Recognition Unit Research Articles

Controllable formation of polydopamine on carbon dots for ultrasensitive detection of alkaline phosphatase and ratiometric fluorescence immunoassay of benzocaine.

Sensing alkaline phosphatase (ALP) activity with high sensitivity and accuracy is critical for both ALP-related health and food safety supervision and the development of ALP-triggered immunoassay platforms. Herein, an ultrasensitive ratiometric fluorescence (RF) sensing system based on the controllable formation of luminescent polydopamine and efficient quenching of carbon dots was proposed for the ALP activity assay, achieving quantitative detection in the range of 0.01-100mU/L. Furthermore, this RF sensing system was integrated with an ALP-based ELISA platform to construct an RF-ELISA for benzocaine, a potentially abused anesthetic in edible fish, and ultrasensitive assay at the level of fg/mL was realized. This ratiometric strategy-based platform effectively shields various interferences through the self-calibration effect, thus providing more accurate and reliable quantification results. This study not only offers an efficient method for ultratrace detection of ALP and benzocaine but also proposes a universal platform for ultrasensitive detection of diverse targets in food analysis by replacing the recognition unit.

Integrating multiple probes for simplifying signal-on photoelectrochemical biosensing of microRNA with ultrasensitivity and wide detection range based on biofunctionalized porous ferroferric oxide and hypotoxic quaternary semiconductor

A facile and signal-on photoelectrochemical (PEC) biosensing strategy was designed based on hypotoxic Cu2ZnSnS4 NPs nanoparticles (NPs) and biofunctionalized Fe3O4 NPs that integrated recognition units with signal elements, without the need for immobilization of probes on the electrode. Cu2ZnSnS4 NPs were used as the PEC substrate to produce intensive and stable photocurrent. The porous magnetic Fe3O4 NPs displayed favorable loading capacity for CdS QDs and easy biofunctionalization by negatively charged capture DNA (cDNA). cDNA sealed the pore of Fe3O4 NPs, avoiding the escape of CdS QDs as a PEC sensitizer. After hybridizing with target microRNA (miRNA), cDNA split away off Fe3O4 NPs whose porous channel might open and release sealed CdS QDs (signal element), resulting in a dramatical enhancement of PEC response. Herein, miRNA hardly contacted with CdS QDs, effectively avoiding harm to the target miRNA. This proposed strategy simplified procedures of assembly and made the biorecognition process sufficient for promoting a stationary quantity of probes, which was expected to obtain satisfactory performance for bioassay. Using miRNA-155 as a model analyte and combining with duplex-specific nuclease (DSN)-assisted amplification, a simplified and signal-on PEC biosensing platform for miRNA-155 with wonderful performance was proposed. DSN-assisted amplification further promoted PEC signal increment, leading to ulteriorly improving sensitivity (detection limit of 0.17 fM) and linear range (6.5 orders of magnitude) for miRNA-155 assay. Moreover, the developed PEC biosensing platform exhibited satisfactory stability, excellent specificity, and favorable accuracy for miRNA-155, which would have a promising prospect for monitoring miRNA expression in tumor cells.

A Comparative Study on Selecting Acoustic Modeling Units for WFST-based Mongolian Speech Recognition

Traditional weighted finite-state transducer– (WFST) based Mongolian automatic speech recognition (ASR) systems use phonemes as pronunciation lexicon modeling units. However, Mongolian is an agglutinative, low-resource language, and building an ASR system based on the phoneme pronunciation lexicon remains a challenge for various reasons. First, the phoneme pronunciation lexicon manually constructed by Mongolian linguists is finite, which is usually used to build a grapheme-to-phoneme conversion (G2P) model to frequently expand new words. However, the data sparsity decreases the robustness of the G2P model and affects the performance of the final ASR system. Second, homophones and polysyllabic words are common in Mongolian, which has a certain impact on the construction of the Mongolian acoustic model. To address these problems, in this work, we first propose a grapheme-to-phoneme alignment model to obtain the mapping relationship between phonemes and subword units. Then, we construct an acoustic subword segmentation set to segment words directly instead of using the traditional G2P method to predict phoneme sequences to expand the pronunciation lexicon. Further, by analyzing the Mongolian encoding form, we also propose an acoustic subword modeling units construction method that removes control characters. Finally, we investigate various acoustic subword modeling units for pronunciation lexicon construction for the Mongolian ASR system. Experiments on a Mongolian dataset with 325 hours of training show that the pronunciation lexicon based on the acoustic subword modeling unit can effectively construct the WFST-based Mongolian ASR system. Further, removing the control characters when building the acoustic subword modeling unit can further improve the ASR system performance.

