Fabrication of perforated isoporous membranes via a transfer-free strategy: enabling high-resolution separation of cells.

Thin perforated membranes with ordered pores are ideal barriers for high-resolution and high-efficiency selective transport and separation of biological species. However, for self-assembled thin membranes with a thickness less than several micrometers, an additional step of transferring the membranes onto porous supports is generally required. In this article, we present a facile transfer-free strategy for fabrication of robust perforated composite membranes via the breath figure process, and for the first time, demonstrate the application of the membranes in high-resolution cell separation of yeasts and lactobacilli without external pressure, achieving almost 100% rejection of yeasts and more than 70% recovery of lactobacilli with excellent viability. The avoidance of the transfer step simplifies the fabrication procedure of composite membranes and greatly improves the membrane homogeneity. Moreover, the introduction of an elastic triblock copolymer increases the interfacial strength between the membrane and the support, and allows the preservation of composite membranes in a dry state. Such perforated ordered membranes can also be applied in other size-based separation systems, enabling new opportunities in bioseparation and biosensors.

[1]  V. Abetz,et al.  Asymmetric superstructure formed in a block copolymer via phase separation. , 2007, Nature materials.

[2]  H. Okano,et al.  Direct isolation and RNA-seq reveal environment-dependent properties of engrafted neural stem/progenitor cells , 2012, Nature Communications.

[3]  Zhi-Kang Xu,et al.  Ordered microporous membranes templated by breath figures for size-selective separation. , 2012, Journal of the American Chemical Society.

[4]  Zhi‐Kang Xu,et al.  Tunable assembly of nanoparticles on patterned porous film. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[5]  Pore shape of honeycomb-patterned films: modulation and interfacial behavior. , 2012, The journal of physical chemistry. B.

[6]  Jian Li,et al.  Fabrication of robust micro-patterned polymeric films via static breath-figure process and vulcanization. , 2011, Journal of colloid and interface science.

[7]  Aijuan Zhang,et al.  Breath figure arrays: unconventional fabrications, functionalizations, and applications. , 2013, Angewandte Chemie.

[8]  Zhi‐Kang Xu,et al.  Nonlithographic Fabrication of Nanostructured Micropatterns via Breath Figures and Solution Growth , 2014 .

[9]  J. Hao,et al.  Fabrication of freestanding honeycomb films with through-pore structures via air/water interfacial self-assembly. , 2011, Chemical communications.

[10]  Zhi Wei,et al.  Generation of folliculogenic human epithelial stem cells from induced pluripotent stem cells , 2014, Nature Communications.

[11]  S. Santra,et al.  Role of nanoparticle valency in the nondestructive magnetic-relaxation-mediated detection and magnetic isolation of cells in complex media. , 2009, Journal of the American Chemical Society.

[12]  T. Russell,et al.  Functionalized Nanoporous Thin Films and Fibers from Photocleavable Block Copolymers Featuring Activated Esters , 2013 .

[13]  Jian-guo Tang,et al.  Preparation of a highly permeable ordered porous microfiltration membrane of brominated poly(phenylene oxide) on an ice substrate by the breath figure method , 2012 .

[14]  Zhi Ma,et al.  Constructing robust 3-dimensionally conformal micropatterns: vulcanization of honeycomb structured polymeric films , 2011 .

[15]  M. Griffiths Improving the Safety and Quality of Milk , 2010 .

[16]  V. Calo,et al.  Self-assembly in casting solutions of block copolymer membranes , 2013 .

[17]  Clemens Bechinger,et al.  Single-file diffusion of colloids in one-dimensional channels. , 2000, Physical review letters.

[18]  Zhi‐Kang Xu,et al.  Polystyrene with hydrophobic end groups: synthesis, kinetics, interfacial activity, and self-assemblies templated by breath figures , 2014 .

[19]  I. Weissman,et al.  Isolation of primitive endoderm, mesoderm, vascular endothelial and trophoblast progenitors from human pluripotent stem cells , 2012, Nature Biotechnology.

[20]  Zhi‐Kang Xu,et al.  Synthesis of polystyrene with cyclic, ionized and neutralized end groups and the self-assemblies templated by breath figures , 2014 .

[21]  H. Bai,et al.  Robust Microsieves with Excellent Solvent Resistance: Cross-Linkage of Perforated Polymer Films with Honeycomb Structure. , 2013, ACS macro letters.

[22]  K. Matyjaszewski,et al.  Design and preparation of porous polymers. , 2012, Chemical reviews.

[23]  T. Gaborski,et al.  Charge- and size-based separation of macromolecules using ultrathin silicon membranes , 2007, Nature.

[24]  Bernard François,et al.  Self-organized honeycomb morphology of star-polymer polystyrene films , 1994, Nature.

[25]  Zhi‐Kang Xu,et al.  Polystyrenes with hydrophilic end groups: synthesis, characterization, and effects on the self-assembly of breath figure arrays. , 2014, The journal of physical chemistry. B.

[26]  Klaus-Viktor Peinemann,et al.  Selective separation of similarly sized proteins with tunable nanoporous block copolymer membranes. , 2013, ACS nano.

