Rb-Doped Perovskite Oxides: Surface Enrichment and Structural Reconstruction During the Oxygen Evolution Reaction.

Alkali-metal doped perovskite oxides have emerged as promising materials due to their unique properties and broad applications in various fields, including photovoltaics and catalysis. Understanding the complex interplay between alkali metal doping, structural modifications, and their impact on performance remains a crucial challenge. In this study, this challenge is addressed by investigating the synthesis and properties of Rb-doped perovskite oxides. These results reveal that the doping of Rb into perovskite oxides function as a structural modifier in the as-synthesized samples and during the oxygen evolution reaction (OER) as well. Electron microscopy and first-principles calculations confirm the enrichment of Rb on the surface of the as-synthesized sample. Further investigations into the electrocatalytic reaction revealed that the Rb-doped perovskite underwent drastic restructuring with Rb leaching and formation of strontium oxide.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Phase-Regulated Sensing Mechanism of MoS2 Based Nanohybrids toward Point-of-Care Prostate Cancer Diagnosis.

Alpha-methylacyl-CoA racemase (AMACR) has been proven to be consistently overexpressed in prostate cancer epitheliums, and is expected to act as a positive biomarker for the diagnosis of prostate carcinoma in clinical practice. Here, a strategy for specific determination of AMACR in real human serum by using an electrochemical microsensor system is presented. In order to implement the protocol, a self-organized nanohybrid consisting of metal nanopillars in a 2D MoS2 matrix is developed as material for the sensing interface. The testing signal outputs are strongly enhanced with the presence of the nanohybrids owing to that the metal pillars provide an efficient mass difussion and electron transfer path to the MoS2 film surface. Furthermore, the phase-regulated sensing mechanism over MoS2 is noticed and demonstrated by density functional theory calculation and experiments. The explored MoS2 based nanohybrids are employed for the fabrication of an electrochemical microsensor, presenting good linear relationship in both ng µL-1 and pg µL-1 ranges for AMACR quantification. The sampling analysis of human serum indicates that this microsensor has good diagnostic specificity and sensitivity toward AMACR. The proposed electrochemical microsensor system also demonstrates the advantages of convenience, cost-effectiveness, and disposability, resulting in a potential integrated microsystem for point-of-care prostate cancer diagnosis.

Sensitive and reversible perylene derivative-based fluorescent probe for acetylcholinesterase activity monitoring and its inhibitor.

A reversible fluorescence probe for acetylcholinesterase activity detection was developed based on water soluble perylene derivative, N,N'-di(2-aspartic acid)-perylene-3,4,9,10-tetracarboxylic diimide (PASP). Based on the photo-induced electron transfer (PET), PASP fluorescence in aqueous is quenched after combining with copper ions (Cu2+). Acetylcholinesterase (AChE) is well known to catalyze the hydrolysis of acetylcholine (ATCh) to produce thiocholine, whose affinity is strong enough to capture Cu2+ by thiol (-SH) group from the complex PASP-Cu, resulting in the fluorescence signal of PASP recovers up to 90%. This optical switch is highly sensitive depended on the coordination and dissociation between PASP and Cu2+. We proposed its application for AChE activity detection, as well as its inhibitor screening. According to the change of fluorescence intensity, quantifying the detection limit of AChE was 1.78 mU·mL-1. Classical inhibitors, tacrine and organophosphate pesticide diazinon, were further evaluated for drug screening. The IC50 value of tacrine was calculated to be 0.43 µM, and the detection limit of diazinon was 0.22 µM. Both of these performances were much better than previous results, revealing our probe is sensitive and reversible for screening applications.

ß-Lactoglobulin amyloid fibril-templated gold nanoclusters for cellular multicolor fluorescence imaging and colorimetric blood glucose assay.