Interference-free multimodal biosensing of adrenaline over other neurotransmitters: Role of 2-iminomethylenephenylboronic acid as the signal transduction unit of fluorescence and impedance

Aberrant levels of the neurotransmitters adrenaline (AD), noradrenaline (NA), and dopamine (DA) are linked to various diseases. Therefore, interference-free biosensing of neurotransmitters has become an important area of research. However, structural similarity (presence of diol/amine functionalities), small size, and neutral charge of the catecholamines add complexity to designing recognition systems and make the detection non-specific. Herein, we report a recognition unit 2-iminomethylenephenylboronic acid (2-IMPBA), which appears to be a remarkable transduction unit for the tailor-made development of biosensors for interference-free detection of the neurotransmitter AD via multiple techniques. Integrating a signaling unit 4-methylbenzothiazole-2-amine to 2- formylphenylboronic acid (2-FPBA), yielded a novel fluorosensor, which showed 38- fold fluorescence enhancement selectively with AD without any competition from other bioanalytes, including NA and DA. The attachment of 2-FPBA on the homemade plastic chip electrode surface afforded an impedimetric sensor that detects AD in the picomolar range without any challenge from its competitors. Both optical and electrochemical sensors have been tested for AD measurement in human plasma samples. We are not aware of any report describing the selective discrimination of AD from NA or other biomolecules commonly found in humanbiofluids.

Carrier-Mediated Delivery of Low-Molecular-Weight N-Containing Drugs across the Blood–Brain Barrier or the Blood–Retinal Barrier Using the Proton-Coupled Organic Cation Antiporter

While it is true that pharmacotherapy has achieved desired health outcomes, significant unmet medical needs persist in the field of central nervous system (CNS) drugs, particularly for neurodegenerative diseases such as Alzheimer’s disease, as well as ocular diseases such as diabetic retinopathy and age-related macular degeneration. Drugs cannot enter the brain from the bloodstream due to the presence of the blood–brain barrier (BBB). Similarly, they cannot enter the eyes from the bloodstream due to the blood–retina barrier (BRB), which is composed of the endothelium or the epithelium. Thus, innovative drug delivery systems that can overcome these barriers based on efflux transporters, hydrophobic lipid bilayer membranes, and tight junctions should be developed using patient-friendly techniques distinct from craniotomy procedures or intravitreal injections. Brain-penetrating CNS drugs and antihistamine drugs commonly share N-containing groups. These findings suggest that certain types of cation transporters are involved in their transportation across the cell membrane. Indeed, the proton-coupled organic cation (H+/OC) antiporter, whose specific characteristics remain unidentified, is responsible for transporting compounds with N-containing groups, such as clonidine and pyrilamine, at the BBB, and likely at the BRB as well. Therefore, well-designed low-molecular-weight drugs containing N-containing groups as transporter recognition units can enter the brain or the eyes through carrier-mediated transport. In this perspective review, I introduce the implementation and potential of H+/OC antiporter-mediated transport across the endothelium at the BBB or the BRB using drugs consciously designed with N-containing groups as their substrates.

Facile and highly selective near-infrared emitting fluorescent indicator for hypochlorous acid signaling and bioimaging

A near-infrared emitting fluorescent chemodosimeter for hypochlorous acid (HOCl), PAM, was designed and synthesized by modifying on the sulfonate porphyrin chromophore with a diaminomaleonitrile substituent to form Schiff-base as the chemodosimetric recognition unit. PAM behaved as a sensitive fluorescence “off-on” reactor to HOCl with satisfying anti-interference capacity over other latent disturbing analytes. The drastic fluorescence enhancement originated from the HOCl-promoted intramolecular cyclization to rigidify the molecular structure to a substituted imidazole, which effectively inhibited the CN isomerization. This chemical process is specific, expeditious and will not release extra compounds other than H2O. 1H NMR, FI-IR, HRMS, and spectral analysis confirmed the proposed mechanism. In addition to facilely synthesis, photo- and chemo-stable, PAM has outstanding features of fully water-soluble, low analytic limitation (6.3 nM), and positive linearity, which makes it practical to quantify HOCl in tap water and serum samples. Furthermore, PAM was efficiently leveraged for monitoring both exogenous and endogenous HOCl in living cells, as well as for differentiating between normal and cancer cells based on differences in basal HOCl levels. The versatility of this probe definitely provided a potential discovery tool for further elucidate the HOCl-associated neurological disorders.

