Directional Activated Exciton Highway via Fractal Electric Field Modulation for Ultrasensitive Carbon Nanotube-Based Sensors.

The electrical vapor sensor based on carbon nanotubes (CNTs) has attracted wide attention due to its excellent conductivity, stable interfacial structure, and low dimensional quantum effects. However, the conductivity and contact interface activity were still limited by the random distribution of coated CNTs, which led to limited performance. We developed a new strategy to unify the CNT directions with image fractal designing of the electrode system. In such a system, directional aligned CNTs were gained under a well-modulated electric field, leading to microscale CNT exciton highways and molecule-scale host-guest site activation. The carrier mobility of the aligned CNT device is 20-fold higher than that of the random network CNT device. With excellent electrical properties, such modulated CNT devices based on fractal electrodes behave as an ultrasensitive vapor sensor for methylphenethylamine, a mimic of illicit drug methamphetamine. The detection limit reached as low as 0.998 ppq, 6 orders of magnitude sensitive than the reported 5 ppb record based on interdigital electrodes with random distributed CNTs. Since the device is easily fabricated in wafer-level and compatible with the CMOS process, such a fractal design strategy for aligned CNT preparation will be widely applied in a variety of wafer-level electrical functional devices.

Investigation on the Compressive Behavior of Hybrid Polyurethane(PU)-Foam-Filled Hyperbolic Chiral Lattice Metamaterial.

In this study, a novel hybrid metamaterial has been developed via fulfilling hyperbolic chiral lattice with polyurethane (PU) foam. Initially, both the hyperbolic and typical body-centered cubic (BCC) lattices are fabricated by 3D printing technique. These lattices are infiltrated in a thermoplastic polyurethane (TPU) solution dissolved in 1,4-Dioxane, and then freeze casting technique is applied to achieve the PU-foam-filling. Intermediate (IM) layers possessing irregular pores, are formed neighboring to the lattice-foam interface. While, the foam far from the lattice exhibits a multi-layered structure. The mechanical behavior of the hybrid lattice metamaterials has been investigated by monotonic and cyclic compressive tests. The experimental monotonic tests indicate that, the filling foam is able to soften the BCC lattice but to stiffen the hyperbolic one, further to raise the stress plateau and to accelerate the densification for both lattices. The foam hybridization also benefits the hyperbolic lattice to prohibit the property degradation under the cyclic compression. Furthermore, the failure modes of the hybrid hyperbolic lattice are identified as the interface splitting and foam collapse via microscopic analysis. Finally, a parametric study has been performed to reveal the effects of different parameters on the compressive properties of the hybrid hyperbolic lattice metamaterial.

Direct Active Site at the Van der Waals Heterostructure Interface with Synthetic Drug Analogue N-Methylphenethylimine Ultrasensitivity.

CNT/organic probe-based chemiresistive sensors suffer from the problem of low sensitivity and poor stability due to the unstable and unfavorable CNT/organic probe interface. A new designing strategy of a one-dimensional van der Waals heterostructure was developed for ultrasensitive vapor sensing. By modifying the perylene diimide molecule at the bay region with phenoxyl and further Boc-NH- phenoxy side chains, a highly stable 1D VDW heterostructure SWCNT-probe molecule system was formed with ultrasensitivity and specificity. Interfacial recognition sites consisting of SWCNT and the probe molecule are responsible for the synergistical and excellent sensing response to MPEA molecules, which was proved by Raman, XPS, and FTIR characterizations together with dynamic simulation. Based on such a sensitive and stable VDW heterostructure system, the measured detection limit reached as low as 3.6 ppt for the synthetic drug analogue N-methylphenethylimine (MPEA) in the vapor phase, and the sensor showed almost no performance degradation even after 10 days. Furthermore, a miniaturized detector was developed for real-time monitoring of drug vapor detection.

One-step synthesis of triethanolamine-capped Pt nanoparticle for colorimetric and electrochemiluminescent immunoassay of SARS-CoV spike proteins.

