Electronic Effect Driven Specific and Sensitive Recognition toward GHB.

Precise detection of a trace substance that intrinsically possesses weak chemical activity and less-distinctive spatial structure is of great significance, but full of challenges, as it could not be effectively recognized via either an active covalent reaction process or multiple noncovalent interactions toward its simple structure. Here, the electronic-effect-driven recognition strategy was proposed to visually sense an illicit drug, γ-hydroxybutyric acid (GHB), which was treated as an analyte model due to its inherent simple structure. In particular, a sensing system composed of two probes substituted by the nitro (-NO2) and the hydrogen (-H), was constructed with the characteristic yellow coloring and blue fluorescence, as well as high sensitivity (0.586 ng/mL), fast response (0.2 s), and specific recognition, even in the presence of 22 interferents. In addition, a portable eyeshadow box-like sensing chip was fabricated and proven to be reliable and feasible in sensing GHB disguised in liquors for self-protection in a covert manner. Hence, this work developed an electronic-effect-driven modulation strategy of the recognition interaction between the probe and the analyte and, thus, would open up a new thought for detecting the analyte with weak activity and a simple structure, as well as propel the relevant application in real scenarios.

Controlled Synthesis of Preferential Facet-Exposed Fe-MOFs for Ultrasensitive Detection of Peroxides.

Exposing different facets on metal-organic frameworks (MOFs) is highly desirable to enhance the performance for various applications, however, exploiting a concise and effective approach to achieve facet-controlled synthesis of MOFs remains challenging. Here, by modulating the ratio of metal precursors to ligands, the facet-engineered iron-based MOFs (Fe-MOFs) exhibits enhanced catalytic activity for Fenton reaction are explored, and the mechanism of facet-dependent performance is revealed in detail. Fully exposed (101) and (100) facets on spindle-shaped Fe-MOFs enable rapid oxidation of colorless o-phenylenediamine (OPD) to colored products, thereby establishing a dual-mode platform for the detection of hydrogen peroxide (H2O2) and triacetone triperoxide (TATP). Thus, a detection limit as low as 2.06 nm is achieved, and robust selectivity against a wide range of common substances (>16 types) is obtained, which is further improved by incorporating a deep learning architecture with an SE-VGG16 network model, enabling precise differentiation of oxidizing agents from captured images. The present strategy is expected will shine light on both the rational synthesis of nanomaterials with modulated morphologies and the exploitation of high-performance trace chemical sensors.

Amination and Protonation Facilitated Novel Isoxazole Derivative for Highly Efficient Electron and Hole Separation.

It is of great importance to understand the intrinsic relationship between phototautomerization and photoelectric properties for the exploration of novel organic materials. Here, in order to chemically control the protonation process, the aminated isoxazole derivative (2,2'-(isoxazolo[5,4-d]isoxazole-3,6-diyl)dibenzenaminium, DP-DA-DPIxz) with -N═ as the proton acceptor was designed to achieve the twisted intramolecular charge transfer (TICT) state which was triggered by an excited-state intramolecular proton transfer (ESIPT) process. This kind of protonation enhanced the intramolecular hydrogen bonding, conjugative effect, and steric hindrance effects, ensuring a barrierless spontaneous TICT process. Through the intramolecular proton transfer, the configuration torsion and conjugation dissociation of the DP-DA-DPIxz molecule was favored, which led to efficient charge separation and remarkable variations in light-emitting properties. We hope the present investigation will provide a new approach to design novel optoelectronic organic materials and shine light on the understanding of the charge transfer and separation process in molecular science.

Coherent Modulation of the Aggregation Behavior and Intramolecular Charge Transfer in Small Molecule Probes for Sensitive and Long-term Nerve Agent Monitoring.

Aggregation-induced emission (AIE) shows promising performance in chemical sensing relying on the change of the emission behavior of the probe molecule monomers to the aggregated product. However, whether the response contrast could be further boosted by utilizing the emission property of the aggregated probe and the aggregated product remains a big challenge. Here, an exciting AIE probe regulation strategy was proposed by coherently modulating the aggregation behavior and the intramolecular charge transfer (ICT) property of the probes and thus an aggregated-to-aggregated colorimetric-fluorescent dual-mode detection was achieved. The blue emissive film obtained with the optimal AIE probe has been proven to be effective to recognize the vapor of nerve agent analog DCP in air by emitting a sharp green fluorescence. In addition, a porous polymer-based wet sensing chip loaded with the probe enables the immediate response to DCP vapor with a limit of detection (LOD) of 1.7 ppb, and it was further integrated into a wearable watch device for long-term monitoring of DCP vapor up to two weeks. We expect the present probe design strategy would greatly deepen the AIE-based science and provide new insights for long-term monitoring sensors toward trace hazardous substances.

