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Ion/molecule transportation in nano- pore/channels: From critical principles to diverse functions Zhongpeng Zhu, Dianyu Wang, Ye Tian, and Lei Jiang J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b00086 • Publication Date (Web): 07 May 2019 Downloaded from http://pubs.acs.org on May 7, 2019

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Journal of the American Chemical Society

Ion/molecule transportation in nano- pore/channels: From critical principles to diverse functions Zhongpeng Zhu, §,

‡

Dianyu Wang,

†

Ye Tian, *, §,

‡

and Lei Jiang §,

‡

§ Key Laboratory of Bio-inspired Materials and Interfacial Science, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China † College of Chemistry, Jilin University, Changchun, 130012, P. R. China ‡ University of Chinese Academy of Sciences, Beijing, 100049, P.R. China ABSTRACT: Nano-pore/channels are universal from biological systems to various artificial materials. Taking advantage of size confinement and tailoring the interior components, numerous functions can be achieved such as selectivity, gating, rectification, and so on, which result from diverse interactions between ion/molecules and nano-pore/channels. In this perspective, on account of the summarized critical principles namely size/shape, wettability, charge, recognition, and other interactions during ion/molecule transportation in nano-pore/channels, we mainly introduce four sections of applications namely selective transportation in separation, controllable gating systems, energy conversion devices, and sensors. Besides, some typical challenges and possible future research endeavors in the related field will also be provided.

Introduction Nano-pore/channels are universal structure and play a critical role both in biological systems and artificial materials.1-7 It is well-known that ion/molecule transportation in living system such as retina, neuro, muscle and so forth is crucial for the vital activities.8 Biological nano-channels such as ion channel, water channel and glucose channel can effectively regulate ion/molecule transportation across the cell membrane based on their unique shape and the interfacial protein.9,10 Taking inspiration from biological nano-channels in cell membranes, bio-mimic artificial nano-pore/channels can be constructed to transport ion/molecules directionally by modulating the interfacial interactions. These artificial materials can be compactly summarized as shown in Figure 1a according to their diverse structure features in different dimensions. In three dimensional (3D) systems, nanochannels are found in interconnected porous fibers,11 anodic aluminum oxides,12 titanium dioxide nano-tube arrays,13 silicon nano-wire arrays,14 aggregation of nano-particles15 and so forth.16 While, two dimensional (2D) systems are usually formed by stacking layered 2D materials like graphene17 and polymeric carbon nitride.18 At the same time, quasi-2D nano-channels can also be found in patterned surfaces.19,20 Bio-mimic one dimensional nano-channels are widely reported, such as polymer nano-channels,21 carbon nano-tubes,22,23 boron nitride nano-tubes,24 silicon nanochannels,25 nano-pores26 and so on. While, zero dimensional (0D) systems are referred to as porous particles for which channels formed within them like porous polymer particles,27,28 silica hollow spheres,29 zeolite,30,31 metal organic frameworks,32 carbon nano-hemispheres,33 and etc.34 Owing to its universal existences and broad applications both in nature and artificial functional materials, extensive researchers have devoted to this field.35,36 To further improve the function of artificial materials in different dimensions, one of the key studies should be addressed on critical principles of ion/molecule transportations in nano-pore/channels with an eye on their potential applications.

Summarized from various ion/molecule transportation phenomena of artificial nano-pore/channel materials in different dimensions, the critical principles can be briefly introduced as shown in Figure 1b namely physical factors of size/shape and chemical factors of wettability, charge (Debye layer), host-guest recognition and other interactions. Firstly, size/shape is the most critical physical feature of nanopore/channel system which can effectively separate ion/molecules with different diameters ranging from angstrom to nano-meter.37-40 Potential applications considering this principle can be extended to selective transportation of ions in the field of ion sieving and effective separation of gases, miscible liquids or emulsions. With the decrease of size, the interfacial wettability within nanopore/channel will play a significant role in controllable transportation of various molecules.41 It was reported that when the distance between two hydrophobic plate is narrower than 100 nm, water density would be essentially similar to the bulk vapor which means the liquid water cannot flow through this area.42 In this case, based on surface modification or external stimulation to adjust the interfacial wettability, controllable transportation of ion/molecules in hydrophilic and hydrophobic nano-pore/channels can be successfully achieved. Further application mainly based on this principle was widely reported, such as stimuli-responsive smart devices,43 directional transportation of gases or liquids.11,44,45 Furthermore, charge influence related to Debye layer is one of the main factor in ion rectification which is the crucial principle mainly in the application field concerning energy conversion devices.46 In channels narrower than the Debye length of the electrolyte, the surface charges on the inner walls repel ions of the same charge and attract the counterions. Such unipolar ionic transport can be applied in energy conversion of various energy resources such as salinity, pressure, light and so on.25,47,48 In addition, host-guest recognition is another typical principle which is widely used in sensors to identify specific species. Ultra-sensitive sensors for DNA sequencing based on the resistive pulse technique and controllable multigating are widely reported.49-55 Last but not least, other