ß-Lactoglobulin amyloid fibril (BLGF)-capped gold nanoclusters (Au NCs) with red, green and blue emissions were fabricated via pH-dependent reduction strategy. The BLGF-Au NCs exhibited 3.2 times enhancement of fluorescence (λex = 500 nm, λem = 684 nm), a significant 42 nm red shift, a 11.57% quantum yield and a 1.4 µs decay time compared with native ß-lactoglobulin (BLG)-stabilized Au NCs. Meanwhile, the multicolor Au NCs were employed for cell imaging via incubation with A549 cells for 14 h. According to the Michaelis-Menten equation, the kinetic parameters of the BLGF-Au NCs showed a lower Km value (66 µmol L-1) for 3,3,5,5-tetramethylbenzidine (TMB) and a higher vmax (3.74 × 10-8 M s-1) for H2O2, which are comparable with other artificial nanoenzymes and natural peroxidases. Based on the highly intrinsic peroxidase-like activity of the BLGF-Au NCs, a colorimetric method was developed for glucose determination with a detection limit of 1.5 µmol L-1 by determining the variation of the absorption at 652 nm, ranging from 5 to 100 µmol L-1. In addition, the glucose assay method also revealed a 101.02 to 104.16% recovery in a real human serum sample.

Label-free iodide detection using functionalized carbon nanodots as fluorescent probes.

A label-free fluorescent nanoprobe for iodide ion (I-) detection was developed based on the direct fluorescence quenching of spermine-functionalized carbon dots (SC-dots), whether in complex biological fluids or living cells. The positively charged SC-dots were fabricated via one-step microwave synthesis and exhibited excellent optical properties. Due to the strong quenching ability of I-, SC-dots were utilized for I- detection with high sensitivity and excellent selectivity, which offered a relatively low detection limit of 0.18 µM. This strategy was also successfully applied for I- detections in human serum and HeLa cells. The detection process is facile, highly sensitive and selective, providing a new insight into the potential applications of SC-dots for anion nanoprobe designs in clinical diagnosis and other biologically related areas. Graphical abstract.

Organ-on-a-chip: recent breakthroughs and future prospects.

The organ-on-a-chip (OOAC) is in the list of top 10 emerging technologies and refers to a physiological organ biomimetic system built on a microfluidic chip. Through a combination of cell biology, engineering, and biomaterial technology, the microenvironment of the chip simulates that of the organ in terms of tissue interfaces and mechanical stimulation. This reflects the structural and functional characteristics of human tissue and can predict response to an array of stimuli including drug responses and environmental effects. OOAC has broad applications in precision medicine and biological defense strategies. Here, we introduce the concepts of OOAC and review its application to the construction of physiological models, drug development, and toxicology from the perspective of different organs. We further discuss existing challenges and provide future perspectives for its application.

miR-545 promoted enterovirus 71 replication via directly targeting phosphatase and tensin homolog and tumor necrosis factor receptor-associated factor 6.

Enterovirus 71 (EV71) is a small, nonenveloped icosahedral RNA virus and is the predominant causative pathogen of hand-foot-and-mouth disease. Recently, microRNAs (miRNAs) are reported to play important roles in the pathogenesis of EV71 replication. This study investigated the role of miR-545 in the EV71 replication and explored the underlying molecular mechanisms. We showed that miR-545 was upregulated in the EV71-infected human embryonic kidney (HEK) 293 cells and rhabdomyosarcoma (RD) cells. Overexpression of miR-545 promoted the viral replication of EV71 and attenuated the inhibitory effects of EV71 on cell viability in HEK293 and RD cells; while knockdown of miR-545 significantly suppressed the EV71 replication in these two cell lines. Bioinformatics analysis and luciferase reporter assay showed that miR-545 directly targeted the 3'untranslated region of phosphatase and tensin homolog (PTEN) and tumor necrosis factor receptor-associated factor 6 (TRAF6) in HEK293 cells. Furthermore, miR-545 negatively regulated the messenger RNA (mRNA) and protein expression of PTEN and TRAF6. The mRNA and protein expression of PTEN and TRAF6 was also suppressed by EV71 infection, which was attenuated by miR-545 knockdown in HEK293 cells. Overexpression of PTEN and TRAF6 both suppressed the EV71 replication in HKE293 cells, and also attenuated the enhanced effects of miR-545 overexpression on the EV71 replication in HEK293 cells. Collectively, our study for the first time showed that miR-545 had an enhanced effect on the EV71 replication in HEK293 and RD cells. Further mechanistic results indicated that miR-545 promoted EV71 replication at least partly via targeting PTEN and TRAF6.