Precise Electron-Withdrawing Strength Modulation of ESIPT Probes for Ultrasensitive and Specific Fluorescence Sensing.

The precise regulation of the electron-withdrawing/electron-donating strength in a probe is of great significance for the design of reaction-based fluorescent probes with specific functionalities. Here, a family of excited-state intramolecular proton transfer (ESIPT)-based probes with fluorescence turn-on sensing properties toward KMnO4 was designed by precisely modulating the electron-withdrawing strength of the substituents located at the para-position of the recognition group. It is found that -F, -CHO, and -H as the electron-withdrawing groups bound at the probe can specifically recognize KMnO4, which ensures a blue emission displayed by the reaction products. Especially with -CHO as the electron-withdrawing group, the reaction product shows the most stable fluorescence. The probe 2-(benzo[d]oxazol-2-yl)-4-formylphenyl acrylate (BOPA-CHO) demonstrated a more superior sensing performance toward KMnO4, including a low limit of detection (LOD, 0.96 nM), a rapid response (<3 s), and a rather good selectivity even in the presence of 21 interferents. Moreover, the practicality of the probe was further verified by a test pen comprising a BOPA-CHO-embedded sponge, which is capable of detecting KMnO4 solid with a naked-eye LOD of 11.62 ng. The present probe design and modulation strategy would open up a new path for the design of high-performance fluorescent probes.

A TD-DFT study of a class of D-π-A fluorescent probes for detection of typical oxidants.

A deep understanding of the fluorescence response mechanisms is the foundation for design-oriented strategies for D-π-A probes for trace hazardous chemicals. Here, from the perspective of electronegativity regulation of the π-bridge recognition site, an electron-donation modulation strategy involving various comprehensive evaluations of the optical and chemical properties is proposed through a series of theoretical analyses. Due to the preferential combined interaction between the π-bridge recognition site and MnO4-, high electrophilic reactivity and feasible chemical reaction energy barrier, a high-performance filter paper chip and hydrogel chip for the detection of aqueous and air-suspended environmental KMnO4 was achieved. We expect the present modulation strategy will facilitate efficient fluorescent probe design and provide a universal methodology for the exploration of functional D-π-A molecules.

A Deep Understanding on the Effective Generation of Twisted Intramolecular Charge Transfer by Protonation in Thiazolo[5,4-d]thiazole Derivatives.

The exploration of the intrinsic relationship between the phototautomerization and photoelectric properties is of great significance for the application of the emerging novel organic materials, such as the (bi)heterocyclic thiazolo[5,4-d]thiazole derivatives (TzTz). Here, by introducing the chemical-controlling protonation, a barrierless spontaneous rotation movement of the designed TzTz derivative (2,5-diyl-amino-thiazolo[5,4-d]thiazole, DA-TzTz) was ensured through the facilitation of the excited-state intramolecular proton transfer (ESIPT) triggered twisted intramolecular charge transfer (TICT) process by the enhancement of the intramolecular hydrogen bonds, steric hindrance effect, and conjugative effect. It is further verified that the hetero S atoms could mostly effect the proton accepting ability of -N═ through comparing with the influences to the intramolecular H-bond between the protonated/nonprotonated amino groups and the -N═ atoms brought by the replacement of them with N or O atoms. As a result, the dissociation and rearrangement of the π conjugation in DA-TzTz accompanying with the variation of the optoelectronic characteristics was benefited from the establishment of the preferential charge-transfer and separation. We expect this tentative study could establish a new concept of designing an efficient charge-transfer and separation method, paving the way for the development of the TzTz derivatives and other optoelectronic organic materials.

D-π-A Dual-Mode Probe Design for the Detection of nM-Level Typical Oxidants.

Although a set of functional molecules with the D-π-A structure has been explored as optical probes for the detection of target analytes, it remains a great challenge to elaborately design a single probe for distinguishing different analytes by their intrinsic oxidation or reduction capabilities and thus to generate distinct optical responses. Here, a unique TCF-based probe (DMA-CN) containing two unsaturated double bonds in the π-conjugation bridge and TCF with different reaction activities that could be cut off by KMnO4 and NaClO in varying degrees was developed, causing remarkably distinguishable responses for both fluorescence and colorimetric channels to discriminate KMnO4 and NaClO from each other. The fluorescence and colorimetric limits of detection (LODs) of the proposed DMA-CN toward KMnO4 were calculated as 60 and 91 nM, respectively, while those for NaClO were 13.3 and 214 nM, and all the optical signal change can be observed within 1 s with good specificity. Based on the proposed probe design strategy, a well-fabricated test strip was proven to be promising for the rapid, in-field detection and risk management. We expect that the present probe design methodology would provide a powerful strategy for efficient probe exploration, especially for discriminating the substances with similar oxidizing properties.