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interactions such as hydrogen bonds, π-π interactions, Van Der Waals’ force, coordination and so on also play intriguing roles during ion/molecule transportation. Effective selective transportation of specific ion or molecule can be achieved based on different interactions between ion/molecules and interfacial molecules within nano-pore/channels, which is one of the key factors in ion sieving and separation of miscible mixtures. Based on these principles, there are broad applications of nano-pore/channel systems such as waste water treatment, sea water desalination, ion serving, real-time separation, controlled drug delivery, nano-fluidic logic devices, salinity gradient based power generation, pressure driven energy conversion, DNA sequencing, environmental monitoring, wearable devices, clinical applications and so forth which can be concisely presented based on the integration of multiple critical principles as shown in Figure

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1c, and can provide more flexible approaches for building functional devices. 41 In this perspective, a brief overview of the state-of-the-art achievements and potential applications based on the critical principles of ion/molecule transportation within nanopore/channel systems will be presented. There are mainly four sections around nano-pore/channel based applications: selective transportation of ion/molecule and its related field of separation; ion/molecule controllable gating systems with single, dual, and multi-state responses; ion rectification applied in clean energy conversion systems introduced from 1D, 2D, 3D, to composite structures; and a brief introduction of sensing in sequencing and detection. Hereinto, a personal view on challenges and suggestions on future developments about nano-pore/channel systems will be discussed at the end of each section. Besides, we will also offer a concise summary and a brief outlook at the end of this perspective.

Figure 1. Critical principles in nano-pore/channels for ion/molecule transportation summarized from different dimensions and the brief introduction of applications. (a) Nano-pore/channel is universal from different dimensions such as three dimensional (3D) interconnected nano-channels, two dimensional (2D) nano-channels formed by stacked laminar sheets, one dimensional (1D) single nano-channels and zero dimensional (0D) porous particles. (b) Based on these typical physical models of different dimensions, the critical principle of nano-pore/channel system can be concisely summarized as size/shape, wettability, charge (Debye layer), recognition, and other interactions. (c) Applications based on these critical principles can be extended into four typical categories: selective transportation of ion/molecule in separation, controllable gating, clean energy conversion, and ultra-sensitive sensing. Reproduced with permission.24,44,56,57 Copyright 2017, American Chemical Society. Copyright 2013, American Chemical Society. Copyright 2013, Nature Publishing Group. Copyright 2008, Nature Publishing Group.

Selective transportation of ion/molecules in separation With the development of green chemistry and in consideration of the fresh water crisis, the separation of ion/molecule is of great significance. In this case, nanopore/channel system shows advantage in controllable transport of ion/molecule concerning the critical principles of size/shape, wettability, or other interfacial interactions, which can be successfully applied in separation of various systems. For example, by controlling the interfacial wettability within nano-pore/channels, specific molecules can be precisely

controlled to pass through the membrane.58 In another hand, molecules or ions with different diameters can be either trapped in or filtered through the nano-pore/channels based on their unique size/shape features which can also achieve selective transportation. Previously, a detailed study on separation of immiscible liquids on nano-porous titanium dioxide fibers with precisely manipulated surface wettability was reported.14 When the surface tension of the nano-porous membrane is manipulated between the intrinsic wetting thresholds of two immiscible


