Analysis of the clinical profile and treatment efficiency of hyperlipidemic acute pancreatitis.

BACKGROUND: The incidence of hyperlipidemic acute pancreatitis (HLAP) has been increasing annually. However, population-based morbidity assessments need to be updated. Early, rapid, and effective lipid-lowering may minimize pancreatic injury and improve clinical prognosis. It is essential to choose the proper treatment. However, treatment options for HLAP are controversial, and there is no uniform treatment protocol. METHODS: In this retrospective study, 127 patients with hyperlipidemic severe acute pancreatitis (HL-SAP) were registered from January 2018 to December 2022 at the General Hospital of Ningxia Medical University. Medical and radiological records of hospitalized patients were collected to determine clinical features, severity, complications, mortality, recurrence rate, and treatment. Risk factors for HL-SAP were analyzed using multifactorial logistic regression. A propensity score matching method was used to compare the clinical outcomes of standard and plasma exchange therapies. RESULTS: In this research, the prevalence of HLAP increased about 1.6 times, and the prevalence of HL-SAP was 50.60%. HL-SAP occurs most often in people between the ages of 30 and 39. Amylase exceeded 110 U/L in 84.3% of patients and 330 U/L in only 47.2%. 83.5% of HL-SAP patients had fatty livers and high body mass index (BMI). A total of 48.0% of patients experienced organ failure, ICU treatment (55.1%), recurrence (33.1%), and death (21.3%). Between the hyperlipidemic group and the biliary group in terms of age, gender, BMI, fatty liver, pleural effusion, abdominal constriction syndrome (ACS), multiple organ dysfunction syndrome (MODS), length of hospital, medical costs, morbidity and mortality, triglyceride, cholesterol, creatinine, blood glucose, D-dimer, amylase, albumin, lactate dehydrogenase, serum phosphorus, serum calcium, oxygenation index, and recurrence rate were statistically significant (P < 0.05). High BMI (P = 0.0038, odds ratio (OR) = 1.336, 95%CI: 0.99-1.804), high C-reactive protein (CRP) (P = 0.022, OR = 1.011, 95%CI: 1.003-1.019), low calcium (P = 0.003, OR = 0.016, 95%CI. 0.001-0.239), low albumin (P = 0.012, OR = 0.045, 95%CI: -0.062-0.192), and high D-dimer (P = 0.041, OR = 0.619, 95%CI: 0.053-2.510) were risk factors for HL-SAP, according to multifactorial logistic regression analysis. Adjusted for propensity score matching (PSM), Serum triglyceride (TG) was significantly lower in both the standard treatment (P < 0.001) and plasma exchange (P < 0.001) groups at 48 h compared with the initial test after the attack. Clearance (83.20% ± 0.0% vs. 84.4% ± 0.0%, P = 0.531), length of hospital stay (19.9 ± 4.9 vs. 19.8 ± 11.1, P = 0.092), and death (26.3% vs. 23.6%, P = 0.791) showed no difference between the two groups. However, the difference in medical costs(P = 0.039)between the two groups was statistically significant. CONCLUSION: The incidence of HLAP exhibited a significant increase, remarkable severity, recurrent trend, and mortality. High BMI, high CRP, low calcium, low albumin, and high D-dimer are risk factors for HL-SAP. Compared with standardized treatment, plasma exchange does not improve the prognosis of HL-SAP patients, and standardized treatment is equally effective, safe, and low-cost in early treatment.

Psychometric properties of the Chinese version of the Exercise Self-Efficacy Scale for the Transtheoretical Model: a confirmatory analysis among Chinese children and adolescents.

BACKGROUND: Self-efficacy has been recognized as a critical component in people's participation and maintenance of physical activity. This study aims to validate the Chinese version of the Exercise Self-Efficacy Scale (ESE) among Chinese children and adolescents using confirmatory factor analysis (CFA). METHODS: A cross-sectional study was conducted on two primary and two secondary schools in central China. The ESE scale was translated into Chinese (ESE-C) using the standard forward-backward translation method. Data were analyzed using Mplus 8 for the CFA. RESULTS: The final model showed a satisfactory level of goodness-of-fit (CFI = 0.918; TLI = 0.905; SRMR = 0.043; RMSEA = 0.066), indicating a good construct validity of the ESE-C for children and adolescents in mainland China. Furthermore, the final ESE-C model achieved composite reliability values of 0.963 and average variance extraction values of 0.597, indicating sufficient convergent and discriminant validity. Besides, the Cronbach's alpha value was 0.964, demonstrating excellent internal consistency of the ESE-C scale. CONCLUSION: The ESE-C scale is a valid instrument for assessing exercise self-efficacy among children and adolescents in mainland China.

