Gating characteristics of thermo-responsive and molecular-recognizable membranes based on poly(N-isopropylacrylamide) and β-cyclodextrin

Abstract Thermo-responsive and molecular-recognizable membranes with the same functional gate exhibiting triple gating functions are prepared by grafting poly(N-isopropylacrylamide-co-glycidyl methacrylate/β-cyclodextrin) (PNG-CD) chains in the pores of porous Nylon-6 substrate membranes with the combination of plasma-induced pore-filling grafting polymerization and chemical reaction. Morphological and componential analyses of the grafted membranes are confirmed by scanning electron microscope (SEM) and Fourier transform infrared spectrometer (FT-IR). The thermo-responsive and molecular-recognizable gating characteristics of the as-prepared membranes with different grafting yields of poly(N-isopropylacrylamide) (PNIPAM) and β-cyclodextrin (CD) are systematically investigated by examining the diffusional permeability of VB12 molecules through membranes in different conditions with changing environmental temperatures and guest molecules. Experimental results show that, besides reversibly thermo-responsive “open/close” gating performance in response to environmental temperature changing across the lower critical solution temperature (LCST) of the grafted PNG-CD chains in water (e.g., 37 °C ↔ 50 °C), the as-prepared membrane gates can not only switch from “close” to “open” state by recognizing certain guest molecules with a hydrophobic side group (e.g., 8-anilino-1-naphthalenesulfonic acid ammonium salt (ANS)) at temperatures below the LCST of grafted PNG-CD chains in water (e.g., at 37 °C), but also can switch from “open” to “close” state by recognizing different guest molecules with a hydrophilic side group or without side group (e.g., 2-naphthalenesulfonic acid (NS)) in different cases at temperatures above the LCST of PNG-CD in water (e.g., at 50 °C). The thermo-responsive and molecular-recognizable gating characteristics of the as-prepared membranes can be adjusted by changing the grafting yields of both PNIPAM and CD on the membranes as well as the molar ratio of PNIPAM in the grafted chains.

[1]  Bror Svarfvar,et al.  Drug Release from pH and Ionic Strength Responsive Poly(acrylic acid) Grafted Poly(vinylidenefluoride) Membrane Bags In Vitro , 2004, Pharmaceutical Research.

[2]  Takeo Yamaguchi,et al.  Osmotic pressure control in response to a specific ion signal at physiological temperature using a molecular recognition ion gating membrane. , 2004, Journal of the American Chemical Society.

[3]  Yu-Ling Cheng,et al.  Electrically-modulated variable permeability liquid crystalline polymeric membrane , 1993 .

[4]  Liang-Yin Chu,et al.  A Molecular‐Recognition Microcapsule for Environmental Stimuli‐Responsive Controlled Release , 2002 .

[5]  Kai Zhang,et al.  Modulated insulin permeation across a glucose-sensitive polymeric composite membrane. , 2002, Journal of controlled release : official journal of the Controlled Release Society.

[6]  Yoshihiro Ito,et al.  pH Control of Transport through a Porous Membrane Self-Assembled with a Poly(acrylic acid) Loop Brush , 2001 .

[7]  Plamen Atanassov,et al.  Photoregulation of Mass Transport through a Photoresponsive Azobenzene-Modified Nanoporous Membrane , 2004 .

[8]  D. Chung,et al.  Control of water permeation by pH and ionic strength through a porous membrane having poly(carboxylic acid) surface-grafted , 1992 .

[9]  Liang-Yin Chu,et al.  A pH‐Responsive Gating Membrane System with Pumping Effects for Improved Controlled Release , 2006 .

[10]  R. Petter,et al.  Cooperative binding by aggregated mono-6-(alkylamino)-.beta.-cyclodextrins , 1990 .

[11]  H. Kitano,et al.  Cyclodextrins Modified with Polymer Chains Which Are Responsive to External Stimuli , 1995 .

[12]  T. Yamaguchi,et al.  An Autonomous Phase Transition−Complexation/Decomplexation Polymer System with a Molecular Recognition Property , 2006 .

[13]  C. Yip,et al.  Characterization of nanostructure of stimuli-responsive polymeric composite membranes. , 2004, Biomacromolecules.

[14]  K. Neoh,et al.  Synthesis and Characterization of Poly(N-isopropylacrylamide)-graft-Poly(vinylidene fluoride) Copolymers and Temperature-Sensitive Membranes , 2002 .

[15]  Yoshihiro Ito,et al.  Nanometer-Sized Channel Gating by a Self-Assembled Polypeptide Brush , 2000 .

[16]  M. Heskins,et al.  Solution Properties of Poly(N-isopropylacrylamide) , 1968 .

[17]  Liang-Yin Chu,et al.  Thermoresponsive gating characteristics of poly(N-isopropylacrylamide)-grafted porous poly(vinylidene fluoride) membranes , 2004 .

[18]  Liang-Yin Chu,et al.  Thermoresponsive transport through porous membranes with grafted PNIPAM gates , 2003 .

[19]  K. Neoh,et al.  Thermo-responsive porous membranes of controllable porous morphology from triblock copolymers of polycaprolactone and poly(N-isopropylacrylamide) prepared by atom transfer radical polymerization. , 2008, Biomacromolecules.

