Bioinspired Membranes Research Articles

Bioinspired EVAL membrane modified with cilia-like structures showing simultaneously enhanced permeability and antifouling properties

A simple and effective strategy to simultaneously enhance the permeability and antifouling properties of ethylene vinyl alcohol (EVAL) membrane was developed based on the bioinspired natural cleaner, cilia. Taking clue from the self-cleaning effect of cilia, supramolecular polyrotaxanes (PRs) with sliding and rotating cyclic molecules along linear chains were synthesized using azide-alkyne click chemistry. Cilia-like PRs were incorporated into EVAL matrix in the fabrication of modified EVAL membranes. Cilia-like structures protruding from the membrane surface have been observed by SEM, TEM and AFM. By imitating natural ciliary movements, these structures provided a proactive self-cleaning system to remove the foulants. The introduction of cilia-like PRs enhanced the surface roughness and hydrophilicity, and significantly enhanced permeability by 55.3% compared to raw EVAL membrane. Moreover, the membrane modified with cilia-like PRs showed an excellent antifouling property with a lower water flux decline (12.6%) and higher water flux recovery (94%) in dynamic fouling tests. Furthermore, this modified membrane develops the scope of bioinspired membranes, inspiring more attractive potential applications in self-cleaning materials, dynamic membranes and supramolecular machines.

Amine-Containing Block Copolymers for the Bottom-Up Preparation of Functional Porous Membranes

The remarkable ability of biological systems to specifically recognize, sort, and process molecules encourages the development of novel bio-inspired membranes and interfaces. Herein, we focus on the functionalization of amphiphilic polystyrene-block-poly(2-hydroxyethyl methacrylate) (PS-b-PHEMA) with the amino acid glycine yielding polar block segments with primary amine functionalities. Excellent control over the tailored block copolymer (BCP) synthesis and functionalization is proven by size exclusion chromatography (SEC), 1H solution NMR, and 15N solid state NMR spectroscopy. For the first time, BCPs containing primary amines were used for the self-assembly and non-solvent induced phase separation (SNIPS) process for the preparation of isoporous and integral asymmetric membranes. Hexagonally arranged open pores with diameters of 19 nm were obtained as shown by scanning electron microscopy (SEM), atomic force microscopy (AFM), and pH-dependent water flux measurements. Additionally, the primary amine was...

Biomimetic and bioinspired membranes for water purification: A critical review and future directions

Various types of channel proteins, broadly named porins, present in the cell membrane of gram‐negative bacteria have specific functionalities depending on their selectivity toward different nutrients or toward water. The high selectivity of porins has led to their incorporation into synthetic systems, in a field called biomimetics. An example is the addition of water channel proteins, or aquaporins, to polymeric separations membranes in order to enhance their performance in terms of selectivity and permeability. The concept of incorporating aquaporins into synthetic membranes has been studied for the last 10 years; however, there are still limitations such as costs, alignment into the membrane assembly, and scalability of membrane fabrication. Therefore, in recent years, there has been an increase in the study of synthesizing molecules with similar structure–function relationships of porins. These artificial channels attempt to mimic the biological porins, while being synthesized using simpler chemistry, being solvent compatible, and requiring less space on the membrane surface which helps to incorporate more channels into the membrane assembly. In summary, the future of biomimetic and bioinspired membranes depends on the design strategies, level of nature imitation, and the performance of these systems on a commercial scale. © 2019 American Institute of Chemical Engineers Environ Prog, 38:e13215, 2019

Hierarchical Optimization of High-Performance Biomimetic and Bioinspired Membranes

Biomimetic and bioinspired membranes have emerged as an innovative platform for water purification and aqueous separations. They are inspired by the exceptional water permeability (∼109 water molecules per second per channel) and perfect selectivity of biological water channels, aquaporins. However, only few successes have been reported for channel-based membrane fabrication due to inherent challenges of realizing coherence between channel design at the angstrom level and development of scalable membranes that maintain these molecular properties at practice-relevant scales. In this article, we feature recent progress toward practical biomimetic membranes, with the review organized along a hierarchical structural perspective that biomimetic membranes commonly share. These structures range from unitary pore shapes and tubular hydrophobic channel geometries to self-assembled bilayer structures and finally to macroscale membranes covering a size range from the angstrom, to the micrometer scale, and finally to the centimeter and larger scales. To maximize the advantage of water channel implementation into membranes, each feature needs to be optimized in an appropriate manner that provides a path to successful scale-up to achieve high performance in practical biomimetic and bioinspired membranes.

