Electrospun Fibers as a Solid‐State Real‐Time Zinc Ion Sensor with High Sensitivity and Cell Medium Compatibility

meso‐2,6‐Dichlorophenyltripyrrinone (TPN‐Cl₂), a probe molecule for zinc II ions, is dispersed in a polymer host. The red fluorescence peak at 620 nm appears when the molecule forms a complex with zinc at its center. TPN‐Cl₂ has a high selectivity for zinc II and tolerates many common metal ions present in the human body. The probe molecules are blended with a hydrogel polymer, poly(2‐hydroxyethyl methacrylate) (poly HEMA), with 30 wt% dimethylformamide (DMF). The fiber structure with 1 μm diameter is made by electrospinning in DMF solution of the probe and poly HEMA mixture. The fibrous film detects zinc ions with concentrations as low as 10^?6 M in real‐time both in water and in the commonly used cell culture liquid media Dulbecco's modified Eagle medium (DMEM) and fetal bovine serum (FBS), which contain many metal ions and proteins. The time‐resolution is 5 min for 10^?6 M and 1 min for 10^?5 M. This sensitivity and response speed satisfy the requirements for non‐invasive biomedical studies.     

Highly‐Cyclable Room‐Temperature Phosphorene Polymer Electrolyte Composites for Li Metal Batteries

Despite significant interest toward solid‐state electrolytes owing to their superior safety in comparison to liquid‐based electrolytes, sluggish ion diffusion and high interfacial resistance limit their application in durable and high‐power density batteries. Here, a novel quasi‐solid Li⁺ ion conductive nanocomposite polymer electrolyte containing black phosphorous (BP) nanosheets is reported. The developed electrolyte is successfully cycled against Li metal (over 550 h cycling) at 1 mA cm^?2 at room temperature. The cycling overpotential is dropped by 75% in comparison to BP‐free polymer composite electrolyte indicating lower interfacial resistance at the electrode/electrolyte interfaces. Molecular dynamics simulations reveal that the coordination number of Li⁺ ions around (trifluoromethanesulfonyl)imide (TFSI^?) pairs and ethylene‐oxide chains decreases at the Li metal/electrolyte interface, which facilitates the Li⁺ transport through the polymer host. Density functional theory calculations confirm that the adsorption of the LiTFSI molecules at the BP surface leads to the weakening of N and Li atomic bonding and enhances the dissociation of Li⁺ ions. This work offers a new potential mechanism to tune the bulk and interfacial ionic conductivity of solid‐state electrolytes that may lead to a new generation of lithium polymer batteries with high ionic conduction kinetics and stable long‐life cycling.     

Transport Properties of Polymer Semiconductor Controlled by Ionic Liquid as a Gate Dielectric and a Pressure Medium

An effective way of using ionic liquid as a gate dielectric as well as a pressure medium to tune the transport of an exemplary polymer semiconductor, poly(2,5‐bis(3‐tetradecyl‐thiophene‐2‐yl)thieno[3,2‐b]thiophene) (pBTTT‐C14) is presented. Working as gate dielectrics, the ionic liquids exhibit the well‐known ability to induce dense carriers (>10²⁰ cm^?3) in the polymer film contributing to the high conductivity (≈10² S cm^?1). In addition, it is found that the ionic liquid works as a pressure medium at the highly charged state, leading to significant enhancement of conductivity. By combining both gating and pressuring, a crossover of transport properties is observed from one‐dimensional to three‐dimensional hopping, as the clear indication that the polymer film has accessed the regime adjacent to the transition region between insulator and metal. These results show an effective way of utilizing pressure effect of ionic liquid as a new degree of freedom in controlling transport of polymers, a method having strong potential to be generalized for even broader range of materials.     

