (LB) films were used as hydrophobic surfaces. The polymer LB films were successfully transferred onto glass substrates by vertical dipping method. The flow rates and the water meniscus shape strongly depended on the microchannel surface wettability. The decrease in flow rate with the increasing number of hydrophobic (polymer LB film) surface was attributed to the higher adhesion energy of hydrophobic surface. The Reynolds number was also characterized to be in the order of 10^− 1, implying a specific feature of microchannel; laminar flow.     

六氮杂苯并菲扩环三蝶烯微孔聚合物的合成及其在二氧化碳捕获与催化转化领域的应用（英文）

作为二氧化碳化学转化的研究热点,利用二氧化碳作为原料合成有机小分子化合物被认为是解决温室效应的有效途径之一.本文合成了一种基于六氮杂苯并菲扩环三蝶烯的有机微孔聚合物(HAT-TP).该多孔聚合物表现出较高比表面积以及较好的二氧化碳吸附能力.通过与锌离子配位,Zn/HAT-TP聚合物还能够作为一类良好的非均相催化剂催化二氧化碳与环氧化物反应生成对应的环状碳酸酯.     

Thermally controlled permeation of ionic molecules through synthetic nanopores functionalized with amine-terminated polymer brushes

We present temperature-dependent ionic transport through an array of nanopores (cylindrical and conical) and a single conical nanopore functionalized with amine-terminated poly(N-isopropylacrylamide) [PNIPAAM-NH(2)] brushes. For this purpose, nanopores are fabricated in heavy ion irradiated polyethylene terephthlate (PET) membranes by a controlled chemical track-etching technique, which leads to the generation of carboxyl (COOH) groups on the pore surface. End-functionalized polymer chains are immobilized onto the inner pore walls via a 'grafting-to' approach through the covalent linkage of surface COOH moieties with the terminal amine groups of the PNIPAAM molecules by using carbodiimide coupling chemistry. The success of the chemical modification reaction is corroborated by measuring the permeation flux of charged analytes across the multipore membranes in an aqueous solution, and for the case of single conical pore by measuring the current-voltage (I-V) characteristics, which are dictated by the electrostatic interaction of the charged pore surface with the mobile ions in an electrolyte solution. The effective nanopore diameter is tuned by manipulating the environmental temperature due to the swelling/shrinking behaviour of polymer brushes attached to the inner nanopore walls, leading to a decrease/increase in the ionic transport across the membrane. This process should permit the thermal gating and controlled release of ionic drug molecules through the nanopores modified with thermoresponsive polymer chains across the membrane.     

A Rational Reconfiguration of Electrolyte for High-Energy and Long-Life Lithium–Chalcogen Batteries

Lithium–chalcogen batteries are an appealing choice for high-energy-storage technology. However, the traditional battery that employs liquid electrolytes suffers irreversible loss and shuttle of the soluble intermediates. New batteries that adopt Li⁺-conductive polymer electrolytes to mitigate the shuttle problem are hindered by incomplete discharge of sulfur/selenium. To address the trade-off between energy and cycle life, a new electrolyte is proposed that reconciles the merits of liquid and polymer electrolytes while resolving each of their inferiorities. An in situ interfacial polymerization strategy is developed to create a liquid/polymer hybrid electrolyte between a LiPF₆-coated separator and the cathode. A polymer-gel electrolyte in situ formed on the separator shows high Li⁺ transfer number to serve as a chemical barrier against the shuttle effect. Between the gel electrolyte and the cathode surface is a thin gradient solidification layer that enables transformation from gel to liquid so that the liquid electrolyte is maintained inside the cathode for rapid Li⁺ transport and high utilization of active materials. By addressing the dilemma between the shuttle chemistry and incomplete discharge of S/Se, the new electrolyte configuration demonstrates its feasibility to trigger higher capacity retention of the cathodes. As a result, Li–S and Li–Se cells with high energy and long cycle lives are realized, showing promise for practical use.     

Polyrhodanine modified anodic aluminum oxide membrane for heavy metal ions removal

Polyrhodanine was immobilized onto the inner surface of anodic aluminum oxide (AAO) membrane via vapor deposition polymerization method. The polyrhodanine modified membrane was applied to remove heavy metal ions from aqueous solution because polyrhodanine could be coordinated with specific metal ions. Several parameters such as initial metal concentration, contact time and metal species were evaluated systematically for uptake efficiencies of the fabricated membrane under continuous flow condition. Adsorption isotherms of Hg(II) ion on the AAO-polyrhodanine membrane were analyzed with Langmuir and Freundlich isotherm models. The adsorption rate of Hg(II) ion on the membrane was obeyed by a pseudo-second order equation, indicating the chemical adsorption. The maximum removal capacity of Hg(II) ion onto the fabricated membrane was measured to be 4.2 mmol/g polymer. The AAO-polyrhodanine membrane had also remarkable uptake performance toward Ag(I) and Pb(II) ions. Furthermore, the polyrhodanine modified membrane could be recycled after recovery process. These results demonstrated that the polyrhodanine modified AAO membrane provided potential applications for removing the hazardous heavy metal ions from wastewater.     

