Machine-Learning-Driven G-Quartet-Based Circularly Polarized Luminescence Materials.

Circularly polarized luminescence (CPL) materials have garnered significant interest due to their potential applications in chiral functional devices. Synthesizing CPL materials with a high dissymmetry factor (glum ) remains a significant challenge. Inspired by efficient machine learning (ML) applications in scientific research, this work demonstrates ML-based techniques for the first time to guide the synthesis of G-quartet-based CPL gels with high glum values and multiple chiral regulation strategies. Employing an "experiment-prediction-verification" approach, this work devises a ML classification and regression model for the solvothermal synthesis of G-quartet gels in deep eutectic solvents. This process illustrates the relationship between various synthesis parameters and the glum value. The decision tree algorithm demonstrates superior performance across six ML models, with model accuracy and determination coefficients amounting to 0.97 and 0.96, respectively. The screened CPL gels exhibiting a glum value up to 0.15 are obtained through combined ML guidance and experimental verification, among the highest ones reported till now for biomolecule-based CPL systems. These findings indicate that ML can streamline the rational design of chiral nanomaterials, thereby expediting their further development.

Truncated Electrochemical Aptasensor with Enhanced Antifouling Capability for Highly Sensitive Serotonin Detection.

Accurate determination of serotonin (ST) provides insight into neurological processes and enables applications in clinical diagnostics of brain diseases. Herein, we present an electrochemical aptasensor based on truncated DNA aptamers and a polyethylene glycol (PEG) molecule-functionalized sensing interface for highly sensitive and selective ST detection. The truncated aptamers have a small size and adopt a stable stem-loop configuration, which improves the accessibility of the aptamer for the analyte and enhances the sensitivity of the aptasensor. Upon target binding, these aptamers perform a conformational change, leading to a variation in the Faraday current of the redox tag, which was recorded by square wave voltammetry (SWV). Using PEG as blocking molecules minimizes nonspecific adsorption of other interfering molecules and thus endows an enhanced antifouling ability. The proposed electrochemical aptamer sensor showed a wide range of detection lasting from 0.1 nM to 1000 nM with a low limit of detection of 0.14 nM. Owing to the unique properties of aptamer receptors, the aptasensor also exhibits high selectivity and stability. Furthermore, with the reduced unspecific adsorption, assaying of ST in human serum and artificial cerebrospinal fluid (aCSF) showed excellent performance. The reported strategy of utilizing antifouling PEG describes a novel approach to building antifouling aptasensors and holds great potential for neurochemical investigations and clinical diagnosis.

Porphyrin Functionalized Carbon Quantum Dots for Enhanced Electrochemiluminescence and Sensitive Detection of Cu2.

Porphyrin (TMPyP) functionalized carbon quantum dots (CQDs-TMPyP), a novel and efficient carbon nanocomposite material, were developed as a novel luminescent material, which could be very useful for the sensitive detection of copper ions in the Cu2+ quenching luminescence of functionalized carbon quantum dots. Therefore, we constructed a sensitive "signal off" ECL biosensor for the detection of Cu2+. This sensor can sensitively respond to copper ions in the range of 10 nM to 10 µM, and the detection limit is 2.78 nM. At the same time, it has good selectivity and stability and a benign response in complex systems. With excellent properties, this proposed ECL biosensor provides an efficient and ultrasensitive method for Cu2+ detection.

Chiral Carbon Dots: Synthesis and Applications in Circularly Polarized Luminescence, Biosensing and Biology.

Chiral carbon dots (CDs) are a novel luminescent zero-dimensional carbon-based nanomaterial with chirality. They not only have the advantages of good biocompatibility, multi-color-emission, easy functionalization, but also exhibits highly symmetrical chiral optical characteristics, which broadens their applicability to enantioselectivity of some chiral amino acids like cysteine and lysine, asymmetric catalysis as well as biomedicine in gene expression and antibiosis. In addition, the exploration of the excited state chirality of CDs has developed its excellent circularly polarized luminescence (CPL) properties, opening up a new application scenario like recognition of chiral light sources and anti-counterfeit printing with information encryption. This review mainly focuses on the mature synthesis approaches of chiral CDs, including chiral ligand method and supramolecular self-assembly method, then we consider emerging applications of chiral CDs in CPL, biosensing and biological effect. Finally, we concluded with a perspective on the potential challenges and future opportunities of such fascinating chiral CDs.

New Horizons for MXenes in Biosensing Applications.