Competitive Delocalized Charge Transfer Boosted by Solvent Induction Strategy for Survivable Colorimetric Detection of ng-Level Urea.

Achieving sensitive and robust colorimetry is of great significance for on-site chemical detection, but has always been a dilemma or at the expense of practicality. Here, from the perspective of solvent, which is commonly the indispensable medium for chemical sensing, the solvent induction strategy concerning the hydrophobic shielding and hydrophilic bonding solvent cage was proposed considering the configuration branching ratio in the reagent and the prevention of the autoxidation channel. Due to the competitive delocalized charge transfer in the probe and the effective viscous drag in the reagent, remarkable sensing signal concentrating and moisture retention capability were achieved. We expect the present strategy would facilitate the active but robust chemical reaction design and provide a universal methodology for the exploration of high-performance chemical sensors.

Complete Inhibition of the Rotation in a Barrierless TICT Probe for Fluorescence-On Qualitative Analysis.

Inhibition of twisting intramolecular charge transfer (TICT) is one of the most attractive methods for fluorescence-on analysis, whereas it remains enigmatic whether the fluorescence in a TICT-based probe could be thoroughly lightened. Here, for maximizing the fluorescence-on signal of the TICT-based probe, we develop a model by employing chemical reaction to directly cleave the linkage between the rotational electron donor and acceptor with a predisposed fluorescent signal close to zero. To validate this assumption, a nonfluorescent probe with barrierless rotation is successfully achieved by grafting acryloyl with -C═C- recognition sites onto coumarin, and 7-hydroxycoumarin with bright blue fluorescence could be released within 3 s upon probing KMnO4 with an amount as low as 0.95 nM and 6.6 pg. We believe that the present strategy could not only deepen the insights of photochemistry but also facilitate the development of a theranostic drug delivery system, energy conversion, pollution control, and health risk reduction.

Electronic Tuning in Reaction-Based Fluorescent Sensing for Instantaneous and Ultrasensitive Visualization of Ethylenediamine.

Manipulation of a multi-physical quantity to steer a molecular photophysical property is of great significance in improving sensing performance. Here, an investigation on how a physical quantity rooted in the molecular structure induces an optical behavior change to facilitate ultrasensitive detection of ethylenediamine (EDA) is performed by varying a set of thiols. The model molecule consisting of a thiol with dual-carboxyl exhibits the strongest fluorescence, which is ascribed to the electron-donating ability and prompted larger orbital overlap and oscillator strength. The elevated fluorescence positively corelated to the increased EDA, endowing an ultrasensitive response to the nanomolar-liquid/ppm-vapor. A gas detector with superior performance fulfills a contactless and real-time management of EDA. We envisage this electron-tuning strategy-enabled fluorescence enhancement can offer in-depth insight in advancing molecule-customized design, further paving the way to widening applications.

One-Step Instantaneous Detection of Multiple Military and Improvised Explosives Facilitated by Colorimetric Reagent Design.

Although colorimetric detection based on reagents has been widely used in the fields of practical trace analysis, its versatility for detecting multitargets remains the most challenging problem. As a proof of concept, a general colorimetric reagent based on potassium isopropanol (C3H7KO) and dimethyl sulfoxide for one-step instantaneous detection and discrimination of typical military and improvised explosives was designed. Vivid colors from none to purple red, blue green, yellow green, and green were shown, respectively, when detecting 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), elemental sulfur (S), and potassium permanganate (KMnO4). The unique design including the specific nucleophilic addition reaction and the base-catalyzed oxidation-induced electron transfer ensures perfect selectivity even upon facing more than 20 interferents. It is further experimentally demonstrated that the confinement effect introduced by Tween-20 plays an essential role in enhancing the color signal on the surface and thus boosts the detection performance even with a mass as low as 1.45 ng. The applicability of this versatile colorimetric reagent was further verified by integrating the reagent onto paper strips for the in-field identification of TNT, DNT, S, and KMnO4 with the help of a portable smartphone-based microscope apparatus, and a practical detection mass of 10.3 ng could be realized. We expect the present colorimetric reagent design strategy would pave a way for one-step instantaneous visual detection toward trace multianalytes.