Immunomodulatory hybrid micro-nanofiber scaffolds enhance vascular regeneration.

The inertness of synthetic polymer materials and the insufficient mechanical strength of reprocessed decellularized extracellular matrix (dECM) limited their promotive efforts on tissue regeneration. Here, we prepared a hybrid scaffold composed of PCL microfibers and human placental extracellular matrix (pECM) nanofibers by co-electrospinning, which was grafted with heparin and further absorbed with IL-4. The hybrid scaffold with improved hemocompatibility firstly switched macrophages to anti-inflammatory phenotype (increased by 18.1%) and then promoted migration, NO production, tube formation of endothelial cells (ECs), and migration and maturation of vascular smooth muscle cells (VSMCs), and ECM deposition in vitro and in vivo. ECs coverage rate increased by 8.6% and the thickness of the smooth muscle layer was 1.8 times more than PCL grafts at 12 wks. Our study realized the complementary advantages of synthetic polymer materials and dECM materials, and opened intriguing perspectives for the design and construction of small-diameter vascular grafts (SDVGs) and immune-regulated materials for other tissue regeneration.

Serum estradiol to testosterone ratio as a novel predictor of severe preeclampsia in the first trimester.

Preeclampsia (PE) is the most common medical complication during pregnancy and the second leading cause of maternal death worldwide. However, a better predictive model of PE remains to be explored. A total of 15 severe preeclampsia (sPE) and 75 healthy control patients were included in this study. Patient data was obtained from September 2019 to September 2021. Nuchal translucency (NT) and crown-rump length (CRL) of the fetus were acquired by ultrasound. Maternal blood samples were collected at 11+0 to 13+6  weeks of gestation. Chemiluminescent immunoassays were used to detect serum testosterone (T) and estradiol (E2) levels. Time-resolved fluorescence analysis was used to examine the levels of serum pregnancy-associated plasma protein A (PAPPA) and ß-human chorionic gonadotrophin (ß-HCG) protein. The sPE group exhibited increased T levels, and decreased E2 levels and E2/T ratios from 11 to 14 weeks of gestation, compared with the control group. E2 and the E2/T ratio showed positive linear correlation with CRL in pregnant women. Body-mass-index (BMI), T, and E2 were determined to be the main factors that affected the occurrence of sPE at the 12-week gestation period time point. The receiver operating characteristic (ROC) curve revealed that the AUC of the E2/T ratio was .717. The imbalanced T and E2 levels in the patients had a specific intrinsic relevance with sPE, which suggests them as novel predictors of the sPE.

Conductive Covalent Organic Frameworks with Conductivity- and Pre-Reduction-Enhanced Electrochemiluminescence for Ultrasensitive Biosensor Construction.

Covalent organic frameworks (COFs) have attracted widespread attention in the electrochemiluminescence (ECL) field owing to their high load capacity of ECL luminophores and porous structures, but their ECL performance is still limited by the intrinsic poor conductivity (generally <10-8 S m-1). To address this shortcoming, we used 2,3,6,7,10,11-hexaaminotriphenylene (HATP) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) to synthesize a conductive COF (HHTP-HATP-COF, conductivity = 3.11 × 10-4 S m-1). Compared with HATP, HHTP, and low-conductive HHTP-DABZ-COF, HHTP-HATP-COF exhibited superior ECL performance, not only because HHTP-HATP-COF possessed massive ECL luminophores but also because its conductive porous framework accelerated charge transport in the whole framework and improved the utilization ratio of ECL luminophores. More interestingly, the ECL intensity of the HHTP-HATP-COF/S2O82- system was further improved after pre-reduction electrolysis due to the accumulation of HHTP-HATP-COF cation radicals. The experimental results showed that the ECL intensity of the HHTP-HATP-COF/S2O82- system after pre-reduction was about 1.64-, 3.96-, 6.88-, and 8.09-fold higher than those of HHTP-HATP-COF/S2O82-, HHTP-DABZ-COF/S2O82-, HHTP/S2O82-, and HATP/S2O82- systems, respectively. Considering the superior ECL property of the HHTP-HATP-COF/S2O82- system after pre-reduction, it was used as a high-efficient ECL beacon together with an aptamer/protein proximity binding-induced three-dimensional bipedal DNA walker to construct an ultrasensitive biosensor for thrombin detection, which displayed broad linearity (100 aM to 1 nM) with a detection limit of 62.1 aM. Overall, the work offered effective ways to increase ECL performance by the enhancement of conductivity and by the pre-reduction, proposing new ideas to design high-efficiency COF-based ECL materials and endowing conductive COFs with ECL biosensor application for the first time.