Over the last few decades, biosensors have made significant advances in detecting non-invasive biomarkers of disease-related body fluid substances with high sensitivity, high accuracy, low cost and ease in operation. Among various two-dimensional (2D) materials, MXenes have attracted widespread interest due to their unique surface properties, as well as mechanical, optical, electrical and biocompatible properties, and have been applied in various fields, particularly in the preparation of biosensors, which play a critical role. Here, we systematically introduce the application of MXenes in electrochemical, optical and other bioanalytical methods in recent years. Finally, we summarise and discuss problems in the field of biosensing and possible future directions of MXenes. We hope to provide an outlook on MXenes applications in biosensing and to stimulate broader interests and research in MXenes across different disciplines.

Biomolecule-Based Circularly Polarized Luminescent Materials: Construction, Progress, and Applications.

Chiral materials related to circularly polarized luminescence (CPL) make up a rapidly developing new field that has broad application prospects in optoelectronic devices, selective recognition, biomedicine, and other fields. Biofunctional chiral materials are also attracting increasing attention because of their unique biocompatibility, chiral recognition, and coding. However, there has been little discussion on biomolecule-based CPL till now. In this Review, the latest progress in CPL materials related with biomolecules are reviewed, including the chiral construction from molecular level to giant microstructure, as well as their emerging applications. In addition, we discuss the challenges and prospects of bio-based CPL materials, hoping this work will provide new perspectives and insights for more related research.

Circularly Polarized Luminescence of Achiral Carbon Dots in Bi-Solvent Systems Triggered by Supramolecular Self-Assembly.

An innovative strategy for circularly polarized luminescence (CPL) of carbon dots (CDs) has been developed: The achiral CDs displayed contrary supramolecular chirality and opposite CPL in two different bi-solvent systems, which are due to the formation of self-assembled helical nanostructures with two diverse assembly modes (P and M) in aggregate state via intermolecular π-π interactions and differential hydrogen bonding (H-bonding) without the need of any additional element of chirality.

Near-infrared phosphorescent carbon dots for sonodynamic precision tumor therapy.

Theranostic sonosensitizers with combined sonodynamic and near infrared (NIR) imaging modes are required for imaging guided sonodynamic therapy (SDT). It is challenging, however, to realize a single material that is simultaneously endowed with both NIR emitting and sonodynamic activities. Herein, we report the design of a class of NIR-emitting sonosensitizers from a NIR phosphorescent carbon dot (CD) material with a narrow bandgap (1.62 eV) and long-lived excited triplet states (11.4 µs), two of which can enhance SDT as thermodynamically and dynamically favorable factors under low-intensity ultrasound irradiation, respectively. The NIR-phosphorescent CDs are identified as bipolar quantum dots containing both p- and n-type surface functionalization regions that can drive spatial separation of e--h+ pairs and fast transfer to reaction sites. Importantly, the cancer-specific targeting and high-level intratumor enrichment of the theranostic CDs are achieved by cancer cell membrane encapsulation for precision SDT with complete eradication of solid tumors by single injection and single irradiation. These results will open up a promising approach to engineer phosphorescent materials with long-lived triplet excited states for sonodynamic precision tumor therapy.

2H-MoS2/Co3O4 nanohybrid with type I nitroreductase-mimicking activity for the electrochemical assays of nitroaromatic compounds.

A type I nitroreductase-mimicking nanocatalyst based on 2H-MoS2/Co3O4 nanohybrids for trace nitroaromatic compounds detection is reported in this work. For the preparation of nanocatalyst, ultrathin Co3O4 nanoflakes array was in-situ grown onto 2H-MoS2 nanosheets forming three-dimensional (3D) nanohybrid with large specific surface area as well as abundant active sites. The as-prepared nanocatalyst shows a specific affinity as well as high catalytic activity towards nitroaromatic compounds. Given the favorable nitroreductase-mimicking catalytic activity of 2H-MoS2/Co3O4 nanohybrid, a sensitive and efficient electrochemical microsensor has been constructed for the detection of 2, 4, 6-trinitrotoluene (TNT). Under optimized conditions, the microsensor displayed sensitive response from µM to pM levels with a limit of detection (LOD) of 1 pM. We further employed photoelectron spectroscopy (XPS) analysis and high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) method to identify the nitroreductase-mimicking mechanism of 2H-MoS2/Co3O4 nanohybrids towards 2, 4, 6- TNT. It was found that the abundant oxygen vacancies in ultrathin Co3O4 nanoflakes played an essential role in determining its catalytic performance. Moreover, the developed MoS2/Co3O4 nanozyme has a lower Michaelis-Menten constant (km) than that of nature nitroreductase demonstrating a good enzymatic affinity towards its substrates, and further generating a high catalytic activity. This research not only proposed a new type of nanozyme, but also developed a portable electrochemical microsensor for the detection of 2, 4, 6-TNT.