Microstructural characterization and quantitative analysis of the interfacial carbides in Al(Si)/diamond composites

The existence of interfacial carbides is a well-known phenomenon in Al/diamond composites, although quantitative analyses are not described so far. The control of the formation of interfacial carbides while processing Al(Si)/diamond composites is of vital interest as a degradation of thermophysical properties appears upon excessive formation. Analytical quantification was performed by GC–MS measurements of gaseous species released upon dissolving the matrix and interfacial reaction products in aqueous NaOH solutions and the CH₄/N₂ ratio of the evolving reaction gases can be used for quantification. Although the formation of interfacial carbides is significantly suppressed by adding Si to Al, also a decline in composite thermal conductivity is observed in particular with increasing contact time between the liquid metal and the diamond particles during gas pressure infiltration. Furthermore, surface termination of diamond particles positively affects composite thermal conductivity as oxygenated diamond surfaces will result in an increase in composite thermal conductivity compared to hydrogenated ones. In order to understand the mechanisms responsible for all impacts on the thermal conductivity and thermal conductance behaviour, the metal/diamond interface was electrochemical etched and characterized by SEM. Selected specimens were also cut by an ultrashort pulsed laser system to characterize interfacial layers at the virgin cross section in the reactive system Al/diamond.     

Robust natural nanocomposites realizing unprecedented ultrafast precise molecular separations

Synthetic polymer membranes can potentially reduce the large energy and carbon footprints that are typically associated with traditional chemical separation technologies. Unfortunately, current production protocols negate the green benefits of membrane separation. To address this bottleneck, here we report the use of natural materials monosaccharide – glucose and polydopamine and Zr-based metal organic frameworks (MOFs) to fabricate ultrathin nanocomposite membranes via interfacial polymerization reaction. The synergistic effect of these three materials on angstrom-scale molecular transport both in organic solvent and aqueous environment was elucidated using a series of complementary techniques. We demonstrate such nature-inspired nanocomposite membranes enable structural stability even in polar aprotic solvents, and unparalleled ultra-fast, low-pressure, precise separations in both nanofiltration modes, which easily surpass state-of-the-art membranes relying on unsustainable materials. The multi-functionality of saccharide nanocomposites was elegantly harnessed to impact separation applications that contribute towards a better living environment.     

原位生长制备ZIF-8/聚酰胺双层复合纳滤膜及其染料分离性能

以2,6-二氨基吡啶、均苯三甲酰氯为水相和油相单体,通过界面聚合法制备吡啶功能化聚酰胺(PA-PY)膜,随后利用酰氯水解羧基和吡啶氮原子与锌离子的配位作用,在膜表面原位生长ZIF-8(类沸石咪唑酯骨架材料-8),制备了ZIF-8/聚酰胺(ZIF-8/PA-PY)双层复合纳滤膜。扫描电镜分析结果表明:原位生长法可在PA-PY分离层生成晶型结构完整、致密的ZIF-8层,且随着原位生长时间的增加,ZIF-8层逐渐增厚。ZIF-8/PA-PY双层复合纳滤膜对负电性染料的截留率较高,原位生长时间为12h时,双层复合纳滤膜对甲基蓝截留率为97.9%,刚果红为99.6%。     

Continuous-flow chemical processing on a microchip by combining microunit operations and a multiphase flow network

A new design and construction methodology for integration of complicated chemical processing on a microchip was proposed. This methodology, continuous-flow chemical processing (CFCP), is based on a combination of microunit operations (MUOs) and a multiphase flow network. Chemical operations in microchannels, such as mixing, reaction, and extraction, were classified into several MUOs. The complete procedure for Co(II) wet analysis, including a chelating reaction, solvent extraction, and purification was decomposed into MUOs and reconstructed as CFCP on a microchip. Chemical reaction and molecular transport were realized in and between continuous liquid flows in a multiphase flow network, such as aqueous/aqueous, aqueous/organic, and aqueous/organic/aqueous flows. When the determination of Co(II) in an admixture of Cu(II) was carried out using this methodology, the determination limit (2sigma) was obtained as 18 nM, and the absolute amount of Co chelates detected was 0.13 zmol, that is, 78 chelates. The sample analysis time was faster than that of a conventional processing system. Moreover, troublesome operations such as phase separation and acid and alkali washing, all necessary for the conventional system, were simplified. The CFCP methodology proposed here can be applied to various on-chip applications.     