Platinum nanoparticles (PtNPs) have been attracted worldwide attention due to their versatile application potentials, especially in the catalyst and sensing fields. Herein, a facile synthetic method of triethanolamine (TEOA)-capped PtNPs (TEOA@PtNP) for electrochemiluminescent (ECL) and colorimetric immunoassay of SARS-CoV spike proteins (SARS-CoV S-protein, a target detection model) is developed. Monodisperse PtNPs with an average diameter of 2.2 nm are prepared by a one-step hydrothermal synthesis method using TEOA as a green reductant and stabilizer. TEOA@PtNPs can be used as a nanocarrier to combine with antigen by the high-affinity antibody, which leads to a remarkable inhibition of electron transfer efficiency and mass transfer processes. On the basis of its peroxidase-like activity and easy-biolabeling property, the TEOA@PtNP can be used to establish a colorimetric immunosensor of SARS-CoV S-protein thought catalyzing the reaction of H2O2 and 3,3',5,5'-tetramethylbenzidine (TMB). Especially, the Ru(bpy)3 2+ ECL reaction is well-achieved with the TEOA@PtNPs due to their great conductivity and loading abundant TEOA co-reactants, resulting in an enhancing ECL signal in immunoassay of SARS-CoV S-protein. As a consequence, two proposed methods could achieve sensitive detection of SARS-CoV S-protein in wide ranges, the colorimetric and ECL detection limits were as low as 8.9 fg /mL and 4.2 fg /mL (S/N = 3), respectively. We believe that the proposed colorimetric and ECL immunosesors with high sensitivity, good reproducibility, and good stability will be a promising candidate for a broad spectrum of applications.

In Situ Turn-On Room Temperature Phosphorescence and Vapor Ultra-sensitivity at Lifetime Mode.

Organic room temperature phosphorescence (RTP) systems are rarely reported for vapor phase sensing due to the contradiction between vapor permeability and phosphorescence ability. Till now, almost all reported works are based on ″turn-off″ mode RTP detection by destroying the compact-packaging oxygen-free environment. ″Turn-on″ mode RTP detection owns additional anti-interference capability due to a lower initial RTP background signal, while its realization is even harder. In this research, in situ phosphorescence ″turn-on″ sensing was realized for methamphetamine (MPEA) vapor detection. Based on the formation of aromatic phenolic aldehyde-secondary amine ion pairs with air-stable RTP performance, the fluorescent tri-formyl phenol (TFP) film was converted into a stable RTP state after being exposed to the MPEA vapor, as supported by nuclear magnetic resonance (NMR) and mass spectrometry together with theoretical calculations. The red-shifted absorption and emission, enhanced emission intensity, and 49.7 µs phosphorescence lifetime allowed multiple mode MPEA vapor sensing from chromaticity to fluorescence to phosphorescence. The lifetime mode detection limit reached 0.4 ppt, 5 orders of magnitude lower than the intensity mode detection limit of 20.3 ppb.

Supramolecule-Originated Emission: A Room-Temperature Phosphorescence 2D Ionic H-Bond Network from Nonemissive Aliphatic Derivatives.

Supramolecular materials exhibiting unique functions unavailable from their individual components are attracting great attention. Here, we report a novel supramolecule emission strategy, where the emission originated from a two-dimensional (2D) ionic hydrogen bond (H-bond) supramolecular network. High-quality crystals were obtained by rapid self-assembly of liquid aliphatic amine and ketone. The 2D ionic H-bonding network was characterized by single-crystal X-ray diffraction (XRD) that shows a planar electron system similar to aromatic species. First-principles calculations demonstrated that the charge-separated transition process and high spin-orbital coupling constants of the rigid supramolecular structure contribute to the enhanced singlet-triplet intersystem crossing process. The emission could be well regulated via the substituents of either the enol or amine part, and a maximum quantum efficiency of 26% was realized. The emission system demonstrated stable room-temperature phosphorescence (RTP), which is even hard to obtain for aromatic species, and the lifetime reached 0.45 s with an 8% luminescence quantum yield. For application, with liquid amine and enol as ink, high-quality RTP patterns can be fabricated by computer-controlled precision printing. Our findings will surely bring completely fresh thinking for photoluminescence and other functions purely originated by the supramolecular structure.

Reactivity triggered by an organic microcrystal interface: a case study involving an environmentally benign, aromatic boric acid reaction.

A novel reactivity-triggering strategy for inert organic molecules was developed via the chemical properties of a crystal-solution interface. Upon self-assembling to form a {002} crystal interface, inactive 9-anthracene boric acid was transformed into an ultra-high active state, triggering a catalyst-free, environmentally benign, aromatic substitution and oxidation reaction, which achieved 99% yield in 1 h under ambient conditions.