Design and Application of Metal Organic Framework ZIF-90-ZnO-MoS2 Nanohybrid for an Integrated Electrochemical Liquid Biopsy.

Limited healthcare capacity highlights the needs of integrated sensing systems for personalized health-monitoring. However, only limited sensors can be employed for point-of-care applications, emphasizing the lack of a generalizable sensing platform. Here, we report a metal organic framework (MOF) ZIF-90-ZnO-MoS2 nanohybrid-based integrated electrochemical liquid biopsy (ELB) platform capable of direct profiling cancer exosomes from blood. Using a bottom-up approach for sensor design, a series of critical sensing functions is considered and encoded into the MOF material interface by programming the material with different chemical and structural features. The MOF-based ELB platform is able to achieve one-step sensor fabrication, target isolation, nonfouling and high-sensitivity sensing, direct signal transduction, and multiplexed detection. We demonstrated the capability of the designed sensing system on differentiating cancerous groups from healthy controls by analyzing clinical samples from lung cancer patients, providing a generalizable sensing platform.

Correction: Efficient and stable electrorheological fluids based on chestnut-like cobalt hydroxide coupled with surface-functionalized carbon dots.

Correction for 'Efficient and stable electrorheological fluids based on chestnut-like cobalt hydroxide coupled with surface-functionalized carbon dots' by Yudai Liang et al., Soft Matter, 2022, DOI: 10.1039/D2SM00176D.

Cytidine-rich hydrogel as an electrochemical signal amplification strategy for microRNA detection.

Signal amplification strategies increase the complexities of biosensors while improving the response signals. Herein, a novel electrochemical biosensor was developed based on a DNA hydrogel for sensitive analysis using microRNA-21 (miRNA-21) as a detection model. Poly C sequences combined with C-Ag(I)-C hydrogel formed a DNA hydrogel by the unique interaction between the cytosines and silver ions. Thus, with a three-way conjunction structure of DNA, this C-Ag(I)-C hydrogel was constructed as a novel biosensor for the detection of miRNAs. With the assistance of this hydrogel, numerous silver ions gathered around DNA strands, which would amplify the signal. Under these conditions, the silver ions produced distinct square wave voltammetry oxidation peak currents. This electrochemical biosensor we designed exhibited a great linear relationship for the logarithm of the concentration of miRNA-21 from 1 fM to 100 pM with a detection limit of 0.117 fM. Furthermore, our sensors were able to differentiate miRNA-21 from its homologous family with satisfactory responsiveness in the dilute bovine serum system.

A molecular crowding thermo-switchable chiral G-quartet hydrogel with circularly polarized luminescence property.

A novel helix hydrogel with a G-quartet structure was synthesized from guanosine (Gua) and its derivative 5'-guanosine monophosphate (5'-GMP) under a molecular crowding environment. The chirality of the hydrogel is adjusted by controlling the gelling speed. The chiral hydrogel can induce an achiral dye Thioflavin T (ThT) to realize circularly polarized fluorescence (CPL). The CPL dissymmetry factor |glum| of the dye-hydrogels can reach 3 × 10-2 and can be switched easily.

Efficient and stable electrorheological fluids based on chestnut-like cobalt hydroxide coupled with surface-functionalized carbon dots.

Intrinsically polarized electrorheological fluids (ERFs) have better thermal stability than ERFs with polar molecules, so they have a broader application prospect. However, the electrorheological efficiency of the common intrinsically polarized ERF is still lower than 1500, which is related to the poor wettability between polarized materials and the continuous phase. Carbon dots (CDs) exhibit good stability, semiconductor properties and low toxicity. We prepared biomimetic chestnut-like cobalt hydroxide coupled with surface-functionalized CD particles (Co(OH)2@CDs) by a simple hydrothermal method. Then we prepared an ERF by mixing Co(OH)2@CDs with silicone oil and studied the effect of CDs on its rheology and electrorheology properties. The synergistic effect of the lipophilic groups on the surface of CDs and the biomimetic chestnut-like structure makes Co(OH)2@CDs exhibit good wettability with silicone oil, and the optimal zero-field viscosity of Co(OH)2@CDs-ERF is only 0.46 Pa s (particle mass fraction of 40%). Exceptional electrorheological efficiency (about 10 000, shear rate 0.1 s-1, 5 kV mm-1) and dynamic shear stress stability of optimal Co(OH)2@CDs-ERF can be attributed to the dielectric enhancement of the biomimetic chestnut-like structure coupled with the semiconductor properties of CDs. In addition, Co(OH)2@CDs-ERF has excellent anti-settling performance, outstanding thermal stability and low current density.