Biosensor Array of Interpenetrating Polymer Network with Photonic Film Templated from Reactive Cholesteric Liquid Crystal and Enzyme‐Immobilized Hydrogel Polymer

A biosensor array is fabricated using an interpenetrating polymer network consisting of photonic film templated from reactive cholesteric liquid crystal (CLC) and enzyme‐immobilized polyacrylic acid (PAA). The solid‐state photonic film on the glass substrate is successfully templated by ultraviolet (UV) curing of the reactive CLC mixture of a reactive mesogen mixture of RMM 727 (from Merck) and a nonreactive chiral dopant of (S)‐4‐cyano‐4′‐(2‐methylbutyl)biphenyl following the extraction of the chiral dopant. The acrylic acid monomer mixed with a cross‐linker of tri(propylene glycol) diacrylate is infiltrated into the extracted space of the photonic film, and UV‐cured with a photomask to obtain a patterned array‐dot film. The interpenetrated cholesteric liquid crystal/hydrogel polymer network (CLC‐hydrogel‐IPN) array is further functionalized in the individual dots with urease, for a model study of biosensor array applications. The dots of the CLC‐hydrogel‐IPN array respond independently to the urea by a color change with high sensitivity and stability. Thus, the patterned CLC‐hydrogel‐IPN can be used as a new biosensor array for cost‐effective and easy visual detection without any sophisticated instruments.     

On the Relation between Morphology and FET Mobility of Poly(3‐alkylthiophene)s at the Polymer/SiO2 and Polymer/Air Interface

The influence of the interface of the dielectric SiO₂ on the performance of bottom‐contact, bottom‐gate poly(3‐alkylthiophene) (P3AT) field‐effect transistors (FETs) is investigated. In particular, the operation of transistors where the active polythiophene layer is directly spin‐coated from chlorobenzene (CB) onto the bare SiO₂ dielectric is compared to those where the active layer is first spin‐coated then laminated via a wet transfer process such that the film/air interface of this film contacts the SiO₂ surface. While an apparent alkyl side‐chain length dependent mobility is observed for films directly spin‐coated onto the SiO₂ dielectric (with mobilities of ≈10^?3 cm² V^?1 s^?1 or less) for laminated films mobilities of 0.14 ± 0.03 cm² V^?1 s^?1 independent of alkyl chain length are recorded. Surface‐sensitive near edge X‐ray absorption fine structure (NEXAFS) spectroscopy measurements indicate a strong out‐of‐plane orientation of the polymer backbone at the original air/film interface while much lower average tilt angles of the polymer backbone are observed at the SiO₂/film interface. A comparison with NEXAFS on crystalline P3AT nanofibers, as well as molecular mechanics and electronic structure calculations on ideal P3AT crystals suggest a close to crystalline polymer organization at the P3AT/air interface of films from CB. These results emphasize the negative influence of wrongly oriented polymer on charge carrier mobility and highlight the potential of the polymer/air interface in achieving excellent “out‐of‐plane” orientation and high FET mobilities.     

An Optically Active Polythiophene Exhibiting Electrochemically Driven Light‐Interference Modulation

Optically active polythiophene (PT*) is successfully prepared by electrochemical polymerization using a cholesteric liquid crystal (CLC) electrolyte solution. Polarizing optical microscopy observations of the polymer reveal a well‐resolved fingerprint texture similar to the optical texture of the CLC. Circular dichroism measurements indicate a Cotton effect. The PT* film produced by the asymmetric polymerization in CLC exhibits a variable diffraction function, electrochemically driven refractive index modulation, and electrochromism originating from the periodic dielectric structure, representing a form of structural electrochromism.     

Supramolecular‐Assembled Nanoporous Film with Switchable Metal Salts for a Triboelectric Nanogenerator

A triboelectric nanogenerators (TENG) are of great interest as emerging power harvesters because of their simple device architecture with unprecedented high efficiency. Despite the substantial development of new constituent materials and device architectures, a TENG with a switchable surface on a single device, which allows for facile control of the triboelectric output performance, remains a challenge. Here, a supramolecular route for fabricating a novel TENG based on an alkali‐metal‐bound porous film, where the alkali metal ions are readily switched among one another is demonstrated. The soft nanoporous TENG contains numerous SO₃^? groups on the surface of nanopores prepared from the supramolecular assembly of sulfonic‐acid‐terminated polystyrene and poly(2‐vinylpyridine) (P2VP), followed by soft etching of P2VP. Selective binding of alkali metal ions, including Li⁺, Na⁺, K⁺, and Cs⁺, with SO₃^? groups enables the development of mechanically robust alkali‐metal‐ion‐decorated TENGs. The triboelectric output performance of the devices strongly depends on the alkali metal ion species, and the output power ranges from 11.5 to 256.5 µW. This wide‐range triboelectric tuning can be achieved simply by a conventional ion exchange process in a reversible manner, thereby allowing reversible control of the output performance in a single device platform.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.     