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liquids, successful separation can be achieved owing to its super-lyophilic behavior for one liquid and super-lyophobic behavior for another. Besides the effective separation of liquids by manipulating the wettability of nanopore/channels, demulsification can be achieved by further reducing the pore/channel size which proved to be critical for separation of emulsions. An ultrathin single wall carbon nanotube was prepared by vacuum-filtering method.59 The free-standing film can effectively separate both surfactantstabilized and surfactant-free water-in-oil emulsions with ultrafast flux compared with the commercial filtration membranes. Another intriguing example showed the wettability can be adjusted by pre-infused liquids for the separation of immiscible multi-phase liquids. A porous TiO2/SiO2 composite nano-fibrous membrane with preinfused organic or aqueous solution was prepared as shown in Figure 2a.11 Further simulation results with density functional theory revealed that the selective transportation of water, nitromethane, and cyclohexane resulted from the different binding energy between the interfacial hydroxyl groups of TiO2/SiO2 composite porous nano-fibrous membrane and the liquid molecules. In another word, composite membrane with hydroxyl groups within the nano-channels pre-infused by one kind of liquid allows the liquid with higher polarity to pass through, but stops the liquid with lower polarity to penetrate. Besides the separation of immiscible liquids, separation of immiscible mixture consisting of liquids and gases with capillary-stabilized liquid infused gating mechanism was also reported as shown in Figure 2b.45 By manipulating the pressure, controllable separation of air-water-oil mixture was also achieved. This integration with sustained antifouling behavior can dynamically modulate the behavior of liquid and gas in a microfluidic device which is expected to be useful in macro-scale fluidic systems. Besides, by modulating the interior, wettability of nanopore/channel systems, selective gas or liquid transport can be achieved which is sigificnt in interfacial chemical reactions. For example, with hydrophobic modification of nanopore/channels, gases can be transferred from one side to another, while water will be stopped from permeating. In this case, it offers an effective way to provide gases from one side of the three-phase interfacial reaction sites for gas involved catalytic reactions. Recently, a glucose oxidase embedded hydrophobic nano-channel reactor supported by porous anodic alumina was reported.44 By adjusting the interfacial wettability of 3D nano-channels to create hydrophobic anodic alumina, selective transportation of oxygen molecules can be achieved which effectively enhanced the three-phase catalytic efficiency. With controlled wettability and gas transportation, the catalytic efficiency of the glucose oxidase is improved up to 80-fold compared with the traditional method which offers oxygen from solutions.

Challenges in renewable energy related to bio-mass and water crisis like desalination are to separate miscible mixtures like ions and molecules.60-62 For example, separation of olefin and paraffin is challenging owing to their similarities in physic-chemical properties. Recently, a post-synthetic ligand exchange method of 2-methylimidazole with 2imidazolecarboxaldehyde in zeolitic imidazolate frameworks-8 membrane was proposed, as shown in Figure 2c.63 The separation productivity was improved approaching 780 × 10-10 mol m-2 s-1 Pa-1 for propylene and propane, which is four times compared with as-synthesized zeolitic imidazolate frameworks -8 membrane with counter-diffusion method. Furthermore, cross-lined ferritin membrane was prepared with protein-surrounded nano-channels and effective separation of protoporphyrin was achieved as shown in Figure 2d.15 Recently, hydrophilic-hydrophobic heterostructured nano-porous polymer particles were synthesized by emulsion interfacial polymerization.27 By switching the solvent polarity, successful separation of low-abundance glycopeptide from complex bio-fluids can be achieved, offering a promising method to separate biomolecules in complex samples. In another hand, a stacked graphene oxide nano-sheet membrane decorated by metal ions exhibits high selective permeability and can efficiently separate miscible solvents such as ethanol/water and ethanol/toluene, as shown in Figure 2e.64 Further experiments demonstrated the simultaneous reaction and product extraction of ester reaction can be successfully carried out. Another study of ultra-fast ion sieving was reported based on the porous PET membrane, as shown in Figure 2f.65 After irradiated by heavy ions and ultraviolet, nano-pore with a radius of ~0.5 nm can be obtained, which showed high transport rate of K+. Despite the encouraging results shown above, there are still many challenges on nano-pore/channels for separation. One of the tough challenges is to create robust nano-pore/channel membrane which possesses both high selectivity and flux. To increase the separation selectivity of miscible liquids, one potential approach referring to the critical principle is to enhance the interactions between the specific ion/molecule and nano-pore/channel by introducing strong interaction sites on the interfaces such as coordinate interaction, hydrogen bond interaction, and etc. To increase the separation flux, membrane with high porosity is preferred. In the field of emulsion separation, besides the successful separation of water from the emulsion, it is of great significance to further separate the surfactant from the oil/surfactant mixture. Moreover, simultaneous separation of miscible liquids during chemical reactions for practical application is another direction of future efforts. In the field of ion sieving, the effective separation of monatomic ions with similar size is another significant endeavor for future research.



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Figure 2. Typical separation of immiscible and miscible mixtures by various nano-pore/channel systems. (a) Separation of immiscible liquids by nano-fibrous membrane based on the polarity difference of pre-infused liquids and separated liquids. Reproduced with permission.11 Copyright 2017, Nature Publishing Group. (b) Separation of immiscible gas and liquid by liquid-infused polytetrafluoroethylene membrane with interconnected nano-pores. Reproduced with permission.45 Copyright 2015, Nature Publishing Group. (c) Separation of miscible gas mixture of propylene and propane by ultrathin zeolite imidazolate framework membrane prepared by a post-synthetic linker exchange method. Reproduced with permission.63 Copyright 2018, Wiley-VCH. (d) Separation of miscible organic molecules by a cross-linked ferritin membrane supported by aluminum oxide. Reproduced with permission.15 Copyright 2009, Nature Publishing Group. (e) Separation of miscible organic liquids by metal-ion-decorated grapheme oxide nano-sheet membrane with 2D nano-channels. Reproduced with permission.64 Copyright 2017, Wiley-VCH. (f) Separation of miscible ions by a polyethylene terephthalate (PET) membrane with negatively charged residues (COO-) within the nano-channel. Reproduced with permission.65 Copyright 2018, Nature Publishing Group.