1T-Phase molybdenum sulfide/cobalt oxide nanopillars hybrid nanostructure coupled with nitrogen-doped carbon thin-film as high efficiency electrocatalyst for oxygen evolution.

High efficient and durable catalysts are always needed to lower the kinetic barriers as well as prolong the service life associated with oxygen evolution reaction (OER). Herein, a sequential synthetic strategy is considered to prepare a hierarchical nanostructure, in which each component can be configured to achieve their full potential so that endows the resulting nanocatalyst a good overall performance. In order to realize this, well-organized cobalt oxide (Co3O4) nanopillars are firstly grown onto ultrathin 1T-molybdenum sulfide (1T-MoS2) to obtain high surface area electrocatalyst, providing electron transfer pathways and structural stability. After that, zeolitic imidazolate framework-67 (ZIF-67) derived carbonization film is further in situ deposited on the surface of nanopillars to generate plentiful active sites, thereby accelerating OER kinetics. Based on the combination of different components, the electron transfer capability, catalytic activity and durability are optimized and fully implemented. The obtained nanocatalyst (defined as 1T-MoS2/Co3O4/CN) exhibits the superior OER catalytic ability with the overpotential of 202 mV and Tafel slope of 57 mV·dec-1 at 10 mA·cm-2 in 0.1 M KOH, and good durability with a minor chronoamperometric decay of 9.15 % after 60,000 s of polarization.

Study Design and Baseline Profiles of Participants in the Tianjin Birth Cohort (TJBC) in China.

BACKGROUND: To investigate the causal link between early-life exposures and long-term health consequences, we established the Tianjin Birth Cohort (TJBC), a large-scale prospective cohort in northern China. METHODS: TJBC aims to enroll 10,000 families with follow-ups from pregnancy until children's six year-old. Pregnant women and their spouses were recruited through a three-tier antenatal healthcare system at early pregnancy, with follow-ups at mid-pregnancy, late pregnancy, delivery, 42 days after delivery, 6 months after delivery, and each year until 6 years old. Antenatal/neonatal examination, biological samples and questionnaires were collected. RESULTS: From August 2017 to January 2019, a total of 3,924 pregnant women have already been enrolled, and 1,697 women have given birth. We observed the prevalence of gestational diabetes mellitus as 18.1%, anemia as 20.4%, and thyroid hypofunction as 2.0%. In singleton live births, 5.6% were preterm birth (PTB), 3.7% were low birth weight, and 7.3% were macrosomia. Based on current data, we also identified maternal/paternal factors which increased the risk of PTB, including paternal age (OR 1.07; 95% CI, 1.01-1.14 for each year increase), vaginal bleeding during pregnancy (OR 2.82; 95% CI, 1.54-5.17) and maternal early-pregnancy BMI (OR 1.08; 95% CI, 1.01-1.15 for each kg/m2 increase). CONCLUSION: TJBC has the strength of collecting comprehensive maternal, paternal, and childhood information. With a diverse range of biological samples, we are also engaging with emerging new technologies for multi-omics research. The study would provide new insight into the causal link between macro/micro-environmental exposures of early life and short/long-term health consequences.

HIV-1 Vpr protein upregulates microRNA-210-5p expression to induce G2 arrest by targeting TGIF2.

MicroRNAs (miRNAs) are important molecules that mediate virus-host interactions, mainly by regulating gene expression via gene silencing. Here, we demonstrated that HIV-1 infection upregulated miR-210-5p in HIV-1-inoculated cell lines and in the serum of HIV-1-infected individuals. Luciferase reporter assays and western blotting confirmed that a target protein of miR-210-5p, TGIF2, is regulated by HIV-1 infection. Furthermore, HIV-1 Vpr protein induced miR-210-5p expression. The use of a miR-210-5p inhibitor and TGIF2 overexpression showed that Vpr upregulated miR-210-5p and thereby downregulated TGIF2, which might be one of the mechanisms used by Vpr to induce G2 arrest. Moreover, we identified a transcription factor, NF-κB p50, which upregulated miR-210-5p in response to Vpr protein. In conclusion, we identified a mechanism whereby miR-210-5p, which is induced upon HIV-1 infection, targets TGIF2. This pathway was initiated by Vpr protein activating NF-κB p50, which promoted G2 arrest. These alterations orchestrated by miRNA provide new evidence on how HIV-1 interacts with its host during infection and increase our understanding of the mechanism by which Vpr regulates the cell cycle.