[20]  X. Wu,et al.  Temperature and pH-responsive polymeric composite membranes for controlled delivery of proteins and peptides. , 2004, Biomaterials.

[21]  B. Ratner,et al.  Glucose-sensitive membrane coated porous filters for control of hydraulic permeability and insulin delivery from a pressurized reservoir , 1995 .

[22]  Shin-ichi Nakao,et al.  Development of a Fast Response Molecular Recognition Ion Gating Membrane , 1999 .

[23]  Cong-jie Gao,et al.  Preparation of pH-responsive phenolphthalein poly(ether sulfone) membrane by redox-graft pore-filling polymerization technique , 2007 .

[24]  Yoshihiro Ito,et al.  pH-Sensitive Gating by Conformational Change of a Polypeptide Brush Grafted onto a Porous Polymer Membrane , 1997 .

[25]  Shin-ichi Nakao,et al.  Development of a molecular recognition separation membrane using cyclodextrin complexation controlled by thermosensitive polymer chains , 2003 .

[26]  K. Neoh,et al.  Drug permeation through temperature-sensitive membranes prepared from poly(vinylidene fluoride) with grafted poly(N-isopropylacrylamide) chains , 2004 .

[27]  Shoji Kimura,et al.  Development of a molecular recognition ion gating membrane and estimation of its pore size control. , 2002, Journal of the American Chemical Society.

[28]  T. Yamaguchi,et al.  Development of molecular recognition membrane showing autonomous adsorption-desorption phenomenon , 2009 .

[29]  E. Rizzarelli,et al.  Coordination properties of 6-deoxy-6-[1-(2-amino) ethylamino]-β-cyclodextrin and the ability of its copper(II) complex to recognize and separate amino acid enantiomeric pairs , 1993 .

[30]  Liang-Yin Chu,et al.  Thermo‐Responsive Gating Characteristics of Poly(N‐isopropylacrylamide)‐Grafted Membranes , 2006 .

[31]  Jin Hong Kim,et al.  Preparation of surface-modified stimuli-responsive polymeric membranes by plasma and ultraviolet grafting methods and their riboflavin permeation , 1995 .

[32]  Liang-Yin Chu,et al.  A Thermoresponsive Membrane for Chiral Resolution , 2008 .

[33]  Shin-ichi Nakao,et al.  Response Mechanism of a Molecular Recognition Ion Gating Membrane , 2004 .

[34]  Liang-Yin Chu,et al.  Preparation of thermo-responsive gating membranes with controllable response temperature , 2007 .

[35]  Liang-Yin Chu,et al.  Preparation of glucose-sensitive microcapsules with a porous membrane and functional gates. , 2004, Colloids and surfaces. B, Biointerfaces.

[36]  K. Hu,et al.  Development and characterization of poly(vinylidene fluoride)–poly(acrylic acid) pore-filled pH-sensitive membranes ☆ , 2007 .

[37]  Yoshihiro Ito,et al.  Visualization of critical pH-controlled gating of a porous membrane grafted with polyelectrolyte brushes , 1997 .

[38]  Liang-Yin Chu,et al.  Characterization of microstructure of poly(N-isopropylacrylamide)-grafted polycarbonate track-etched membranes prepared by plasma-graft pore-filling polymerization , 2005 .

[39]  Yoshihiro Ito,et al.  pH-Controlled Gating of a Porous Glass Filter by Surface Grafting of Polyelectrolyte Brushes , 1997 .

[40]  Y. Lee,et al.  Preparation of pH/temperature responsive polymer membrane by plasma polymerization and its riboflavin permeation , 1997 .

[41]  H. Tenhu,et al.  Grafting of Poly(N-isopropylacrylamide) with Poly(ethylene oxide) under Various Reaction Conditions , 2000 .

[42]  T. Kanamori,et al.  Synthesis and characterization of an ultrathin polyion complex membrane containing β-cyclodextrin for separation of organic isomers , 2004 .

[43]  Liang-Yin Chu,et al.  Molecular‐Recognition‐Induced Phase Transitions of Two Thermo‐Responsive Polymers with Pendent β‐Cyclodextrin Groups , 2008 .

[44]  K. Himmelstein,et al.  Effect of an applied electric field on liquid crystalline membranes: control of permeability , 1985 .

[45]  Liang-Yin Chu,et al.  Temperature-dependent molecular-recognizable membranes based on poly(N-isopropylacrylamide) and β-cyclodextrin , 2009 .

[46]  Hongzhi Xie,et al.  Synthesis of Chemical Modified β-cyclodextrin and its Inclusion Behavior in Alcohol/Water Mixed Solvents , 2001 .

[47]  Liang-Yin Chu,et al.  Negatively thermoresponsive membranes with functional gates driven by zipper-type hydrogen-bonding interactions. , 2005, Angewandte Chemie.

[48]  M. Ulbricht,et al.  Permeability and electrokinetic characterization of poly(ethylene terephthalate) capillary pore membranes with grafted temperature-responsive polymers. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[49]  Liang-Yin Chu,et al.  Control of pore size and permeability of a glucose-responsive gating membrane for insulin delivery. , 2004, Journal of controlled release : official journal of the Controlled Release Society.