Properties of Omp2a-Based Supported Lipid Bilayers: Comparison with Polymeric Bioinspired Membranes.

Omp2a β-barrel outer membrane protein has been reconstituted into supported lipid bilayers (SLBs) to compare the nanomechanical properties (elastic modulus, adhesion forces, and deformation) and functionality of the resulting bioinspired system with those of Omp2a-based polymeric nanomembranes (NMs). Protein reconstitution into lipid bilayers has been performed using different strategies, the most successful one consisting of a detergent-mediated process into preformed liposomes. The elastic modulus obtained for the lipid bilayer and Omp2a are ∼19 and 10.5 ± 1.7 MPa, respectively. Accordingly, the protein is softer than the lipid bilayer, whereas the latter exhibits less mechanical strength than polymeric NMs. Besides, the function of Omp2a in the SLB is similar to that observed for Omp2a-based polymeric NMs. Results open the door to hybrid bioinspired substrates based on the integration of Omp2a-proteoliposomes and nanoperforated polymeric freestanding NMs.

Aquaporin-Based Biomimetic and Bioinspired Membranes for New Frontiers in Sustainable Water Treatment Technology: Approaches and Challenges

Biomimetic and bioinspired membranes are the efficient membrane technology when it comes to multiple usage scenarios, including next generations of biomaterials within the commercial separation applications, as well as, water and wastewater treatment technologies. In recent years, aquaporin biomimetic membranes for water separation have raised considerable interest. These membranes have displayed distinguished properties and outstanding performances, as diverse interactions, varying selective transport mechanisms, superior stability, maximum resistance to membrane fouling, and distinct adaptability. The biomimetic membranes have made significant contributions when it comes to water stress, environmental threats and energy. It has the potential to produce clean water more efficiently than reverse osmosis membranes (RO), while saving up to 80% of the energy used for desalination processes. More than half of the 15000 desalination plants around the world utilize RO technologies, and the implementation of biomimetic membranes on a large scale could save hundreds of millions of dollars in energy cost annually (potential savings of $1.45 million/year for 100 ML/day desalination plant). This paper discusses the interplay of the main components of aquaporin biomimetic membranes: aquaporin proteins, block copolymers for aquaporin proteins reconstitution, and polymer-based supporting structures. We focus specifically on the challenges and review recent developments on the interplay between aquaporin proteins and block copolymers. The recent efforts in embedding reconstituted aquaporin proteins in membrane designs that are based on conventional thin film interfacial polymerization techniques are evaluated. In addition, emerging challenges and opportunities for biomimetic membranes are studied from the perspective of current and future applications.

Bio-inspired Membrane Operations in P Systems with Active Membranes

In this paper we define a general class of P systems covering some biological operations with membranes, including evolution, communication, and modifying the membrane structure, and we describe and formally specify some of these operations: membrane merging, membrane separation, membrane release. We also investigate a particular combination of types of rules that can be used in solving the SAT problem in linear time.

Recent Advances of Membrane-Cloaked Nanoplatforms for Biomedical Applications.

In terms of the extremely small size and large specific surface area, nanomaterials often exhibit unusual physical and chemical properties, which have recently attracted considerable attention in bionanotechnology and nanomedicine. Currently, the extensive usage of nanotechnology in medicine holds great potential for precise diagnosis and effective therapeutics of various human diseases in clinical practice. However, a detailed understanding regarding how nanomedicine interacts with the intricate environment in complex living systems remains a pressing and challenging goal. Inspired by the diversified membrane structures and functions of natural prototypes, research activities on biomimetic and bioinspired membranes, especially for those cloaking nanosized platforms, have increased exponentially. By taking advantage of the flexible synthesis and multiple functionality of nanomaterials, a variety of unique nanostructures including inorganic nanocrystals and organic polymers have been widely devised to substantially integrate with intrinsic biomoieties such as lipids, glycans, and even cell and bacteria membrane components, which endow these abiotic nanomaterials with specific biological functionalities for the purpose of detailed investigation of the complicated interactions and activities of nanomedicine in living bodies, including their immune response activation, phagocytosis escape, and subsequent clearance from vascular system. In this review, we summarize the strategies established recently for the development of biomimetic membrane-cloaked nanoplatforms derived from inherent host cells (e.g., erythrocytes, leukocytes, platelets, and exosomes) and invasive pathogens (e.g., bacteria and viruses), mainly attributed to their versatile membrane properties in biological fluids. Meanwhile, the promising biomedical applications based on nanoplatforms inspired by diverse moieties, such as selective drug delivery in targeted sites and effective vaccine development for disease prevention, have also been outlined. Finally, the potential challenges and future prospects of the biomimetic membrane-cloaked nanoplatforms are also discussed.