Advantages of Electro-deposited Gold on Carbon Electrodes for NT-proBNP Immunosensor for Development of Heart Failure Test Kit

Accurate measurement of the N-terminal pro B-type natriuretic peptide (NT-proBNP) in serum is important for the diagnosis of heart failure (HF). Carbon screen-printed electrodes (SPCEs) modified with graphene oxide (GO) or gold (Au) were compared for the construction of NT-proBNP immunosensors. NT-proBNP and its recognition unit, a single-chain variable fragment fused with alkaline phosphatase (scFv-AP), were expressed and purified. The currents of the electrodes immobilized with scFv-AP were measured after adding an ethanolamine (ETA), blank and NT-proBNP in either phosphate buffer saline (PBS) or human serum. SPCE/Au had lower mean baseline slopes than for SPCE/GO for all measurements, in both PBS and serum, indicating greater accuracy for SPCE/Au. None of the measurements in PBS had statistically different peak currents between SPCE/GO and SPCE/Au; however, there was a significant difference with the serum. The significant reduction of SPCE/GO peak currents after applying serum blank implied non-specific absorption on the surface. The peak current of 300 pg/mL of NT-proBNP in the serum measured on SPCE/Au was significantly higher (by a factor of three) than on SPCE/GO, suggesting the possibility of using SPCE/Au to detect NT-proBNP at higher concentrations. The binding efficiency of scFv-AP to NT-proBNP did not depend on the electrodes, as shown by the similar delta peak-currents (Blank-Target). Thus, immobilized scFv-AP on SPCE/Au electrodes had good potential to accurately detect NT-proBNP in serum, for use in the fabrication of an HF test kit.

Domain-Incremental Continual Learning for Mitigating Bias in Facial Expression and Action Unit Recognition

As Facial Expression Recognition (FER) systems become integrated into our daily lives, these systems need to prioritise making <i>fair</i> decisions instead of only aiming at higher individual accuracy scores. From surveillance systems, to monitoring the mental and emotional health of individuals, these systems need to balance the <i>accuracy versus fairness</i> trade-off to make decisions that do not unjustly discriminate against specific under-represented demographic groups. Identifying <i>bias</i> as a critical problem in facial analysis systems, different methods have been proposed that aim to mitigate bias both at data and algorithmic levels. In this work, we propose the novel use of Continual Learning (CL), in particular, using Domain-Incremental Learning (Domain-IL) settings, as a potent bias mitigation method to enhance the <i>fairness</i> of Facial Expression Recognition (FER) systems. We compare different non-Continual Learning (CL)-based and CL-based methods for their <i>performance</i> and <i>fairness scores</i> on expression recognition and Action Unit (AU) detection tasks using two popular benchmarks, the RAF-DB and BP4D datasets, respectively. Our experimental results show that CL-based methods, on average, outperform other popular bias mitigation techniques on both <i>accuracy</i> and <i>fairness</i> metrics.

Bi2WO6/Ti3C2 MXene Quantum Dots Heterostructure-Based Label-Free Photoelectrochemical Aptamer Sensor for Ultrasensitive Kanamycin Monitoring

As Kanamycin (KAN) is an amino-glycoside antibiotic and has seriously negative effects towards human health, it is urgent to develop an effective way for KAN monitoring. Herein, Bi2WO6/Ti3C2 MXene quantum dots (Bi2WO6/Ti3C2 QDs) heterostructure was synthesized by electrostatically driven assembly and hydrothermal method. On the basis of a Bi2WO6/Ti3C2 QDs heterostructure, a novel aptamer-based anodic photoelectrochemical (PEC) sensing platform was constructed. Through the formation of Au–S bond, the mercapto-group modified aptamers were immobilized as a recognition unit for KAN. Under visible light irradiation, this PEC platform exhibits excellent signal-on photocurrent in the presence of KAN. A log-linear response is observed over a KAN concentration range from 0.01 nM to 50 nM, with a detection limit of 0.005 nM. Moreover, this aptamer-sensor can accurately detect KAN in animal product samples, with recoveries ranging from 94.2% to 101.3%. Overall, this work demonstrates the considerable potential of component reconstitution in PEC biosensors for real sample analysis, providing a new perspective on PEC sensor development.