Pre-Polymerization Enables Controllable Synthesis of Nanosheet-Based Porphyrin Polymers towards High-Performance Li-Ion Batteries.

The precise regulation of nucleation growth and assembly of polymers is still an intriguing goal but an enormous challenge. In this study, we proposed a pre-polymerization strategy to regulate the assembly and growth of polymers by facilely controlling the concentration of polymerization initiator, and thus obtained two kinds of different nanosheet-based porphyrin polymer materials using tetrakis-5,10,15,20-(4-aminophenyl) porphyrin (TAPP) as the precursor. Notably, due to the π-π stacking and doping of TAPP during the preparation process, the obtained PTAPP-nanocube material exhibits a high intrinsic bulk conductivity reaching 1.49×10-4  S m-1 . Profiting from the large π-conjugated structure of porphyrin units, closely stacked layer structure and excellent conductivity, the resultant porphyrin polymers, as electrode materials for lithium ion batteries, deliver high specific capacity (≈650 mAh g-1 at the current density of 100 mA g-1 ), excellent rate performance and long-cycle stability, which are among the best reports of porphyrin polymer-based electrode materials for lithium-ion batteries, to the best of our knowledge. Therefore, such a pre-polymerization approach would provide a new insight for the controllable synthesis of polymers towards custom-made architecture and function.

Constructing polymers towards ultrathin nanosheets with dual mesopores and intrinsic photoactivity.

We developed ultrathin dual-mesoporous polymer nanosheets by combining co-assembly of different templates with in situ synthesis of functional polymers, which featured inherent smaller and template-directed larger mesopores (2.6 nm and 15 nm, respectively), ultrathin nanolayers (20 nm), high surface area (268 m2 g-1), intrinsic fluorescent properties and effective detectability for organophosphates.

Self-Stabilized Amorphous Organic Materials with Room-Temperature Phosphorescence.

The stability of pure organic room-temperature phosphorescent (RTP) materials in air has been a research hotspot in recent years. Without crystallization or encapsulation, a new strategy was proposed to obtain self-stabilized organic RTP materials, based on a complete ionization of a photo-induced charge separation system. The ionization of aromatic phenol 4-carbazolyl salicylaldehyde (CSA) formed a stable H-bonding anion-cation radical structure and led to the completely amorphous CSA-I film. Phosphorescent lifetimes as long as 0.14 s at room temperature and with direct exposure to air were observed. The emission intensity was also increased by 21.5-fold. Such an amorphous RTP material reconciled the contradiction between phosphorescence stability and vapor permeability and has been successfully utilized for peroxide vapor detection.

A very sensitive and highly selective organic selector in CNTs composite chemiresistive for efficient differentiation of organic amine vapours.

With the call for the IoE (Internet of Everything), stable and efficient electric noses/tongues have become the most critical part of the sensor network. Identifying target gases efficiently and rapidly at ambient air becomes a focus on sensor research. We designed a chemiresistive sensor based on a composite of a specific selector and single-walled carbon nanotubes (SWNTs) for the detection and differentiation of organic amine vapours in air (25 ℃, 55% RH). The synergetic combination of F4-TCNQ (2,3,5,6-Tetrafluoro-7,7',8,8'-tetracyanoquinodimethane) and SWCNTs could modulate the electrical properties of sensor leading to the enhancement of response up to ppb-level for primary amine vapor detection. Different from traditional chemiresistive sensor, this sensing materials exhibit unique differences in response to different types of amines thought different mechanisms. We have proven the practical possibilities through the detection of the simulated complexed environmental atmosphere in industrial production. Furthermore, we explored the working mechanism of high-performance sensors, which could provide theoretical guidance for sensor design for more commercial applications. This study provided a simple, convenient, and highly efficient practical method for organic amine detection at ambient air for real-life applications.

Rational Construction of Highly Tunable Organic Charge-Transfer Complexes for Chemiresistive Sensor Applications.

Organic charge-transfer (CT) complexes with a unique electrical performance are attractive materials for organic electronics. However, achieving breakthroughs in the practical application of CT complexes through rational design have always been a challenge. For the first time, a chemiresistive sensor for nerve agent that mimics (diethyl chlorophosphate) vapor detection is rationally designed based on organic CT complexes. Such CT complex chemiresistive sensor realizes a subppb detection of diethyl chlorophosphate (DCP) within 5 s under atmospheric conditions at room temperature with a high selectivity. Meanwhile, based on the highly tunable characteristics of CT complexes, the influence of morphology and intermolecular interaction on the sensing response are investigated. It is worth noting that a stronger intermolecular interaction results in lower sensing responses for CT complexes with a different D/A combination but with the same ratio. The organic charge-transfer materials not only provide a highly tunable platform for the chemiresistive sensor but also have the special properties such as solution processability, flexibility, and molecular recognition, which provides more possibilities for the application of flexible and wearable biosensors.