Bioinspired Diatomite Membrane with Selective Superwettability for Oil/Water Separation

Membranes with selective superwettability for oil/water separation have received significant attention during the past decades. Hierarchical structures and surface roughness are believed to improve the oil repellency and the stability of Cassie-Baxter state. Diatoms, unicellular photosynthetic algae, possess sophisticated skeletal shells (called frustules) which are made of hydrated silica. Motivated by the hierarchical micro- and nanoscale features of diatom, we fabricate a hierarchical diatomite membrane which consists of aligned micro-sized channels by the freeze casting process. The fine nano-porous structures of frustules are well preserved after the post sintering process. The bioinspired diatomite membrane performs both underwater superoleophobicity and superhydrophobicity under various oils. Additionally, we demonstrate the highly efficient oil/water separation capabililty of the membranes in various harsh environments. The water flux can be further adjusted by tuning the cooling rates. The eco-friendly and robust bioinspired membranes produced by the simple, cost-effective freeze casting method can be potentially applied for large scale and efficient oil/water separation.

A Theoretical Characterization of Curvature Controlled Adhesive Properties of Bio-Inspired Membranes

Some biological systems, such as the tree frog, Litoria caerulea, and the bush-cricket, Tettigonia viridissima, have developed the ability to control adhesion by changing the curvature of their pads. Active control systems of adhesion inspired by these biological models can be very attractive for the development of devices with controllable adhesive properties. In this paper, we present a theory describing the adhesive behavior of an artificial system consisting of an inflatable membrane clamped to a metallic cylinder and filled with air. In such a system, by controlling the internal pressure acting on the membrane, it is possible to modulate the adhesive strength. In particular, an increase of the internal pressure and, hence, the curvature of the membrane, results in a decrease of the pull-off force. Results predicted by the theoretical model are in good agreement with experimental data. The model explains the apparent contradictory results observed for the thick membrane with zero curvature. In fact, in this case, large pull-off forces should be expected, but zero values are measured due to an initial small misalignment between indenter and membrane, which is not possible to control with precision during the experiments. The present model might help to achieve a better understanding of the adhesion behavior of biological systems and of the fingertips that, in a broad sense, may be regarded as shell-like structures.

Bio-inspired cell membrane ingredient cholesterol-conjugated chitosan as a potential material for bone tissue repair

We prepared a cholesterol-conjugated chitosan(CHCS) material and evaluated its potential application as a bone tissue repair material by in vitro cell experiments. Cell proliferation, differentiation and morphology on CHCS membrane surfaces with different graft degrees were assessed in mouse pre-osteoblasts MC3T3-E1 cells. The results indicate that CHCS materials could promote the proliferation of MC3T3-E1 cells at low graft degrees, but the CHCS material with high graft degree inhibits the proliferation of cells in contrast to the pure chitosan membrane. However, the alkaline phosphatase(ALP) activity of MC3T3-E1 cells on different CHCS membrane surface increased with increasing graft degrees of cholesterol. The area of cells stretched onto the surface of CHCS materials was larger than on the surface of CS materials, and more microfilaments and stress fibers in cells were observed on CHCS materials than on the pure chitosan material surface. After 7 d, the expression of related osteogenic marker genes, such as runt-related transcription factor 2(Runx2), osterix(OSX), osteocalcin(OCN), osteopontin(OPN), ALP and collagen I(COL-I) were all up-regulated in CHCS materials to different degrees compared to pure chitosan material, which indicated that the CHCS materials facilitated MC3T3-E1 cell differentiation and maturation. Characterizing CHCS materials is useful in designing and developing strategies for bone tissue engineering.

Membrane parallelism for discrete Morse theory applied to digital images

In this paper, we propose a bio-inspired membrane computational framework for constructing discrete Morse complexes for binary digital images. Our approach is based on the discrete Morse theory and we work with cubical complexes. As example, a parallel algorithm for computing homology groups of binary 3D digital images is designed.