Transition-Metal-Doped p-Type ZnO Nanoparticle-Based Sensory Array for Instant Discrimination of Explosive Vapors.

The development of portable, real-time, and cheap platforms to monitor ultratrace levels of explosives is of great urgence and importance due to the threat of terrorism attacks and the need for homeland security. However, most of the previous chemiresistor sensors for explosive detection are suffering from limited responses and long response time. Here, a transition-metal-doping method is presented to remarkably promote the quantity of the surface defect states and to significantly reduce the charge transfer distance by creating a local charge reservoir layer. Thus, the sensor response is greatly enhanced and the response time is remarkably shortened. The resulting sensory array can not only detect military explosives, such as, TNT, DNT, PNT, PA, and RDX with high response, but also can fully distinguish some of the improvised explosive vapors, such as AN and urea, due to the huge response reaching to 100%. Furthermore, this sensory array can discriminate ppb-level TNT and ppt-level RDX from structurally similar and high-concentration interfering aromatic gases in less than 12 s. Through comparison with the previously reported chemiresistor or Schottky sensors for explosive detection, the present transition-metal-doping method resulting ZnO sensor stands out and undoubtedly challenges the best.

Surface Superoxide Complex Defects-Boosted Ultrasensitive ppb-Level NO2 Gas Sensors.

Sn(4+) -O2 (-•) centers are intentionally created in SnO2 nanoflowers by a thermodynamically instable synthetic process. The resulting SnO2 nanoflower-based sensor is confirmed to be the most sensitive ppb-level chemiresistor NO2 sensor to date. The Sn(4+) -O2 (-•) centers with strong gas-adsorbing and high eletron-donating capability towards NO2 molecules decisively determine the sensor sensitivity.

Precise counter anion modulation of the self-assembly behavior-endowed ultrasensitive and specific dual-mode visualization of nitrate.

Pt(II) polypyridine complex-based probe exhibits promising performance in anion detection by the change of the absorption and emission properties based on supramolecular self-assembly. However, whether one can develop a modulation strategy of the counter anion to boost the detection sensitivity and anti-interference capability of the Pt(II) complex-based probe remains a big challenge. Here, an effective modulation strategy was proposed by precisely regulating the interaction energy through adjusting the type of the counter anions, and a series of probes have been synthesized by counter anion (X = Cl-, ClO4-, PF6-) exchange in [Pt(tpy)Cl]·X (tpy=2,2':6',2''-terpyridine), and thus the colorimetric-luminescence dual-mode detection toward nitrate was achieved. The optimal [Pt(tpy)Cl]·Cl probe shows superior nitrate detection performance including a limit of detection (LOD) (8.68 nM), rapid response (<0.5 s), an excellent selectivity and anti-interference capability even facing 14 common anions. Moreover, a polyvinyl alcohol (PVA) sponge-based sensing chip loaded with the probe enables the ultra-sensitive detection of nitrate particles with an ultralow detection limit of 7.6 pg, and it was further integrated into a detection pen for the accurate recognition of nitrate particles in real scenarios. The proposed counter-anion modulation strategy is expected to start a new frontier for the exploration of novel Pt(II) complex-based probes.

Design of Highly Efficient Electronic Energy Transfer in Functionalized Quantum Dots Driven Specifically by Ethylenediamine.

The exploration of emerging functionalized quantum dots (QDs) through modulating the effective interaction between the sensing element and target analyte is of great significance for high-performance trace sensing. Here, the chromone-based ligand grafted QDs (QDs-Chromone) were initiated to realize the electronic energy transfer (EET) driven specifically by ethylenediamine (EDA) in the absence of spectral overlap. The fluorescent and colorimetric dual-mode responses (from red to blue and from colorless to yellow, respectively) resulting from the expanded conjugated ligands reinforced the analytical selectivity, endowing an ultrasensitive and specific response to submicromolar-liquid of EDA. In addition, a QDs-Chromone-based sensing chip was constructed to achieve the ultrasensitive recognition of EDA vapor with a naked-eye observed response at a concentration as low as 10 ppm, as well as a robust anti-interfering ability in complicated scenarios monitoring. We expect the proposed EET strategy in shaping functionalized QDs for high-performance sensing will shine light on both rational probe design methodology and deep sensing mechanism exploration.

A Self-Accelerating Naphthalimide-Based Probe Coupled with Upconversion Nanoparticles for Ultra-Accurate Tri-Mode Visualization of Hydrogen Peroxide.