Simple and Efficient Chromophoric-Fluorogenic Probes for Diethylchlorophosphate Vapor.

In this work, we developed two small-molecule probes for real-time and onsite detecting of diethylchlorophosphate (DCP) vapor by incorporating amine groups into Schiff base skeletons. Both probes can be easily synthesized with high yield through one-step and low-cost synthesis. They can detect DCP vapor in the chromophoric-fluorogenic dual mode, which combines both the advantages of the visualization of color sensing and the high sensitivity of the fluorescence sensing. Furthermore, its sensing is based on the "turn-on" mode which can avoid the interference arising from photobleaching or fluorescence quenching agents based on "turn-off" mode. The detection limit was quantified to be as low as 0.14 ppb.

Attogram "Meth" Detection Enabled by Selective Organic Crystal Disaggregation via Directed Crystal Level Interactions.

In this contribution, completely different from traditional probes based on molecular host-guest interaction, crystal level interaction was proposed as an ultrasensitive design strategy for molecule detection. In such a strategy, crystal-guest interaction triggered rapid crystal disaggregation to gain great signal change, far more efficient than molecule scale coupling. Highly ordered pyrene methanol (PM) crystal was self-assembled with hydrogen bond chain and π-π stacking force. Its {011} surface can be destabilized by methamphetamine hydrochlorate (MA, heavily used illicit drug) selectively and efficiently. The detection limit was improved to an amazing attogram level (5.4 ag/mL, 29.1 fM), 9 orders of magnitude lower than the best reported host-guest result.

Highly Efficient Multiple-Anchored Fluorescent Probe for the Detection of Aniline Vapor Based on Synergistic Effect: Chemical Reaction and PET.

A multiple-anchored fluorescent probe ((((hexane-1,6-diylbis(2,7-bis(4-formyl)-phenyl)-9H-fluorine-9,9-diyl))-bis(hexane-6,1-diyl))-bis(9H-carbazole-9,3,6-triyl))-tetrakis(benzene-4,1-diyl))-tetraformyl-(8FP-2F) with eight aldehyde groups was designed and synthesized. The molecule has four branches and highly twisted structure. Furthermore, it tends to self-assemble into nanospheres, which is beneficial for gaseous analyte penetration and high fluorescence quantum efficiency. Among gaseous analytes, detection of aniline vapor is extraordinarily important in the control of environmental issues and human diseases. Herein, 8FP-2F was introduced to detect aniline vapor with distinguished sensitivity and selectivity via simple Schiff base reaction at room temperature. After exposure to saturate aniline vapor, the 89% fluorescence of 8FP-2F was quenched in 50 s and the detection limit was as low as 3 ppb. Further study showed the suitable HOMO/LUMO energy levels and matched orbital symmetry between probe and aniline molecules ensured chemical reaction and PET process work together. The synergistic effect resulted in a significant sensing performance and fluorescence quenching toward aniline vapor. Moreover, the multiple active sites structure of 8FP-2F means it could be applied for constructing many interesting structures and highly efficient organic optoelectronic functional materials.

Schiff Base Substituent-Triggered Efficient Deboration Reaction and Its Application in Highly Sensitive Hydrogen Peroxide Vapor Detection.

The organic thin-film fluorescence probe, with the advantages of not polluting the analyte and fast response, has attracted much attention in explosive detection. Different with nitro explosives, the peroxide-based explosives are hardly to be detected because of their poor ultraviolet absorption and lack of an aromatic ring. As the signature compound of peroxide-based explosives, H2O2 vapor detection became more and more important. Boron ester or acid is considered to be a suitable functional group for the detection of hydrogen peroxide due to its reliable reactive activity. Its only drawback lies on its slow degradation velocity. In this work, we try to introduce some functional group to make the boron ester to be easily oxidized by H2O2. Herein, 4-(phenyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amino)benzaldehyde (OTB) was synthesized and its imine derivatives, OTBXAs, were easily obtained just by putting OTB films in different primary amines vapors. OTBXAs show fast deboronation velocity in H2O2 vapor compared with OTB. The complete reaction time of (E)-N-phenyl-4-((propylimino)methyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline (OTBPA) was even shortened 40 times with a response time of seconds. The detection limit for H2O2 vapor was as low as 4.1 parts per trillion (ppt). Further study showed that it is a general approach to enhance the sensing performance of borate to hydrogen peroxide (H2O2) vapor by introducing an imine into an aromatic borate molecule via a solid/vapor reaction.