Liquid‐Crystalline Perylene Diester Polymers with Tunable Charge‐Carrier Mobility

New classes of liquid‐crystalline semiconductor polymers based on perylene diester benzimidazole and perylene diester imide mesogens are reported. Two highly soluble side‐chain polymers, poly(perylene diester benzimidazole acrylate) (PPDB) and poly(perylene diester imide acrylate) (PPDI) are synthesized by nitroxide‐mediated radical polymerization (NMRP). PPDB shows n‐type semiconductor performance with electron mobilities of 3.2 × 10^?4 cm² V^?1 s^?1 obtained in a diode configuration by fitting the space‐charge‐limited currents (SCLC) according to the Mott–Gurney equation. Interestingly, PPDI performs preferentially as a p‐type material with a hole mobility of 1.5 × 10^?4 cm² V^?1 s^?1, which is attributed to the less electron‐deficient perylene core of PPDI compared to PPDB. Optical properties are investigated by UV‐vis and fluorescence spectroscopy. The extended π‐conjugation system due to the benzimidazole unit of PPDB leads to a considerably broader absorption in the visible region compared to PPDI. HOMO and LUMO levels of the polymers are also determined by cyclic voltammetry; the resulting energy band‐gaps are 1.86 eV for PPDB and 2.16 eV for PPDI. Thermal behavior and liquid crystallinity are studied by differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction measurements. The results indicate liquid‐crystalline order of the polymers over a broad temperature range. These thermal, electrical, and optical properties make the perylene side‐chain polymers attractive materials for organic photovoltaics.     

Self‐Powered Optical Switch Based on Triboelectrification‐Triggered Liquid Crystal Alignment for Wireless Sensing

Here, a self‐powered optical switch (OS) composed of a surface‐etched single‐electrode triboelectric nanogenerator (TENG) and a polymer‐dispersed liquid crystal (PDLC) film is reported. The working principle of the developed OS is that the liquid crystal alignment can be driven by triboelectrification‐generated voltage, inducing the PDLC film to rapidly switch its initial translucent state to an instantaneous transparent state. An output voltage of 360 V is generated upon the PDLC film when a nitrile rubber film contacts with the TENG at an area of 25 cm² and a velocity of 0.4 m s^?1. As such, a wide dimming range with the relative transmitted light intensity from 0.05 to 0.85 can be achieved for the OS. Enabled by the unique mechano‐electro‐optical reaction, the effects of a series of structural parameters on the performance of the OS are methodically studied. Particularly, through integrating the OS with a visible‐light‐operated signal‐processing circuit, a complete wireless sensing system with a fully power‐free sensing node is developed. The paradigms of hand touching and foot stepping triggered wireless alarms are demonstrated, explicitly showing great potential for the system in many possible interactive human–machine interface applications, such as surveillance, security systems, remote operation, and automatic control.     

Liquid‐Metal Electrode for High‐Performance Triboelectric Nanogenerator at an Instantaneous Energy Conversion Efficiency of 70.6%

Harvesting ambient mechanical energy is a key technology for realizing self‐powered electronics, which has tremendous applications in wireless sensing networks, implantable devices, portable electronics, etc. The currently reported triboelectric nanogenerator (TENG) mainly uses solid materials, so that the contact between the two layers cannot be 100% with considering the roughness of the surfaces, which greatly reduces the total charge density that can be transferred and thus the total energy conversion efficiency. In this work, a liquid‐metal‐based triboelectric nanogenerator (LM‐TENG) is developed for high power generation through conversion of mechanical energy, which allows a total contact between the metal and the dielectric. Due to that the liquid–solid contact induces large contacting surface and its shape adaptive with the polymer thin films, the LM‐TENG exhibits a high output charge density of 430 μC m^?2, which is four to five times of that using a solid thin film electrode. And its power density reaches 6.7 W m^?2 and 133 kW m^?3. More importantly, the instantaneous energy conversion efficiency is demonstrated to be as high as 70.6%. This provides a new approach for improving the performance of the TENG for special applications. Furthermore, the liquid easily fluctuates, which makes the LM‐TENG inherently suitable for vibration energy harvesting.     