A mitochondria-targeted phosphorescent probe for sequentially detecting Cu2+ and cysteine and its imaging in living cells and in vivo

This study reported a unique mitochondria-targetable phosphorescent 'on-off-on' probe, Ir-DPA, based on an iridium(III) complex derivative for the sequential and specific detection of Cu2+ and Cys in vitro and in vivo. Probe Ir-DPA was constructed by a lipophilic cation unit as the chromophore as well as the mitochondria biomarker and a dipicolylamine (DPA) group as the recognition unit for Cu2+, followed by removal of Cu2+ specifically in the presence of Cys. The probe itself was strongly emissive at 570 nm. Upon addition of Cu2+, marked quenching occurred as result of the binding of Cu2+ with DPA moiety of this probe, accompanied by a distinct naked-eye luminescence color change from orange yellow to colorless. Additionally, further addition of Cys, the displacement of Cu2+ from in situ generated Ir-DPA-Cu ensemble because of the large nucleophilicity of cysteine toward Cu2+ led to the release of probe, giving rise to the luminescence recovery, as well as a relevant chromogenic change from colorless to orange yellow. Ir-DPA showed a large Stokes shift of 200 nm and high selectivity and sensitivity for the rapid detection of Cu2+ and Cys under physiological conditions, with low detection limits of 0.04 μM and 1.21 μM for Cu2+ and Cys, respectively. More importantly, the probe successfully targeted mitochondria, sensitively detected Cu2+ and exogenously or endogenously generated Cys both in mitochondria of living cells and zebrafish. Finally, Ir-DPA was capable of quantifying Cu2+ level in water samples and the in situ generated ensemble identifying Cys in human serum. These results indicated the great potential of Ir-DPA for monitoring Cu2+ and Cys in environmental, biological systems, and mitochondrial processes.

Complementary Homogeneous Electrochemical and Photothermal Dual-Modal Sensor for Highly Sensitive Detection of Organophosphorus Pesticides via Stimuli-Responsive COF/Methylene Blue@MnO2 Composite.

Credible and on-site detection of organophosphorus pesticides (OPs) in complex matrixes is significant for food security and environmental monitoring. Herein, a novel COF/methylene blue@MnO2 (COF/MB@MnO2) composite featured abundant signal loading, a specific recognition unit, and robust oxidase-like activity was successfully prepared through facile assembly processes. The multifunctional composite acted as a homogeneous electrochemical and photothermal dual-mode sensing platform for OPs detection through stimuli-responsive regulation. Without the presence of OPs, the surface MnO2 coating could recognize thiocholine (TCh), originating from acetylcholinesterase (AChE)-catalyzed hydrolysis of acetylthiocholine (ATCh), and exhibited a distinctly amplified diffusion current due to the release of plentiful MB; while the residual MnO2 nanosheets could only catalyze less TMB into oxidized TMB (oxTMB) with a typical near-infrared (NIR) absorption, enabling NIR-driven photothermal assay with a low temperature using a portable thermometer. Based on the inhibitory effect of OPs on AChE activity and OP-regulated generation of TCh, chlorpyrifos as a model target can be accurately detected with a low limit of detection of 0.0632 and 0.108 ng/mL by complementary electrochemical and photothermal measurements, respectively. The present dual-mode sensor was demonstrated to be excellent for application to the reliable detection of OPs in complex environmental and food samples. This work can not only provide a complementary dual-mode method for convenient and on-site detection of OPs in different scenarios but also expand the application scope of the COF-based multifunctional composite in multimodal sensors.