Nano-pore/channel based controllable gating Controllable gating is of great potential applications in drug sustained release, nano-fluidic logic devices and etc.41,66,67 Smart nano-pore/channel systems based on shape, charge, wettability and so forth can be constructed after modification of various functional molecules. Typical responsive molecules can be briefly introduced from four aspects, namely photo responsive molecules such as photoacid molecule 8-hydroxypyrene-1,3,6-trisulfonate and photoalkali molecule malachite green carbinol base,68 azobenzene, spiropyran, cinnamic acid and etc;69 pH responsive molecules such as C-quadruplex DNA,70 polymer brush71 and etc;56,72 temperature responsive molecules such as poly(Nisopropylacrylamide),73 block copolymer,74 and etc;75 ion responsive molecules such as G-quadruplex DNA,70 DNA hydrogel,76 and etc;77 molecule responsive molecules such as supramolecule,78 imidazole-containing polymers,79 and etc.80 Based on the external stimuli-factors, the controllable gating nano-pore/channel system can be mainly divided into the following three parts: single stimuli-responsive nanochannels, dual stimuli-responsive nano-channels with asymmetric modifications, and multi-state stimuli-responsive nano-channels with tunable states. As to single stimuli-responsive nano-pore/channels, the stimuli-factors can further be divided into three categories:

ions like H+,71,81 K+,76 Zn2+,77 Hg2+,82 Ca2+,83 and etc; molecules like ATP,80,84 H2O2,85 proteins,86 and etc87,88; environments like light,89,90 voltage,43 temperature,91 and etc. Previously, a bio-mimic DNA motor modified symmetric poly(ethylene terephthalate) (PET) nano-channel was prepared.92 With the increase of pH, this nano-channel can change from close to open state. Laterally, another bio-mimic nano-channel for K+ responsive gating with G-quadruplex modified PET nano-channel was also prepared.93 Besides the ion-responsive nano-pore/channels, to achieve successful drug delivery in human body, bio-molecules triggered stimuli-responsive nano-channels are also widely needed.94 Previously, a high efficient cylindrical PET nano-pore gated by cross-lined DNA superstructures was reported.95 Further study demonstrated that it can be reopened by ATP and DNase I. The ON-OFF ratio of 103-105 for the nano-channel with diameter around 650 nm was found which offered an effective way for controllable release of drugs in human body. In another case, chitosan capped drug delivery by mesoporous silica nanoparticles for cancer treatments was reported.96 The anticancer drugs can be delivered to targeted CCL cells where the stimulus of pH and lysozyme can reopen the capped nanochannels. Moreover, dual-compartment Janus mesoporous silica nanoparticles were synthesized through an anisotropic island nucleation and growth method.97 The dual-drugs controllable release by heat and near-infrared light of these


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porous silica nanoparticles can be further applied in nanobiomedicine which showed high efficiency to kill cancer cells. In addition to the stimulations in liquid, stimulations from environments are also very significant for smart devices. A hydrophobic PET nano-pore controlled by electric field was reported as shown in Figure 3a.43 Fully modified hydrophobic nano-pore didn’t respond to electric field, in contrast, locally modified hydrophobic nano-channel can respond to the external electric field resulted from the local vapor pockets. Recently, a magnetic gated nano-fluidic based on the integration of superhydrophilic nano-channels and reconfigurable ferrofluid for controlling nano-scale mass flux was reported as shown in Figure 3b.98 Due to the changeable shape of the ferrofluid under water, the gating could be controlled by the competition of the magnetic force and the interfacial tension. Further investigation of the membrane wettability reveals that bound water on the superhydrophilic surface plays as a protective layer, and leads to the high gating ratio accompanied by the good stability. In another hand, with asymmetric modification dual stimuliresponsive nano-channels can be fabricated. In this case, the nano-channel can only be opened with the simultaneous stimulation of both sides with various combinations of stimuli-factors, such as pH/light,99 pH/voltage,100 pH/temperature,73,101-103 K+/H+,70 pH/protein,104,105 106,107 108 pH/ion, and etc. One typical example is a single PET nano-channel modified with poly(N-isopropylacrylamide) (PNIPA) and poly(acrylic acid) (PAA) with asymmetric responsive feature by pH and temperature (Figure 3c).73 This unique property results from the competition of pore size and interfacial wettability and the maximum ratio is over 3.5 at the condition of 23˚C and pH 2.8. Another typical experiment