溶胶-凝胶法制备含氟聚丙烯酸酯/SiO2杂化材料的结构与性能

用酸催化溶胶-凝胶法制得SiO2溶胶,与丙烯酸酯单体原位聚合,制备了含氟聚丙烯酸酯/SiO2杂化材料。利用红外光谱、场发射扫描电镜、X射线光电子能谱等表征了杂化材料的结构、形态及表面化学组成;研究了SiO2相的形态、分布和界面状况等与杂化材料的表面性能、热学性能和力学性能的关联与影响。结果表明,SiO2在杂化体系中以Si-O网络的形式存在,并与有机相之间有良好键合;杂化材料的疏水性、热稳定性和硬度随着SiO2含量的增加逐渐增强,附着力则先增大后减小。     

Paper–paraffin composites prepared by interfacial polymerisation reaction on paper surface and its function of thermal energy storage

Paper–paraffin composites were prepared by an interfacial polymerisation reaction on the paper surface and its function of thermal energy storage was studied. Filter paper impregnated with O/W emulsion, which was composed of ethylenediamine, NaOH and paraffin microcapsules prepared by methyl methacrylate polymer (PMMA), was left in a beaker containing a cyclohexane solution of terephthaloyl chloride. The paraffin could fix on the treated paper surface and the encapsulation of the paraffin before the interfacial polymerisation reaction on the paper surface was effective in the preparation of paper with the function of heat storage.     

Ionic Hydrogen-Bonded Organic Frameworks for Ion-Responsive Antimicrobial Membranes

Functionalization of hydrogen-bonded organic frameworks (HOFs) for specific applications has been a long-lasting challenge in HOF materials. Here, an efficient way to integrate functional species in the HOF structure through constructing an anionic framework is presented. The obtained HOFs, taking PFC-33 (PFC = porous materials from FJIRSM,CAS) as an example, integrate a porphyrin photosensitizer as a porous backbone and a commercial biocide as counterions in the structure. The permanent channels and the electrostatic interaction between the framework and the counterions provide PFC-33 ion-responsive biocide-release behavior in various physiological environments, thus exhibiting synergistic photodynamic and chemical antimicrobial efficiency. The unbonded carboxyl groups residing on the HOF surface further allow for manipulating the interfacial interaction between the PFC-33 and the polymer matrix for membrane fabrication. Therefore, a polyHOF membrane with high stability, desired flexibility, and good permeability is obtained, which demonstrates noticeable bacterial inhibition toward Escherichia coli. This study may shed light on the functionalization of HOF materials for broad application potentials.     

巯基接枝氧化石墨烯/聚酰胺复合膜制备及反渗透脱盐性能

反渗透膜技术作为脱盐的核心技术,在海水和苦咸水淡化、超纯水制备、污水回水等领域具有广泛应用前景,但其渗透性-选择性之间的 “trade-off” 效应仍是限制反渗透技术发展的一大挑战。本研究将表面功能化(接枝巯基官能团)的氧化石墨烯(GO)掺入间苯二胺水相溶液中,通过水相间苯二胺和有机相均苯三甲酰氯界面聚合的方法制备出巯基接枝氧化石墨烯(GO-SH)/聚酰胺(PA)反渗透复合膜。利用TEM、SEM、EDS、FTIR和NMR对接枝后粉体进行表征,利用2 g·L?1 NaCl水溶液测试膜的脱盐性能,优化了界面聚合水相pH和反应时间的设定。研究结果表明,GO-SH能够更均匀地分散在PA中,优化后的pH为11,反应时间为4 min,当改性后粉体含量为0.09wt%时,复合膜水通量可达48 L·m?2·h?1,脱盐率达到99.6%,相较于本实验接枝前纳米材料复合的PA膜分别提高了30% 和2.54%。表面功能化的GO有效地解决了无机纳米粒子和有机聚合物的相容性,提高膜脱盐性能,有望进一步降低反渗透项目的运行成本。      

纳米Ti02接枝改性后与PTFE共混制备中空超滤膜纤维

水处理膜材料多为有机聚合物,在机械强度、化学稳定性等方面的缺陷限制了有机膜的使用范围。为克服膜材料本身的局限性,提高其水处理性能,引入Ti02粒子,制备一种中空超滤膜。在纳米TiO2粒子的制备过程中引入咪唑类离子液体,将甲基硅氧烷甲基丙烯酸酯（MS—MA）与甲基丙烯酸甲酯（MMA）的聚合物接枝到TiO2表面。接枝的Ti0：与PTFE进行共混,可制得一种全新的中空超滤膜纤维。