A single recognition unit-based virtual sensor Array: Applying 3D fluorescence spectroscopy to inner filter effect-based sensing

A convenient, fast, low-cost detection and discrimination method is demanded for environmental monitoring but still it remains more technological challenges. Herein, we demonstrate that the inner filter effect (IFE), in combination with three-dimensional fluorescence spectroscopy, can offer a virtual sensor array (VSA) as apropersolution. And with the aid of pattern recognition techniques, it is feasible to recognize compounds with structural similarities economically and effectively. In this study, with the help of visual clustering plots of principal component analysis (PCA), a prediction model based on hierarchical strategy was made using support vector machine (SVM) method for the qualitative profiling of aromatic pollutants. The VSA was constructed by a single metal–organic framework (MOF) recognition unit (MOF-74 (Zn)) with the excitation wavelength as external regulatory factors. Pattern characteristics of four aromatics with very similar structures (phenylamine, chlorobenzene, nitrobenzene, and phenol), both single analyte and binary mixtures, were acquired. The primary constituents of multi-dimensional spectral signals were subsequently extracted and fed into a vector machine to construct a prediction model through 10-fold cross-validation optimization, resulting in a classification accuracy of 100% for single analytes and 96% for mixtures. Quantitative research has shown that, except for chlorobenzene, all three other analytes can be predicted in concentration within an acceptable error range, and the mixture can be predicted proportionally. Moreover, the VSA can be used to distinguish these pollutants in tap and river water also. We propose for the first time a new tack for the construction of VSA in a general manner, namely using three-dimensional full range fluorescence scanning for IFE based sensing to get multiple times of information resulting from different weak interaction between analyte and sensor for decision-making.

Dual-signal fluorescence aptasensing system for adenosine triphosphate assisting by MoS2 nanosheets

Adenosine triphosphate (ATP) has an irreplaceable role in the maintenance of many physiological processes and biological functions, and can be employed as an indicator of many diseases. In this work, we constructed a simple and sensitive dual-signal fluorescence aptasensing system for ATP detection with berberine as the signal reporter, ATP-aptamer as the recognition unit and MoS2 nanosheets as the signal amplification. In the absence of ATP, berberine can bind to the single-stranded DNA (ssDNA) of ATP-aptamer and selectively assemble on the surface of MoS2 nanosheets, leading to the fluorescence quenching of bererbine based on the fluorescence resonance energy transfer, denoted by “OFF”. Accordingly, the fluorescence anisotropy signal is enhanced due to restriction on rotate of the fluorescent probe and denoted as “ON”. Conversely, in the presence of ATP, it specifically interacts with ATP-aptamer and switches the free-curled single-stranded of ATP-aptamer to the G-quadruplex structure of ATP-aptamer/ATP/berberine, causing the detachment from the surface of the MoS2 nanosheet. Accordingly, the fluorescence signal was reversed from “OFF” to “ON”, and the fluorescence anisotropy signal was turned “ON” to “OFF”. The developed aptasensing system achieved a desirable sensitivity of 40.0 nM with fluorescent mode, and of 20.8 nM with fluorescent anisotropic mode. The sensing system has demonstrated high quality detection performance in human serum sample, and obtained the satisfactory recovery results for fluorescent of 93.0–108.5%, fluorescent anisotropic of 96.4–106.7%.

High-Performance Cannabinoid Sensor Empowered by Plant Hormone Receptors and Antifouling Magnetic Nanorods.

The misuse of cannabinoids and their synthetic variants poses significant threats to public health, necessitating the development of advanced techniques for detection of these compounds in biological or environmental samples. Existing methods face challenges like lengthy sample pretreatment and laborious antifouling steps. Herein, we present a novel sensing platform using magnetic nanorods coated with zwitterionic polymers for the simple, rapid, and sensitive detection of cannabinoids in biofluids. Our technique utilizes the engineered derivatives of the plant hormone receptor Pyrabactin Resistance 1 (PYR1) as drug recognition elements and employs the chemical-induced dimerization (CID) mechanism for signal development. Additionally, the magnetic nanorods facilitate efficient target capture and reduce the assay duration. Moreover, the zwitterionic polymer coating exhibits excellent antifouling capability, preserving excellent sensor performance in complex biofluids. Our sensors detect cannabinoids in undiluted biofluids like serum, saliva, and urine with a low limit of detection (0.002 pM in saliva and few pM in urine and serum) and dynamic ranges spanning up to 9 orders of magnitude. Moreover, the PYR1 derivatives demonstrate high specificity even in the presence of multiple interfering compounds. This work opens new opportunities for sensor development, showcasing the excellent performance of antifouling magnetic nanorods that can be compatible with different recognition units, including receptors and antibodies, for detecting a variety of targets.