Growth of Vertically Aligned Tunable Polyaniline on Graphene/ZrO2 Nanocomposites for Supercapacitor Energy‐Storage Application

In‐situ hydrothermal method is employed to synthesize graphene/zirconium oxide composite from respective precursors graphene oxide and zirconium oxy‐nitrate. In this method, the graphene oxide is reduced itself to graphene and simultaneously metal oxide gets anchor on the graphene sheets. A novel method is also developed for the preparation of vertically aligned tunable polyaniline on the graphene/zirconium oxide nanocomposite, which leads to achieve high surface area (207.1 m² g^?1), high electrical conductivity (70.8 S cm^?1), high specific capacitance (1359.99 Fg^?1 at 1 mV s^?1), and high electrochemical performances as supercapacitor electrode materials. This vertically aligned conducting polymer gets easy contact with electrolyte ions and provides numerous redox active sites during charging and discharging. Moreover, such a simple and low cost assembly approach can be a pioneer for the large‐scale production of various functional architectures for energy storage and conversions.     

Chemically Resistant,Shapeable, and Conducting Metal‐Organic Gels and Aerogels Built from Dithiooxamidato Ligand

Metal‐organic gels (MOGs) appear as a blooming alternative to well‐known metal‐organic frameworks (MOFs). Porosity of MOGs has a microstructural origin and not strictly crystalline like in MOFs; therefore, gelation may provide porosity to any metal‐organic system, including those with interesting properties but without a porous crystalline structure. The easy and straightforward shaping of MOGs contrasts with the need of binders for MOFs. In this contribution, a series of MOGs based on the assembly of 1D‐coordination polymer nanofibers of formula [M(DTA)]_n (M^II: Ni, Cu, Pd; DTA: dithiooxamidato) are reported, in which properties such as porosity, chemical inertness, mechanical robustness, and stimuli‐responsive electrical conductivity are brought together. The strength of the M? S bond confers an unusual chemical resistance, withstanding exposure to acids, alkalis, and mild oxidizing/reducing chemicals. Supercritical drying of MOGs provides ultralight metal‐organic aerogels (MOAs) with densities as low as 0.03 g cm^?3 and plastic/brittle behavior depending on the nanofiber aspect ratio. Conductivity measurements reveal a semiconducting behavior (10^?12 to 10^?7 S cm^?1 at 298 K) that can be improved by doping (10^?5 S cm^?1). Moreover, it must be stressed that conductivity of MOAs reversibly increases (up to 10^?5 S cm^?1) under the presence of acetic acid.     

Bithienopyrroledione‐Based Copolymers,Versatile Semiconductors for Balanced Ambipolar Thin‐Film Transistors and Organic Solar Cells with V oc > 1 V

Conjugated polymer semiconductors P1 and P2 with bithienopyrroledione (bi‐TPD) as acceptor unit are synthesized. Their transistor and photovoltaic performances are investigated. Both polymers display high and balanced ambipolar transport behaviors in thin‐film transistors. P1‐ based devices show an electron mobility of 1.02 cm² V^?1 s^?1 and a hole mobility of 0.33 cm² V^?1 s^?1, one of the highest performance reported for ambipolar polymer transistors. The electron and hole mobilities of P2 transistors are 0.36 and 0.16 cm² V^?1 s^?1, respectively. The solar cells with PC₇₁BM as the electron acceptor and P1/P2 as the donor exhibit a high V _oc about 1.0 V, and a power conversion efficiency of 6.46% is observed for P1‐ based devices without any additives and/or post treatment. The high performance of P1 and P2 is attributed to their crystalline films and short π–π stacking distance (<3.5 Å). These results demonstrate (1) bi‐TPD is an excellent versatile electron‐deficient unit for polymer semiconductors and (2) bi‐TPD‐based polymer semiconductors have potential applications in organic transistors and organic solar cells.     