The design and development of ultra-accurate probe is of great significance to chemical sensing in complex practical scenarios. Here, a self-accelerating naphthalimide-based probe with fast response and high sensitivity toward hydrogen peroxide (H2O2) is designed. By coupling with the specially selected upconversion nanoparticles (UCNPs), an ultra-accurate colorimetric-fluorescent-upconversion luminescence (UCL) tri-mode platform is constructed. Owing to the promoted reaction process, this platform demonstrates rapid response (< 1 s), an ultra-low detection limit (4.34 nM), and superb anti-interferent ability even in presence of > 21 types of oxidants, explosives, metallic salts, daily compounds, colorful or fluorescent substances. In addition, the effectiveness of this design is further verified by a sponge-based sensing chip loaded with the UCNPs/probe in recognizing trace H2O2 vapor from interferents with the three characteristic colors existing simultaneously. The proposed design of probe and tri-mode visualization detection platform is expected to open up a brand-new methodology for ultra-accurate sensing.

Solvation effect enabled visualized discrimination of multiple metal ions.

Highly efficient detection of environmental residual potentially toxic species is of concern worldwide as their presence in an excessive amount would greatly endanger the health of human beings as well as environmental sustainability. The solvation effect is a critical factor to be considered for understanding chemical reaction progress as well as the photophysical behaviors of substances and thus is promising for visualized detection of metal ions. Herein, by applying 5-amino-1,10-phenanthroline (APT) as the optical probe, a sensing strategy was proposed based on the solvation effect modulated complexation of APT towards different metal ions to achieve the visualized discrimination of four critical ions (Cu(II), Zn(II), Cd(II), and Al(III)). How the crucial intrinsic properties of the solvent (e.g., polarity, solvent free energy, and electrostatic potential) influenced the complexation and the product emission was clarified, and the detection performances were systematically evaluated with detection limits as low as the nM level and good recognition selectivity. Furthermore, a portable sensing chip was developed with potential for highly efficient analysis in complicated scenes; thus, this strategy offers a new insight into determining multiple metal ions or other critical substances upon solvation manipulation.

Electrophilicity Modulation for Sub-ppm Visualization and Discrimination of EDA.

Precise and timely recognition of hazardous chemical substances is of great significance for safeguarding human health, ecological environment, public security, etc., especially crucial for adopting appropriate disposition measures. Up to now, there remains a practical challenge to sensitively detect and differentiate organic amines with similar chemical structures with intuitive analysis outcomes. Here, a unique optical probe with two electrophilic recognition sites for rapid and ultra-sensitive ratiometric fluorescence detection of ethylenediamine (EDA) is presented, while producing distinct fluorescence signals to its structural analog. The probe exhibits ppb/nmol level sensitivity to liquidous and gaseous EDA, specific recognition toward EDA without disturbance to up to 28 potential interferents, as well as rapid fluorescence response within 0.2 s. By further combining the portable sensing chip with the convolutional algorithm endowed with image processing, this work cracked the problem of precisely discriminating the target and non-targets at extremely low concentrations.

Amorphous Copper-Based Nanoparticles with Clusterization-Triggered Phosphorescence for Ultrasensing 2,4,6-Trinitrotoluene.

Amorphous metal-based nanostructures have attracted great attention recently due to their facilitative electron transfer and abundant reactive sites, whereas it remains enigmatic as to whether amorphous copper-based nanoparticles (CuNPs) can be achieved. Here, for synthesizing amorphous CuNPs, glutathione is adopted as a ligand to inhibit the nucleation and crystallization process via its electrostatic repulsion. By subtly tailoring the solvent polarity, not only can amorphous glutathione-functionalized CuNPs (GSH-CuNPs) with phosphorescent performance be achieved after transferring the non-conjugation of GSH ligand to through-space conjugation, namely clusterization-triggered emission, but also the phosphorescence-off of GSH-CuNPs toward 2,4,6-trinitrotoluene (TNT) can be realized by the photoinduced electron-transfer process through the hydrogen bond channel, which is established between carboxyl and amino groups of GSH-CuNPs with the nitryl group of TNT. Benefitting from the intrinsic superiorities of the amorphous CuNPs, desired phosphorescence and detection performances of GSH-CuNPs toward airborne TNT microparticulates are undoubtedly realized, including high quantum yield (13.22%), excellent specificity in 33 potential interferents, instantaneous response, and ultralow detection limit (1.56 pg). The present GSH-CuNPs are expected to stretch amorphous metal-based nanostructures and deepen the insights into amorphous materials for optical detection.