was carried out in a cigar-shaped PET nano-channel, which is modified with acid driven polyvinylpyridine (PVP) and basedriven PAA molecules at two sides as shown in Figure 3d.56 Improved from the single and dual stimuli-responsive nanochannels, multi-state stimuli-responsive nano-channels with tunable switches were demonstrated. After modification of T/C-rich ssDNAs on alumina nano-channel arrays, the multistate responsive states can be achieved by Hg2+, Ag+, and pH.108 Similarly, a multi-state DNA hydrogel integrated nanochannel was reported with adjustable selective ionic transportation by regulating the modification time (Figure 3e).76 And by using this method, multi-gating states can be successfully achieved. In another study, with the extension of stimulation time or the increased concentration of carbonate, the 1-(4-amino-phenyl)-2, 2, 2-trifluoro-ethanone modified polyimide conical nano-channel can be switched into two states with different flux rate due to the wettability and charge distribution.109 Recently, a conical PET nano-channel was reported modified by supra-molecular self-assembly method. With the adjustment of modification, a reversible three gating states can be successfully obtained (Figure 3f).78 Despite the promising achievements, nano-pore/channel based separation still faces some challenges. One typical challenge in the controllable gating nano-pore/channel system is to develop nano-pore/channels with steady responsive cycles and high durability. In the future, it is expected that smart rectification of ion/molecules can be achieved in micro/sub-micro sized nano-pore/channels which can offer both high flux and gating ratio after interfacial modification with numerous new materials.110 Last but not least, the precisely controllable multi-gating system in energy conversion generator is also needed for further smart devices.



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Figure 3. Smart stimuli-responsive nano-channels after surface modification with responsive molecules showing single, dual, and multi gating states. (a) Single stimuli-responsive PET nano-channel controlled by electric field. Reproduced with permission.43 Copyright 2011, Nature Publishing Group. (b) Single stimuli-responsive superhydrophilic alumina nano-channels with ferrofluid gate controlled by magnetic field. Reproduced with permission.98 Copyright 2018, Wiley-VCH. (c) Dual stimuli-responsive PET nano-channel with asymmetric modification of poly(N-isopropylacrylamide) (PNIPA) and poly(acrylic acid) (PAA) controlled by temperature and pH. Reproduced with permission.73 Copyright 2010, Wiley-VCH. (d) Dual stimuli-responsive PET nano-channel with asymmetric modification of polyvinylpyridine (PVP) and PAA regulated by acid and base. Reproduced with permission.56 Copyright 2013, American Chemical Society. (e) Three-dimensional DNA hydrogel network modified conical nano-channel with multiple gating features. Reproduced with permission.76 Copyright 2018, American Chemical Society. (f) Multi-state stimuli-responsive nano-channels modified by self-assembled super-molecules with tunable gating states. Reproduced with permission.78 Copyright 2016, American Chemical Society.

Clean energy conversion of nano-pore/channel systems As the population grows, the energy crisis becomes more and more serious. Due to the overlapped Debye layers in nanoconfined areas, the nano-pore/channel system can achieve a high ion selectivity which shows great potential in efficient clean energy generation devices. The topic of clean energy conversion has been one of the most concerned questions in the past few decades due to the increase of population, environmental pollution and serious crisis of fossil fuel.111 Extensive efforts have been devoted to design high efficient harvesting devices to capture clean energy such as light, salinity, heat, pressure and so forth.112-115 Of all existing energy harvesting devices, nano-pore/channel based systems show great potential in high-efficiency energy conversion owing to its huge surface area and unique rectification behavior.116-118 In this section, based on the critical principle of interfacial charge concerning Debye layer for asymmetric transmission of ions, some typical energy conversion systems will be introduced based on different energy resources such as concentration, pressure, light and heat. The broad application will also be discussed according to their structure feature in different dimensions ranging from 1D, 2D, 3D to composite systems. For better understanding of the mechanism in energy conversion system including effect of surface charge, membrane thickness, hydrodynamic slip, and so on, tremendous efforts have been devoted to the 1D single nanopore/channels.119 Recently, a single-layer MoS2 with a single nano-pore as a nano-power generator based on a salt gradient was fabricated (Figure 4a).47 The estimated power density can reach 106 W m-2 by salt gradient resulting from the atomically thin membrane. In another work, detailed studies on single nano-channel were performed with a boron nitride nanochannel piercing through a silicon nitride membrane connecting two fluid reservoirs, as shown in Figure 4b.24 The maximum power density based on salinity gradient for this system can reach 4 kW m-2 originating in the anomalously high surface charge carried by the nanotube’s internal surface in water at large pH. Moreover, the hydrostatic energy related to waterfall and human’s activities is another potential clean energy resource. When liquids flow through a charged nanochannel driven by pressure gradient, the free charge of the