Ultrathin,Organic, Semiconductor/Polymer Blends by Scanning Corona‐Discharge Coating for High‐Performance Organic Thin‐Film Transistors

A new thin‐film coating process, scanning corona‐discharge coating (SCDC), to fabricate ultrathin tri‐isopropylsilylethynyl pentacene (TIPS‐PEN)/amorphous‐polymer blend layers suitable for high‐performance, bottom‐gate, organic thin‐film transistors (OTFTs) is described. The method is based on utilizing the electrodynamic flow of gas molecules that are corona‐discharged at a sharp metallic tip under a high voltage and subsequently directed towards a bottom electrode. With the static movement of the bottom electrode, on which a blend solution of TIPS‐PEN and an amorphous polymer is deposited, SCDC provides an efficient route to produce uniform blend films with thicknesses of less than one hundred nanometers, in which the TIPS‐PEN and the amorphous polymer are vertically phase‐separated into a bilayered structure with a single‐crystalline nature of the TIPS‐PEN. A bottom‐gate field‐effect transistor with a blend layer of TIPS‐PEN/polystyrene (PS) (90/10 wt%) operated at ambient conditions, for example, indeed exhibits a highly reliable device performance with a field‐effect mobility of approximately 0.23 cm² V^?1 s^?1: two orders of magnitude greater than that of a spin‐coated blend film. SCDC also turns out to be applicable to other amorphous polymers, such as poly(α‐methyl styrene) and poly(methyl methacrylate) and, readily combined with the conventional transfer‐printing technique, gives rise to micropatterned arrays of TIPS‐PEN/polymer films.     

Novel Film‐Casting Method for High‐Performance Flexible Polymer Electrodes

A new film‐casting method for polymer electrodes is reported, in which thickness‐controlled drop‐casting (TCDC), using polyaniline doped with camphorsulfonic acid (PANI:CSA) is used. By combining the advantages of conventional spin‐casting and drop‐casting methods, and by rigorously controlling the film formation parameters, flexible polymer electrodes with high conductivity and excellent transmittance can be produced. The PANI:CSA electrodes cast by the TCDC method exhibited constant thickness‐independent conductivities of ～600 S cm^?1 down to a film thickness of 0.2 μm, and a high optical transmittance of about 85% at 550 nm. Furthermore, the new casting method significantly reduced the sheet resistance (～90 Ω/square) of the PANI:CSA electrodes compared with the conventional spin‐cast films, enhancing the performance of the devices deposited on plastic substrates. The flexible polymer light‐emitting diode produced a brightness of 6000 cd m^?2, and the flexible polymer solar cell exhibited a power conversion efficiency of 2%, both of which were much higher than those of the devices fabricated by the conventional spin‐casting method.     

Porous Cu(I) Triazolate Framework and Derived Hybrid Membrane with Exceptionally High Sensing Efficiency for Gaseous Oxygen

Phosphorescent complexes of precious metal ions are widely studied as optical sensing materials for molecular oxygen. Combining the advantages of luminescent complexes and porous matrixes, porous coordination polymers show great potential for oxygen‐sensing, although their sensitivity, requirement of precious metal, and device fabrication remain challenging issues. In this work, the photoluminescence and oxygen‐sensing properties of the porous Cu(I) triazolate framework [Cu(detz)] (MAF‐2, Hdetz = 3,5‐diethyl‐1,2,4‐trizole) is studied in detail, which shows high chemical stability in moisture and water, very long phosphorescent lifetime (116 μs) and large Stokes shift (14 562 cm^?1), as well as considerable oxygen permeability (1.7 × 10^?11 mol cm^?1 s^?1 bar^?1) at ambient conditions, giving rise to exceptionally high luminescence quenching efficiency of 99.7% at 1 bar O₂ (I ₀/I ₁₀₀ = 356) with a perfectly linear Stern‐Volmer plot (K _SV = 356 bar^?1, R ² = 0.9998), fast response and good reversibility. Further, a counter‐diffusion crystal‐growth method was developed to fabricate MAF‐2 thin films protected by silicone rubbers as the first example of soft membrane oxygen sensor based on coordination polymer or metal‐organic framework, which exhibited extraordinary oxygen‐sensing performance (limit of detection = 0.047 mbar) and outstanding mechanical property, as well as outstanding chemical stability even in an acidic atmosphere.     