[27]  Hai-Qing Gong,et al.  Capturing and recovering of Cryptosporidium parvum oocysts with polymeric micro-fabricated filter , 2011 .

[28]  Xiaofeng Wang,et al.  Developing porous honeycomb films using miktoarm star copolymers and exploring their application in particle separation. , 2014, Macromolecular rapid communications.

[29]  Klaus-Viktor Peinemann,et al.  Ultraporous Films with Uniform Nanochannels by Block Copolymer Micelles Assembly , 2010 .

[30]  Arnan Mitchell,et al.  Microfluidics and Raman microscopy: current applications and future challenges. , 2013, Chemical Society reviews.

[31]  R. Stocker,et al.  Synergistic Prevention of Biofouling in Seawater Desalination by Zwitterionic Surfaces and Low‐Level Chlorination , 2013, Advanced materials.

[32]  Jin Kon Kim,et al.  Virus Filtration Membranes Prepared from Nanoporous Block Copolymers with Good Dimensional Stability under High Pressures and Excellent Solvent Resistance , 2008 .

[33]  Penghui Zhang,et al.  Multi-shell structured fluorescent-magnetic nanoprobe for target cell imaging and on-chip sorting. , 2013, ACS applied materials & interfaces.

[34]  C. Dekker Solid-state nanopores. , 2007, Nature nanotechnology.

[35]  Kornelius Nielsch,et al.  Fast fabrication of long-range ordered porous alumina membranes by hard anodization , 2006, Nature materials.

[36]  T. Hayakawa,et al.  From angstroms to micrometers: self-organized hierarchical structure within a polymer film. , 2003, Angewandte Chemie.

[37]  C. Lim,et al.  Isoporous micro/nanoengineered membranes. , 2013, ACS nano.

[38]  V. Dyakonov,et al.  Self-Organized Networks Based on Conjugated Polymers , 2001 .

[39]  Tomoko Yoshino,et al.  Size-selective microcavity array for rapid and efficient detection of circulating tumor cells. , 2010, Analytical chemistry.

[40]  Hang Sun,et al.  Functional Free‐Standing Graphene Honeycomb Films , 2013 .

[41]  Masatsugu Shimomura,et al.  Fabrication of honeycomb film of an amphiphilic copolymer at the air-water interface , 2002 .

[42]  Paul I. Okagbare,et al.  Highly efficient circulating tumor cell isolation from whole blood and label-free enumeration using polymer-based microfluidics with an integrated conductivity sensor. , 2008, Journal of the American Chemical Society.

[43]  A. Turner,et al.  Biomedical Materials and Diagnostic Devices: Tiwari/Biomedical , 2012 .

[44]  Matthias Wessling,et al.  Hierarchically Structured Assembly of Polymer Microsieves, made by a Combination of Phase Separation Micromolding and Float‐Casting , 2012, Advanced materials.

[45]  Klaus-Viktor Peinemann,et al.  Switchable pH-responsive polymeric membranes prepared via block copolymer micelle assembly. , 2011, ACS nano.

[46]  Zhi‐Kang Xu,et al.  Multiple interfaces in self-assembled breath figures. , 2014, Chemical communications.

[47]  M. Hillmyer,et al.  Nanoporous membranes derived from block copolymers: from drug delivery to water filtration. , 2010, ACS nano.

[48]  M. Ulbricht,et al.  Photo-irradiation for preparation, modification and stimulation of polymeric membranes , 2009 .

[49]  Thomas P. Russell,et al.  Nanoporous Membranes with Ultrahigh Selectivity and Flux for the Filtration of Viruses , 2006 .

[50]  D. Kasper,et al.  Isolation of carbohydrate-specific CD4+ T cell clones from mice after stimulation by two model glycoconjugate vaccines , 2012, Nature Protocols.

[51]  Zhi‐Kang Xu,et al.  Patterned biocatalytic films via one-step self-assembly. , 2012, Chemical communications.

[52]  Klaus-Viktor Peinemann,et al.  Self-assembled isoporous block copolymer membranes with tuned pore sizes. , 2014, Angewandte Chemie.

[53]  Zhi‐Kang Xu,et al.  Synthesis of core cross-linked star polystyrene with functional end groups and self-assemblies templated by breath figures , 2014 .

[54]  S. Jang,et al.  Hierarchically self-organized monolithic nanoporous membrane for excellent virus enrichment. , 2014, ACS applied materials & interfaces.

[55]  Marta Fernández-García,et al.  Towards hierarchically ordered functional porous polymeric surfaces prepared by the breath figures approach , 2014 .

[56]  Hong Chen,et al.  Aptamer-modified micro/nanostructured surfaces: efficient capture of Ramos cells in serum environment. , 2013, ACS applied materials & interfaces.

[57]  Igor Jurisica,et al.  Isolation of Single Human Hematopoietic Stem Cells Capable of Long-Term Multilineage Engraftment , 2011, Science.

[58]  Yong Wang,et al.  An Emerging Pore‐Making Strategy: Confined Swelling‐Induced Pore Generation in Block Copolymer Materials , 2011, Advanced materials.