double layer on the surface will move in the direction of the liquid flow which in turn produce a streaming current and streaming potential in external circuits. On this context, the streaming current generated in an individual rectangular silica nano-channel resulting from the pressure gradient was reported as shown in Figure 4c.25 It is found the streaming current is proportional to the applied pressure and channel height. Further modeling by nonlinear Poisson-Boltzmann theory indicates that the silica surface is in salt-dependent hydration state, and the maximum energy conversion is around 6% with 145 nm channel height and 10-5 M KCl aqueous solution. Furthermore, sun light is one of the huge resource of clean energy.120 Inspired by rhodopsin, a DNA modified PET nano-channel was reported as a smart lightdriven proton pump for light-current generation as shown in Figure 4d.48 With the irradiation of UV light, the 8hydroxypyrnen-1, 3, 6-trisulfonate (HA) molecules can generate A- and H+ gradient. Due to the unidirectional transportation of H+ ions through the nano-channel membrane, a maximum photo-current of 6 μA m-2 can be obtained. Although the 1D system can achieve effective energy conversion, its complex preparation process and low porosity limit its prospects in practical applications. Hence, 2D nanochannel with production potential such as graphene membrane which can be fabricated by vacuum filtration method came to our eyes.121 As shown in Figure 4e, a selfassembled graphene hydrogel nano-fluidic generator to convert hydraulic motion into ion current was prepared.122 With the large interlayer spacing around 10 nm, negatively charged surfaces and 2D capillary force, the maximum streaming current approaching 16.8 μA cm-2 bar-1 was observed. This study suggests that this device can be further applied in harvesting the hydraulic pressure from footsteps, body fluid and so forth. In another case, an intriguing device for effective thermo-osmotic energy conversion process was reported which is prepared by a three dimensional polytetrafluoroethylene membrane (Figure 4f).123 Owing to the hydrophobic property of this nano-porous membrane, air can be trapped within the nano-channel in liquid, and power density up to 3.5 W m-2 can be achieved with a temperature change of 40˚C between the hot and cold sources.


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Figure 4. Ion transportation based on interfacial charge of energy conversion systems from various resources typically concentration, pressure, light, heat and etc. Inset was reproduced with permission.124 Copyright 2016, the American Association for the Advancement of Science. (a) Schematic diagram of concentration-electric conversion system based on 1D nano-pore of MoS2. Reproduced with permission.47 Copyright 2016, Nature Publishing Group. (b) Sketch of osmotic pressure-current conversion system with a boron nitride 1D nano-channel (purple) piercing through a silicon nitride membrane connecting two fluid reservoirs. Reproduced with permission.24 Copyright 2013, Nature Publishing Group. (c) Schematic diagram of pressure-electric conversion system based on 1D nano-channel of silicon dioxide. Reproduced with permission.25 Copyright 2005, American Physical Society. (d) Schematic diagram of light-electric conversion system based on 1D conical PET nano-channel modified with DNA. Reproduced with permission.48 Copyright 2010, WileyVCH. (e) Schematic illustration of hydraulic pressure-current conversion system with 2D grapheme hydrogel membrane. Reproduced with permission.122 Copyright 2013, Wiley-VCH. (f) Schematic diagram of heat-electric conversion system based on polytetrafluoroethylene membrane with 3D nano-channels. Reproduced with permission.123 Copyright 2016, Nature Publishing Group. (g) Schematic diagram of osmotic energy conversion system based on 2D oppositely charged lamellar graphene oxide membrane prepared by vacuum filtration. Reproduced with permission.125 Copyright 2017, Wiley-VCH. (h) Schematic diagram of osmotic energy conversion system based on ultrathin and ion-selective Janus membranes prepared via the phase separation of two block copolymers. Reproduced with permission.126 Copyright 2017, American Chemical Society.