Schiff-base reaction induced selective sensing of trace dopamine based on a Pt41Rh59 alloy/ZIF-90 nanocomposite.

Zeolitic imidazole frameworks (ZIFs) are a new class of functional porous materials with attractive characters, such as gas storage, selective separation, catalysis, and drug delivery. We report herein using nanoscale ZIF-90 crystals with free aldehyde group of imidazole-2-carboxaldehyde (ICA) ligand for the selective electrochemical detection of dopamine. The averaged adsorption enthalpy ΔH (i.e., isosteric heat) of ZIF-90 to dopamine is estimated as 72 kJ mol-1 according to grand canonical Monte Carlo (GCMC) simulation. With further modification of a Pt41Rh59 alloy nanocatalyst, the electrochemical sensing performances towards dopamine are improved. The synergetic effect generated by a Pt41Rh59/ZIF-90 nanocomposite endows it a low detection limit of 1 nM and good specificity. The different anti-interference mechanisms to coexisting redox active species and amino analogues are also included in this work. The strategy demonstrated here may be extended to tune metal nodes as well as ligands of ZIFs crystals and further regulating their functionalities for different target molecules identification.

Fibrinogen-templated gold nanoclusters for fluorometric determination of cysteine and mercury(II).

Gold nanoclusters (Au NCs) using fibrinogen (FBG) protein as template are fabricated via one-pot reduction strategy, and applied for fluorometric detections of cysteine (Cys) and mercury(II). The modified FBG-Au NCs exhibit red fluorescence, with excitation/emission maxima at 360/620 nm, a 7% quantum yield, and a 2.2 µs decay time. The fluorescence of the nanoprobe is quenched by Cys and Hg(II). Cys can be determined by fluorometry in the 0.01 to 150 µmol L-1 concentration range and with a detection limit of 0.79 µmol L-1. Due to the oxidation of Hg(II), it can be detected in the 0.01 to 10 µmol L-1 concentration range. The properties of the FBG-Au NCs and the analytical performance are comparable with previously reported peptide/protein-templated Au NCs, supplying a promising candidate for Au NCs nanoprobes synthesis and applications. Graphical abstractSchematic representation of the preparation of gold nanoclusters (Au NCs) using fibrinogen (FBG) as the template. The modified Au NCs were applied to the fluorometric detection of cysteine (Cys) and mercury ion (Hg(II)).

Accelerating the Peroxidase-Like Activity of Gold Nanoclusters at Neutral pH for Colorimetric Detection of Heparin and Heparinase Activity.

The peroxidase-like catalytic activity of gold nanoclusters (Au-NCs) is quite low around physiological pH, which greatly limits their biological applications. Herein, we found heparin can greatly accelerate the peroxidase-like activity of Au-NCs at neutral pH. The catalytic activity of Au-NCs toward the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) oxidation by H2O2 was 25-fold increased in the presence of heparin at pH 7. The addition of heparin not only accelerated the initial catalytic rate of Au-NCs but also prevented the Au-NCs from catalyst deactivation. This allows the sensitive colorimetric detection of heparin at neutral pH. In the presence of heparinase, heparin was hydrolyzed into small fragments, weakening the enhancement effect of catalytic activity. On the basis of this phenomenon, the colorimetric determination of heparinase in the range from 0.1 to 3 µg·mL-1 was developed with a detection limit of 0.06 µg·mL-1. Finally, the detection of heparin and heparinase activity in diluted serum samples was also demonstrated.