Interactions of Bio-Inspired Membranes with Peptides and Peptide-Mimetic Nanoparticles

Via Dissipative Particle Dynamics (DPD) and implicit solvent coarse-grained (CG) Molecular Dynamics (MD) we examine the interaction of an amphiphilic cell-penetrating peptide PMLKE and its synthetic counterpart with a bio-inspired membrane. We use the DPD technique to investigate the interaction of peptide-mimetic nanoparticles, or nanopins, with a three-component membrane. The CG MD approach is used to investigate the interaction of a cell-penetrating peptide PMLKE with single-component membrane. We observe the spontaneous binding and subsequent insertion of peptide and nanopin in the membrane by using CG MD and DPD approaches, respectively. In addition, we find that the insertion of peptide and nanopins is mainly driven by the favorable enthalpic interactions between the hydrophobic components of the peptide, or nanopin, and the membrane. Our study provides insights into the mechanism underlying the interactions of amphiphilic peptide and peptide-mimetic nanoparticles with a membrane. The result of this study can be used to guide the functional integration of peptide and peptide-mimetic nanoparticles with a cell membrane.

A pH-responsive smart surface for the continuous separation of oil/water/oil ternary mixtures

To handle the serious issue of increasing oil spill accidents, many strategies have been proposed to either clean spilt oil or separate water/oil mixture. Especially, superhydrophilic/underwater superoleophobic smart materials have recently shown advantages in overcoming problems of oil blocking and water barriers during conventional oil/water-separating process of oil-rich mixtures with superhydrophobic/superoleophilic materials. However, to the best of our knowledge, no prior reports have detailed smart materials with the wetting properties of superhydrophobic/superoleophilic that can be applied in continuous in situ separations of oil/water/oil ternary mixtures, which are common in practical oil spill cases. Herein, we describe the fabrication and efficacy of a pH-responsive smart device for continuous in situ separations of such oil/water/oil ternary mixtures without the need for ex situ treatments. In air, the superhydrophobic/superoleophilic surface of the device allowed dichloromethane to permeate through while preventing water from passing. The superhydrophilicity/underwater superoleophobicity of the device surface following alkaline treatments prevented the passage of hexane while allowing water to penetrate the device. Recent efforts to find quick and simple ways to remediate oil spills have focused on bio-inspired membranes that selectively filter either oil or water from a mixture. Real-world oil pollution, however, often contains complex, oil–water–oil emulsions that can clog single-purpose membranes. Now, a team led by Feng Shi from Beijing University of Chemical Technology in China has developed a pH-responsive ‘smart’ device that can separate three component oil–water mixtures on demand. Their device — a porous copper foam cube coated with silver aggregates and self-assembled organic films — initially absorbs oil while blocking water. Increasing the mixture's pH transforms the device wettability from superhydrophobic to superhydrophilic, meaning that only water can now be absorbed. Sequential pH changes enable efficient separation of tertiary oil spills without additional treatments. By fabricating a pH-responsive smart device with tunable surface-wetting properties, we have realized continuous in situ separations of oil/water/oil ternary mixtures without ex situ treatments of cleaning or drying. In air, the superhydrophobic/superoleophilic surface of the smart device allowed heavy oil to permeate through while preventing water from passing. When exposed to alkaline water, the superhydrophilicity/underwater superoleophobicity of the smart device surface prevented the passage of hexane while allowing water to penetrate. In this way, efficient separation and collection of the individual components of a complex oil/water/oil mixture was realized in a continuous process with no ex situ treatments. This method could provide a strategy for continuous separations of oil/water/oil ternary mixtures, which are common in practical oil spill cases.

Computational Design of Multi-component Bio-Inspired Bilayer Membranes

Our investigation is motivated by the need to design bilayer membranes with tunable interfacial and mechanical properties for use in a range of applications, such as targeted drug delivery, sensing and imaging. We draw inspiration from biological cell membranes and focus on their principal constituents. In this paper, we present our results on the role of molecular architecture on the interfacial, structural and dynamical properties of bio-inspired membranes. We focus on four lipid architectures with variations in the head group shape and the hydrocarbon tail length. Each lipid species is composed of a hydrophilic head group and two hydrophobic tails. In addition, we study a model of the Cholesterol molecule to understand the interfacial properties of a bilayer membrane composed of rigid, single-tail molecular species. We demonstrate the properties of the bilayer membranes to be determined by the molecular architecture and rigidity of the constituent species. Finally, we demonstrate the formation of a stable mixed bilayer membrane composed of Cholesterol and one of the phospholipid species. Our approach can be adopted to design multi-component bilayer membranes with tunable interfacial and mechanical properties. We use a Molecular Dynamics-based mesoscopic simulation technique called Dissipative Particle Dynamics that resolves the molecular details of the components through soft-sphere coarse-grained models and reproduces the hydrodynamic behavior of the system over extended time scales.