Concise and Efficient Fluorescent Probe via an Intromolecular Charge Transfer for the Chemical Warfare Agent Mimic Diethylchlorophosphate Vapor Detection.

Sarin, used as chemical warfare agents (CWAs) for terrorist attacks, can induce a number of virulent effects. Therefore, countermeasures which could realize robust and convenient detection of sarin are in exigent need. A concise charge-transfer colorimetric and fluorescent probe (4-(6-(tert-butyl)pyridine-2-yl)-N,N-diphenylaniline, TBPY-TPA) that could be capable of real-time and on-site monitoring of DCP vapor was reported in this contribution. Upon contact with DCP, the emission band red-shifted from 410 to 522 nm upon exposure to DCP vapor. And the quenching rate of TBPY-TPA reached up to 98% within 25 s. Chemical substances such as acetic acid (HAc), dimethyl methylphosphonate (DMMP), pinacolyl methylphosphonate (PAMP), and triethyl phosphate (TEP) do not interfere with the detection. A detection limit for DCP down to 2.6 ppb level is remarkably achieved which is below the Immediately Dangerous to Life or Health concentration. NMR data suggested that a transformation of the pyridine group into pyridinium salt via a cascade reaction is responsible for the sensing process which induced the dramatic fluorescent red shift. All of these data suggest TBPY-TPA is a promising fluorescent sensor for a rapid, simple, and low-cost method for DCP detection, which could be easy to prepare as a portable chemosensor kit for its practical application in real-time and on-site monitoring.

A simple but highly efficient multi-formyl phenol-amine system for fluorescence detection of peroxide explosive vapour.

A simple, highly stable, sensitive and selective fluorescent system for peroxide explosives was developed via an aromatic aldehyde oxidation reaction. The high efficiency arises from its higher HOMO level and multiple H-bonding. The sensitivity is obtained to be 0.1 ppt for H2O2 and 0.2 ppb for TATP.

Femtogram level detection of nitrate ester explosives via an 8-pyrenyl-substituted fluorene dimer bridged by a 1,6-hexanyl unit.

Compared with nitroaromatic explosives detection, nitrate esters are far from wide attention possibly because of their shortage of aromatic ring and difficulty in being detected. Three fluorescent chemical probes for trace nitrate ester detection: an intramolecular dimer (P3) of 8-pyrenyl-substituted fluorenes bridged by a 1,6-hexanyl unit as well as its counterparts 2PR-F (P1) and 2PR-Cz (P2) has been synthesized and characterized. Their chemical structures and photophysical and electrochemical properties show that the dimer P3 film has a higher molar extinction coefficient, larger steric hindrance, higher area-to-volume ratio, and matching energy level with nitrate ester explosives, which contributes to higher sensitivity and moderate selectivity for sensing of nitrate ester explosives such as nitroglycerin (NG). The fluorescence of the P3 film is rapidly about 90% quenched upon exposure to a saturated vapor of NG for 50 s and almost 100% quenched for 300 s at room temperature due to photoinduced electron transfer between the probe and analyte. In addition, a very sensitive, rapid, simple, and low-cost surface-sensing method by disposable filter-paper-based test strips is demonstrated. The contact-mode approach exhibits a detection limit as low as 0.5 fg/cm(2) for NG. These results reveal that the multiple-pyrenyl-unit-substituted fluorene dimer P3 is suitable for preparing a highly sensitive and efficient thin-film device for detecting nitrate esters.

A mild and catalyst-free conversion of solid phase benzylidenemalononitrile/benzylidenemalonate to N-benzylidene-amine and its application for fluorescence detection of primary alkyl amine vapor.

A new rapid and catalyst-free solid/vapor reaction between benzylidenemalonate/benzylidenemalononitrile and primary alkyl amines was found. With these as sensory units of fluorescent polymers, probes for primary amine vapor with high sensitivity and selectivity were developed.