Electrochemical properties of hydroxyapatite immobilization material for potential cytosensor fabrication

Aim: The biorecognition unit of an electrochemical biosensor requires molecules that are immobilised to serve as a bridge between the recognition unit and the transducing surface. Unique materials that enhance immobilisation of biorecognition molecules and improve electrochemical signal transduction are important in overcoming challenges based on the sensitivity of biosensors. In this regard, the electrochemical properties (EPs) of hydroxyapatite (HAp) material for the direct immobilisation of cells was investigated. Methods: Snail shell HAp (SHAp) material was synthesised from Achatina achatina snail shells and phosphate-containing solutions. The SHAp material was characterised using X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy to determine the structural configuration, after which it was blended with a conductive polymer [poly(3,4-ethylenedioxythiophene): poly-4-styrene sulfonate (PEDOT: PSS)] to improve the electrochemical responses. The SHAp/PEDOT: PSS blend was used to modify a screen-printed carbon electrode (SPCE) by drop-casting, followed by seeding of pheochromocytoma (PC 12) and human embryonic kidney (HEK)-293T cells on the modified SPCE to record the EP using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Red blood cells (RBCs) were used as a control. Results: The CV analysis showed lower peak currents for HEK 293T (50 µA) and PC 12 (120 µA) compared to the RBC (230 µA). Also, the EIS showed impedance values of 0.70 for HEK 293T, 0.62 for PC 12, and 0.52 mΩ for RBC. The findings indicate that SHAp/PEDOT: PSS enables the differentiation of cell proliferation signals through voltammetric and impedimetric measurements. Conclusions: The unique current and impedance differences among the cells could serve as potential markers for rapid cell detection.

Single-Walled Carbon Nanotube Sensor Selection for the Detection of MicroRNA Biomarkers for Acute Myocardial Infarction as a Case Study.

MicroRNAs (miRNAs) are single-stranded non-coding short ribonucleic acid sequences that take part in many cellular and biological processes. Recent studies have shown that altered expression of miRNAs is involved in pathological processes, and they can thus be considered biomarkers for the early detection of various diseases. Here, we demonstrate a selection and elimination process of fluorescent single-walled carbon nanotube (SWCNT) sensors for miRNA biomarkers based on RNA-DNA hybridization with a complementary DNA recognition unit bound to the SWCNT surface. We use known miRNA biomarkers for acute myocardial infarction (AMI), commonly known as a heart attack, as a case study. We have selected five possible miRNA biomarkers which are selective and specific to AMI and tested DNA-SWCNT sensor candidates with the target DNA and RNA sequences in different environments. Out of these five miRNA sensors, three could recognize the complementary DNA or RNA sequence in a buffer, showing fluorescence modulation of the SWCNT in response to the target sequence. Out of the three working sensors in buffer, only one could function in serum and was selected for further testing. The chosen sensor, SWCNT-miDNA208a, showed high specificity and selectivity toward the target sequence, with better performance in serum compared to a buffer environment. The SWCNT sensor selection pipeline highlights the importance of testing sensor candidates in the appropriate environment and can be extended to other libraries of biomarkers.

Synthesis, characterization and sensing mechanism of a novel fluorescence probe for Fe(III) in semi-aqueous solution based on a Schiff base hexadentate receptor