Nonlinear Relationship Between Macrocytic Anemia and Decompensated Hepatitis B Virus Associated Cirrhosis: A Population-Based Cross-Sectional Study.

Background: Mean corpuscular volume (MCV) is major used as an indicator for the differential diagnosis of anemia. Macrocytic anemia in decompensated cirrhosis is common. However, the relationship between macrocytic anemia and decompensated hepatitis B virus (HBV) associated cirrhosis has not been fully addressed. Methods: In this cross-sectional study, a total of 457 patients diagnosed decompensated HBV associated cirrhosis who met all inclusion criteria from 2011 to 2018 were analyzed. Association between macrocytic anemia and the liver damaged (Model for End Stage Liver Disease (MELD) score) were examined using multiple logistic regression analyses and identified using smooth curve fitting. Results: Compared with normocytic anemia, MCV and MELD are significantly positively correlated in macrocytic anemia (p < 0.001). A non-linear relationship of MCV and MELD association was found though the piecewise linear spline models in patients with decompensated HBV associated cirrhosis. MCV positive correlated with MELD when the MCV was greater than 98.2 fl (regression coefficient = 0.008, 95% CI 0.1, 0.4). Conclusion: Macrocytic anemia may be a reliable predictor for mortality because it is closely related to the degree of liver damage in patients with decompensated HBV associated cirrhosis.

IGF-1 alleviates CCL4-induced hepatic cirrhosis and dysfunction of intestinal barrier through inhibition TLR4/NF-κB signaling mediated by down-regulation HMGB1.

INTRODUCTION AND OBJECTIVES: Cirrhosis has gradually become a serious public health issue, especially the national prevalence of cirrhosis was 29.2% in northwest China. Recent evidence has revealed that intestinal barrier (IB) dysfunction results from and contributes to cirrhosis. Our previous results have indicated that insulin-like growth factors (IGF-1) improved the impaired IB function and downregulated high mobility group protein box-1 (HMGB-1). Nevertheless, the role of the IGF-1/HMGB1 axis in cirrhosis remains largely unknown. MATERIALS AND METHODS: Western blotting and qRT-PCR were used to detect protein and mRNA levels of related genes. The levels of AST, ALT, IL-1ß, and TNF-α were examined using commercial kits. Immunofluorescence was used to evaluate the expression of HMGB1 in tissues. RESULTS: In carbon tetrachloride (CCl4)-treated rat, the levels of AST (380.12 vs. 183.97), ALT (148.12 vs. 53.56), IL-1ß (155.94 vs. 55.60), and TNF-α (155.00 vs. 48.90) were significantly increased compared with the control group, while IGF-1 treatment significantly alleviated CCL4-induced inflammatory response and IB dysfunction by downregulating HMGB1-mediated the TLR4/MyD88/NF-κB signaling pathway. In vitro experiments, HMGB1 treatment promoted inflammatory cytokines secretion and reduced cell viability and tight junctions by activating the TLR4/MyD88/NF-κB signaling pathway in Caco-2 cells, but IGF-1 alleviated these effects. CONCLUSION: Our findings suggest that IGF-1 might serve as a potential therapeutic target for cirrhosis and IB dysfunction via inactivation of the TLR4/MyD88/NF-κB pathway through down-regulation HMGB1.