Hyperphosphorylation of Tau Due to the Interference of Protein Phosphatase Methylesterase-1 Overexpression by MiR-125b-5p in Melatonin Receptor Knockout Mice.

Melatonin has been indicated to ameliorate tau hyperphosphorylation in the pathogenesis of tau diseases, but the role of melatonin-receptor signal transduction has not been clearly discovered. In this study, we found intensive tau hyperphosphorylation in melatonin receptor knockout mice. Bielschowsky silver staining showed ghostlike neurofibrillary tangles in melatonin receptor-2 knockout (MT2KO) as well as melatonin receptors-1 and -2 knockout (DKO) mice, and an argyrophilic substance was deposited in melatonin receptor-1 knockout (MT1KO) mice. Furthermore, we found significantly decreased activity of protein phosphatase 2A (PP2A) by Western blot and enzyme-linked immunosorbent assay (ELISA), which was partly due to the overexpression of protein phosphatase methylesterase-1 (PME-1), but not glycogen synthase kinase-3ß (GSK-3ß), cyclin-dependent kinase 5 (CDK5) or protein kinase B (Akt). Finally, we observed a significant increase in cyclic adenosine monophosphate (cAMP) and a decrease in miR-125b-5p levels in MT1KO, MT2KO and DKO mice. Using a luciferase reporter assay, we discovered that miR-125b-5p largely decreased the expression of firefly luciferase by interfering with the 3'UTR of PME-1. Furthermore, miR-125b-5p mimics significantly decreased the expression of PME-1, while miR-125b-5p inhibitor induced tau hyperphosphorylation. These results show that melatonin-receptor signal transduction plays an important role in tau hyperphosphorylation and tangle formation.

Kinetic control of chirality and circularly polarized luminescence in G-quartet materials.

The formation of chirality of G-quartet materials has been of concern for a long time, however, the helix-handedness of G-quartet materials is still ambiguous, as well as the novel circularly polarized luminescence (CPL) properties. Here, we demonstrated that the handedness of G-quartet materials highly depends on their formation kinetics. By controlling the temperature or the initial concentration of reactants, we found that right-handed helical G-quartet nanostructures were synthesized in the slow process, while left-handed structures were synthesized in the fast process via orderly stacking. The phenomenon can be explained by the theory of kinetic trapping, in which a slow process leads to the thermodynamic equilibrium, while a fast process results in the kinetic trap state. Furthermore, the first kinetic trapping-controlled reversal CPL system was designed in G-quartet materials via chirality transfer, which has potential applications in CPL materials design and application.

Signal-on electrochemical aptasensors with different target-induced conformations for prostate specific antigen detection.

Prostate specific antigen (PSA) has become a potential biomarker for detecting prostate cancer (PCa) in the early stage. Herein, we report a target-induced resolution for the detection of PSA sensitively and specifically by amperometric electrochemical measurements. To meet a satisfactory performance, three conformations of pre-design DNA aptamers including two stem-loop structures and a double strand structure have been investigated and compared. All of them are immobilized on gold electrode as capture probes with redox-active molecular. The mechanism of signal transduction depends on molecular recognition events involving aptamer conformational changes, thus influencing the charge transfer. A short, single-stranded DNA (ssDNA) pseudoknot forming two stem-loop structural aptamers with labeled MB at the 3' -terminus was found to posse the highest signal variation than other structure when induced by PSA due to the strong conformational change. With the optimized capture strand, the aptasensor showed the peak current increase of MB by the binding relationship between PSA and the sensor over a wide concentration range of 4 magnitude orders. The proposed aptasensor exhibited a wide detection range from 10 pg/mL to 500 ng/mL with a low detection limit of 1.24 pg/mL (S/N = 3). Moreover, the electrochemical aptasensor demonstrated good reproducibility, sensitivity, selectivity, and reliability for the detection of PSA. We also found the aptasensor had a good response in the human serum samples, making this device easy to operate for the detection of the PSA physiological concentration.