To further improve the conversion efficiency, hybridization membrane with negatively charged and positively charged part was proposed. After pre-assembly modification, the negatively charged and positively charged graphene oxide membrane was constructed (Figure 4g).125 Further experiments revealed the inter-layer distance of 2D nanochannel is around 1 nm and the output power density in NaCl solution is around 0.77 W m-2. In another hand, an asymmetric hetero-junctions between negatively charged and positively charged part was proposed which could greatly enhance the ion selectivity. In another hand, an ultrathin and ion-selective Janus membranes prepared via the phase separation of two block copolymers were engineered, which enable osmotic energy conversion with power densities of approximately 2.04 W m-2 by mixing natural seawater and fresh water (Figure 4h).126

Besides the achievements mentioned above, some challenges in this field are still low energy conversion efficiency and high costs resulting from the complex preparation processes. In another hand, free-standing ultra-thin film is needed to obtain high flux which can in turn create high power density. Moreover, for the hydraulic pressure-current system, robust membrane is needed to endure the high pressure. Except for the mentioned three kinds of energy conversion systems, more diverse conversion systems based on nanopore/channels need to be developed such as respiration, oscillation, magnetic field and so forth. Nano-pore/channel based sensing Sensing and single molecule sequencing are promising fields for future environmental monitoring, clinical applications, wearable devices and so on.127,128 So far, extensive studies



have proved that nano-pore/channel system with confined space is a promising capacity for high sensitivity and accuracy detection and molecule sequencing.129,130 For example, bare nano-pore based on resistive-pulse technique or nano-pore/channel based on recognition interactions of various molecules showed great advantage in DNA sequencing and specific detection of ion/molecule.131,132 Bio-molecules sequencing like DNA and proteins based on the resistive-pulse technique has been already used in daily life.133,134 A membrane with a single nano-pore is created connecting two electrolytic solutions. Charged molecules, such as DNA and protein, can be driven through the nanopore by the applied potential. The conductance versus time signals clearly show the difference before and after the addition of DNA. Furthermore, DNA conformations can be identified by the signature of conductance curve. Recently, a wide type aerolysin nano-pore with high resolution in discriminating polydeoxyadenines based on the geometry and electrostatic interactions was reported.135 Furthermore, the successful real-time monitor of a stepwise degradation of polydeoxyadenines was achieved based on the current levels. As to the ‘third generation’ instruments, it is encouraging to know that sequence mammalian genome within 1000 dollars in 24 hours can be achieved.57 In another study, a AFM assisted nano-pore detector of protein was reported.136 By monitoring the force and current, the composite devices can discriminate residue substitutions in protein molecules. Recently, a real-time monitoring of nicotinamide adenine nucleotide in respiration chain was reported taking advantage of asymmetric nano-pore electrodes.137 Based on the asymmetric geometry, a bubble-induced transient ionic current pattern was created which showed high sensitivity of nicotinamide adenine nucleotide concentration as low as 1 pM. Previously, a conical polyimide nano-channel by asymmetric track-etch technique was reported.82 Further immobilization of thymine-rich ssDNA showed high sensitivity to mercury ions with the current ratio over 3.6 at the concentration of Hg2+ near 8 nM. In another hand, detection in biological system is a vital topic applied in wearable devices for human health. Based on a single conical PET nano-channel modified with glucose oxidase, the successful detection of D-glucose was achieved which can be applied for the detection in monitoring human blood.138 Successful distinction of Dglucose and L-glucose was achieved by monitoring the ion current with various concentrations. Further experiments on the tip diameter around 30 nm showed the highest sensing capability around 2.0 with 1 nM D-glucose. Besides, a carbon dioxide detector was demonstrated with grafted imidazolecontaining polymers on conical PET nano-channels mimicking olfactory sensory neurons. This sensing device can be switched between CO2-activated state to N2-closed state with ion rectification ratio up to 23 which can be applied in monitoring of human breath.79 Another intriguing study demonstrated a nano-fluidic sensing device for sub-nanomolar DNA and sub-micro-molar ATP with high sensitivity.139 An integrated DNA super-sandwich structure was introduced to detect oligonucleotides and small molecules. The I-V curve clearly showed the difference for bare nano-pore, and changes after addition of 10 fM and 1 nM Systems