A new acyclic Schiff base chemosensor L was synthesized by the one pot condensation reaction of 2-[3-(formyl phenoxy)2-hydroxypropoxy]benzaldehyde and 2-aminophenol in a 1:2 molar ratio and was characterized by elemental analysis, FTIR, 1H- and 13C NMR, and fluorescence spectroscopies. These studies were complemented with a thorough conformational study at the molecular mechanics and density functional theory (DFT) levels of theory to further elucidate the structure of the compound in solution. The chemosensor L displays high sensitivity and selectivity for Fe3+ in semi-aqueous (H2O-DMF, 1:1) solution, except in the presence of a significant amount of Ni2+, with the presence of Fe3+ being signaled through the total fluorescence quenching of the fluorophore when Fe3+ binds to the recognition unit. The synthesized ligand also shows high selectivity for Fe3+ compared to the metal ions Cu2+, Zn2+, Mg2+, Mn2+, Pb2+, Hg2+, Na+, Ba2+ and Cd2+, and reasonable selectivity in the presence of Ag+, Co2+ and Cr3+. The stoichiometry and structure of the complex formed between Fe3+ and the probe L were determined from a Job’s plot and DFT calculations, respectively. The complex was characterized as a high-spin 1:1 octahedral species, in which the ligand coordinates to the metal through the two ether oxygen atoms, two nitrogen atoms and two terminal hydroxyl groups. Time dependent (TD-DFT) calculations were performed to provide information on the type of mechanism causing the quenching of the fluorescence in the presence of Fe3+.

A Readily Available Red‐Emitting Methylthio‐Substituted Salicylaldehyde Azine with AIE Feature for Ratiometric Detection of HClO

AbstractDeveloping a simple, selective, and rapid reliable method to monitor hypochlorous acid (HClO) in vivo is very meaningful due to its important physiological and pathological functions. In this research, a novel AIE based fluorescent probe for ratiometric detection of HClO was fabricated by a simple one‐step synthesis, in which the methyl sulfide group and salicylaldehyde azine serve as the recognition unit and fluorophore, respectively. This probe was visible‐light‐excitable, and showed a palpable aggregation‐induced emission into the red region with high stability to Cu2+ and pH. Oxidation of the methyl sulfide group can be achieved rapidly and specifically by HClO in physiological condition, which enables it to display a rapid, ratiometric fluorescent response to HClO with high selectivity over other biologically pertinent species. By exploiting the probe‐based tool, we successfully validated its practical utility in selectively recognizing HClO in living cells via ratiometric fluorescence signals, thereby providing a potential method for investigating the relevant functions of HClO in biosystems.

Supramolecular Motifs in the Crystal Structures of Triethylbenzene Derivatives Bearing Pyridinium Subunits in Combination with Pyrimidinyl or Pyridinyl Groups.

A series of mono- and dicationic 1,3,5-trisubstituted 2,4,6-triethylbenzenes containing pyridinium groups in combination with aminopyrimidine-/aminopyridine-based recognition units were synthesized and crystallographically studied. The combination of neutral and ionic building blocks represents a promising strategy for the development of effective and selective artificial receptors for anionic substrates. In the crystalline state, the investigated compounds show a tendency to bind the counterion PF6- in the cavity formed by the three functionalized side-arms. The intermolecular interactions with the PF6- ion comprise N-H∙∙∙F and C-H∙∙∙F bonds. Detailed analysis of various supramolecular motifs, including interactions with solvent molecules, provides deeper insights into the processes of molecular recognition. The information obtained is useful in the development of new receptor molecules for anions and in the selection of the most appropriate counterion.

Macroporous Polymer Cantilever Resonators for Chemical Sensing Applications

AbstractA novel, cost‐effective strategy for sensing performance enhancement of cantilever‐shaped, mass‐sensitive sensors is presented. The developed strategy relies on the introduction of macroporosity in the recognition unit. The developed sensors are successfully applied in air humidity monitoring as well as in chemical sensing. As mass‐sensitive transducers, polymer microelectromechanical systems (MEMS) in the form of poly(vinylidene fluoride‐trifluoroethylene) [P(VDF‐TrFE)] cantilever resonators are specifically developed. These resonators are modified with a hierarchically structured macroporous poly(2,3′‐bithiophene) film, acting as a sensing layer. The design of the recognition layer takes advantage of the synergistic combination of inverse opal structuring, surface imprinting, and semi‐covalent imprinting of proteins. The resulting cantilever resonators are first successfully tested for air humidity monitoring in the whole relative humidity range (ca.10 – 90%). When the recognition layer is composed of human serum albumin‐imprinted polymer (HSA‐MIP) with a hierarchical structure, it can also be used as a selective chemosensor in a concentration range from 10 pM to 20 µM. The obtained results demonstrate that the macroporosity of the receptor film significantly enhances the sensor performance.