Alkoxy‐Functionalized Thienyl‐Vinylene Polymers for Field‐Effect Transistors and All‐Polymer Solar Cells

π‐conjugated polymers based on the electron‐neutral alkoxy‐functionalized thienyl‐vinylene (TVTOEt) building‐block co‐polymerized, with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks, or NDI (naphthalenediimide) as an acceptor block, are synthesized and characterized. The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all‐polymer organic photovoltaic (OPV) cells is reported. Co‐monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X‐ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μ_e = 5.1 × 10^?3 cm² V^–1 s^–1 and μ_h = 3.9 × 10^?3 cm² V^–1 s^–1 in ambient, among the highest mobilities reported to date for all‐polymer bulk heterojunction TFTs, and all‐polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI‐polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI‐type materials promising acceptors for all‐polymer solar cell applications.     

Development of Film Sensors Based on Conjugated Polymers for Copper (II) Ion Detection

A fluorescent film sensor was prepared by chemical modification of a polyfluorene derivative on a glass‐plate surface. X‐ray photoelectron spectroscopy and ellipsometry measurements demonstrate the covalent attachment of the polyfluorene derivative to the glass‐plate surface. The sensor was used to detect Cu²⁺ ions in aqueous solution by a mechanism exploiting fluorescence quenching of conjugated polymers. Among the tested metal ions, the film sensor presents good selectivity towards Cu²⁺ ions. Further experiments show that the sensing process is reversible. Moreover, sensory microarrays based on conjugated polymers targeting Cu²⁺ ions are constructed, which display similar sensing performance to that of the film sensor. The structural motif in which conjugated polymers are covalently confined to a solid substrate surface offers several attractive advantages for sensing applications. First, in comparison with film sensors in which small fluorescent molecules are employed as sensing elements, the sensitivity of our new film sensor is enhanced due to the signal‐amplifying effect of the conjugated polymers. Second, the film sensors or microarrays can be used in aqueous environments, which is crucial for their potential use in a wide range of real‐world systems. Since the sensing process is reversible, the sensing materials can be reused. Third, unlike physically coated polymer chains, the covalent attachment of the grafted chains onto a material surface precludes desorption and imparts long‐term stability of the polymer chains.     

Optical Nanoscale Pool‐on‐Surface Design for Control Sensing Recognition of Multiple Cations

General design of optical chemical nanosensors is needed to develop efficient sensing systems with high flexibility, and low capital cost for control recognition of toxic analytes. Here, we designed optical chemical nanosensors for simple, high‐speed detection of multiple toxic metal ions. The systematic design of the nanosensors was based on densely patterned chromophores with intrinsic mobility, namely, “building‐blocks” onto three‐dimensional (3D) nanoscale structures. The ability to precisely modify the nanoscale pore surfaces by using a broad range of chromophores that have different molecular sizes and characteristics enables detection of multiple toxic ions. A key feature of this building‐blocks design strategy is that the surface functionality and good adsorption characteristics of the fabricated nanosensor arrays enabled the development of “pool‐on‐surface” sensing systems in which high flux of the metal analytes across the probe molecules was achieved without significant kinetic hindrance. Such a sensing design enabled sensitive recognition of metal ions up to sub‐picomolar detection limits (～10^?11 mol dm^?3), for first time, with rapid response time within few seconds. Moreover, because these sensing pools exhibited long‐term stability, reversibility and selectivity in detecting most pollutant cations, for example, Cr(VI), Pb(II), Co(II), and Pd(II) ions, they are practical and inexpensive. The key result in our study is that the pool‐on‐surface design for optical nanosensors exhibited significant ion‐selective ability of these target ions from environmental samples and waste disposals.