Separation

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target DNA. Compared with the traditional sandwich method, this super-sandwich method showed high signal gain and improved detection limit. Some challenges in the DNA sequencing and ion/molecule detection based on nano-pore/channel system still lie on the in situ, fast and real-time with high accuracy. For example, high selectivity and accuracy is still a challenge in food industry owing to its complicated detection environments. For human body detection, the noninvasive and simultaneous detection with high selectivity and accuracy is also a challenge. In another hand, beside the detection of structure, conformation and sequence based on volume-exclusion effect with nano-pore/channels, directly observing the dynamic functional properties of single molecules are in great demand. Recently, the electrochemical confinement effect was proposed which may provide new insights into the sensing mechanisms for a broad range of future applications.140 Conclusion and perspective This perspective is devoted to explore the critical principles of ion/molecule transportation among nano-pore/channel with an eye on their applications in separation, stimuliresponsive gating, energy conversion and sensing. Taking advantage of the size/shape, interfacial wettability and surface charges during ion/molecule transportation, successful separation of immiscible liquids, liquids/gases, and miscible mixtures based on nano-pore/channel system is briefly introduced. Stimuli-responsive gating behaviors among nanopore/channels with single, dual and multi states are also presented which has potential applications in drug sustained release, nano-fluidic logic devices and etc. With the perspective of the special ion transportation behavior of rectification, energy conversion system can be built converting various kinds of energy resources including osmotic pressure, hydraulic pressure, light, heat, and so on which is a promising field in regard to energy crisis. Besides, nano-pore/channel based sensing to sequence DNA or protein series and detect ions or molecules are also introduced offering an overview of future clinical applications. Despite the significant achievements in the field of nanopore/channels in the past decades, there are still many challenges. Generally, integrated nano-pore/channels with multi-functions and robust membrane with reliable sustainability are critical challenges for practical applications. Besides, a universal and comprehensive model is still needed concerning the critical principles to explain the ion/molecule transportation behaviors in nano-pore/channel systems. We concisely summarized typical achievements, challenges and possible measures for future applications as shown in Table 1. Fortunately, with the discovery of novel phenomena concerning nano-pore/channels, future progress may reveal new theories and intriguing liquid behaviors.141-143 Hence research efforts can be devoted to systematically study single nano-pore or nano-tube with precisely controllable environments to narrow the gap between the critical principles and diverse functions. Furthermore, efforts in developing facile fabrication process to create regular and size-controlled robust large-area nano-pore/channel arrays for practical applications are also in great demand.

Typical achievements

Challenges

Possible measures for future applications

Immiscible multi-phases ： water/cyclohexane/nitromethane.11 tetrachloromethane/formamide,14 air/water/oil,45 and etc.

Construction of robust nanopore/channel membrane for harsh environments Construction of pore/channel membrane with high selectivity and

Fabrication of nano-pore/channels on materials with high mechanical property Introduce specific interactions combined with unique structures


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Controllable gating

Energy conversion

Sensing

Gases: propylene /propane,63 acetylene/carbon and ethylene mixture,144 and etc. Miscible liquids: ethanol/water, ethanol/toluene, 64 Ions: K+/Cl-,65 and etc. Single responsive gating: ions like H+,71,81 K+,76 Zn2+,77 Hg2+,82 Ca2+,83 and etc; molecules like ATP,80,84 H2O2,85 proteins,86 and etc87,88; environments like light,89,90 43 91 voltage, temperature, magnetic field98 and etc. Dual-responsive gating: pH/light,99 pH/voltage,100 pH/temperature,73,101-103 K+/H+,70 pH/protein,104,105 pH/ion,106,107 and etc.108 Multi-responsive gating: Hg2+, Ag+, and pH,108 CO2,109 supra-molecular self-assembly,78 and etc.

flux to separate miscible ions/molecules Fouling of nano-pore/channels

Fabrication of anti-fouling nanopore/channels such as liquid infused membrane, superhydrophilic surfaces

Multi-gating system with steady responsive cycles and high durability

Precise shape control of micro/sub-micro sized nanopore/channels combined with modification of multiple reversible smart macromolecules

Energy conversion of concentration;24,47 pressure,25,122 light;48 heat123 and etc.120

Low energy conversion efficiency and high costs Robust membrane Conversion of diverse energy forms

Introduce free-standing ultra-thin robust film such as construction of sandwich structure with functional nano-pore/channel system in the middle and strength enhanced membrane Discover new material with unique properties, such as opto-electronic property, intrinsic multi-responsive property and etc

Ion/molecule detection: Hg2+,82 Dglucose,138 CO2,79,109 nicotinamide adenine nucleotide,137 and etc. Molecule sequencing: DNA,133 protein,136 and etc.145

Nano-pore/channel based sequencing of protein and other long-chain molecules Universal nano-pore/channel system for identification of various ions/molecules

Introduce specific molecules with specific recognition interactions Asymmetric modification of nanopore/channel membrane with reversible interactions

Table 1. Typical achievements, challenges and possible measures for future applications in separation, controllable gating, energy conversion and sensing.

AUTHOR INFORMATION Corresponding Author [email protected] Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS Zhongpeng Zhu and Dianyu Wang contribute equally to this perspective. This research is supported by the National Program on Key Basic Research Project of China (2018YFA020850, 2017YFA0204504), National Natural Science Foundation of China (21722309, 21671194).

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