Computational Design of Multi-component Bio-Inspired Bilayer Membranes

Our investigation is motivated by the need to design bilayer membranes with tunable interfacial and mechanical properties for use in a range of applications, such as targeted drug delivery, sensing and imaging. We draw inspiration from biological cell membranes and focus on their principal constituents. In this paper, we present our results on the role of molecular architecture on the interfacial, structural and dynamical properties of bio-inspired membranes. We focus on four lipid architectures with variations in the head group shape and the hydrocarbon tail length. Each lipid species is composed of a hydrophilic head group and two hydrophobic tails. In addition, we study a model of the Cholesterol molecule to understand the interfacial properties of a bilayer membrane composed of rigid, single-tail molecular species. We demonstrate the properties of the bilayer membranes to be determined by the molecular architecture and rigidity of the constituent species. Finally, we demonstrate the formation of a stable mixed bilayer membrane composed of Cholesterol and one of the phospholipid species. Our approach can be adopted to design multi-component bilayer membranes with tunable interfacial and mechanical properties. We use a Molecular Dynamics-based mesoscopic simulation technique called Dissipative Particle Dynamics that resolves the molecular details of the components through soft-sphere coarse-grained models and reproduces the hydrodynamic behavior of the system over extended time scales.

Modulation of yeast hexokinase on bio-inspired membranes

Hexokinase (HK) is the first enzyme of the glycolytic pathway and is known to modulate its own activity by binding to the mitochondrial membrane. In this study, the enzymatic activity of HK was measured in the presence of various liposomes. The positively charged liposome with an appropriate charge density was found to increase the HK activity. The HK activity was enhanced 1.5-fold in the presence of 5mol% didodecyldimethylammonium bromide (DDAB) and 1.8-fold with 5–10mol% 3β-[N-(N′,N′-dimethylaminoethane)-carbamoyl] cholesterol hydrochloride (DC-Cholesterol) on the POPC (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocoline) liposome. Analysis of (i) HK binding onto liposome, (ii) intrinsic Trp fluorescence, and (iii) circular dichroism of HK suggested that the HK activity was enhanced on positively charged microdomain because of its slight conformational change through the electrostatic and hydrophobic interactions.

A “Membranome”- Based Approach toward “Bio-Inspired Membrane”

A “Membranome”- Based Approach toward “Bio-Inspired Membrane”

A review of water treatment membrane nanotechnologies

Nanotechnology is being used to enhance conventional ceramic and polymeric water treatment membrane materials through various avenues. Among the numerous concepts proposed, the most promising to date include zeolitic and catalytic nanoparticle coated ceramic membranes, hybrid inorganic–organic nanocomposite membranes, and bio-inspired membranes such as hybrid protein–polymer biomimetic membranes, aligned nanotube membranes, and isoporous block copolymer membranes. A semi-quantitative ranking system was proposed considering projected performance enhancement (over state-of-the-art analogs) and state of commercial readiness. Performance enhancement was based on water permeability, solute selectivity, and operational robustness, while commercial readiness was based on known or anticipated material costs, scalability (for large scale water treatment applications), and compatibility with existing manufacturing infrastructure. Overall, bio-inspired membranes are farthest from commercial reality, but offer the most promise for performance enhancements; however, nanocomposite membranes offering significant performance enhancements are already commercially available. Zeolitic and catalytic membranes appear reasonably far from commercial reality and offer small to moderate performance enhancements. The ranking of each membrane nanotechnology is discussed along with the key commercialization hurdles for each membrane nanotechnology.

New Bioinspired Membrane Made of a Biological Ion Channel Confined into the Cylindrical Nanopore of a Solid-State Polymer.

A hybrid nanoporous membrane made of a solid-state polymeric thin film in which an ion channel is confined is realized. The primary and extremely encouraging results obtained by confocal fluorescence spectroscopy and ion diffusion measurement demonstrate respectively that (i) the considered ion channel, that is, Gramicidin-A, can be confined selectively inside the nanopores and (ii) the ionic permeability of the membrane is enhanced. Atomistic molecular simulations are also reported and fruitfully compared to the experimental findings.