Overcoming Aggregation-Induced Quenching by Metal-Organic Framework for Electrochemiluminescence (ECL) Enhancement: Zn-PTC as a New ECL Emitter for Ultrasensitive MicroRNAs Detection.

Polycyclic aromatic hydrocarbons (PAHs) as traditional electrochemiluminescence (ECL) luminophores have been widely applied in the analysis field. However, their ECL intensity and efficiency are still limited due to the aggregation-induced quenching (ACQ) effect of PAHs. Hence, to overcome this limitation, we put forward a new strategy to increase the ECL intensity and efficiency by eliminating the ACQ effect of PAHs through the coordinative immobilization of PAHs within metal-organic frameworks (MOFs). As anticipated, the proof-of-concept experiment indicated that the coordinative immobilization of perylene-3,4,9,10-tetracarboxylate (PTC) into a Zn-PTC MOF could distinctly increase the ECL intensity and efficiency compared with H4PTC aggregates and H4PTC monomers. The reason for the ECL enhancement of Zn-PTC was that the immobilization of PTC within the MOF effectively amplified the distance between perylene rings of PTC ligands and thus eliminated the ACQ effect. Furthermore, the PTC into Zn-PTC was stacked in an edge-to-edge mode to form J-aggregation, which was also conducive to ECL enhancement. On the basis of the excellent ECL performance, we utilized Zn-PTC as a new ECL emitter combined with exonuclease III-stimulated target cycling and DNAzyme-assisted cycling dual amplification strategies to construct an ECL sensor for microRNA-21 detection, which had a wide signal response (100 aM to 100 pM) with a detection limit of 29.5 aM. Overall, this work represents a new and convenient method to overcome the ACQ effect of PAHs and boost the ECL performance, which opens a new horizon for developing high-performance ECL materials, thus offering more opportunities for building highly sensitive ECL biosensors.

Change and development law of adolescents' physical health exercise behavior / Lei de mudança e desenvolvimento do comportamento de exercício de saúde física de adolescentes com base nos antecedentes da ecologia social / Investigación sobre la ley de cambio y desarrollo de la conducta de ejercicio de salud física de los adolescentes basada en los antecedentes de la ecología social

ABSTRACT Background: The generation of individual behavior is closely related to the environment in which it is located and is easily affected by environmental factors. Objective: The thesis takes the social ecology model theory as the starting point, applies the five different levels of influencing factors in the theoretical model to the field of youth physical exercise behavior, and seeks the interrelationship between the various influencing factors. Methods: Using questionnaire surveys, interviews, and other research methods, the paper makes a simple theoretical combing and analysis of the healthy behavior ecology model, seeks the interrelationship between the influencing factors, propose complementary intervention strategies, and promote the development of adolescents' physical exercise habits through effective ways. Results: The motivation of sports participation, the protection of physical health, family health awareness, economic and educational environment, professional quality of physical education teachers and school exercise environment and community facilities affect the direction of the development of adolescents' physical exercise behavior. Conclusions: Only by comprehensively considering the relationship between various related factors can we better understand adolescent physical exercise development characteristics, propose complementary intervention strategies, and promote physical exercise habits effectively. Level of evidence II; Therapeutic studies - investigation of treatment results.

RESUMO Antecedentes: A geração do comportamento individual está intimamente relacionada ao ambiente em que está inserida e é facilmente afetada por fatores ambientais. Objetivo: A tese toma como ponto de partida a teoria do modelo da ecologia social, aplica os cinco diferentes níveis de fatores influenciadores do modelo teórico ao campo do comportamento de exercício físico juvenil e busca a inter-relação entre os vários fatores influenciadores. Métodos: Utilizando questionários, entrevistas e outros métodos de pesquisa, o artigo faz uma análise teórica simples do modelo de ecologia do comportamento saudável, busca a inter-relação entre os fatores que influenciam, propõe estratégias de intervenção complementares e promove o desenvolvimento físico dos adolescentes. hábitos de exercício através de formas eficazes. Resultados: A motivação para a prática de esportes, a proteção da saúde física, a conscientização sobre a saúde da família, o ambiente econômico e educacional, a qualidade profissional dos professores de educação física e o ambiente de exercício escolar e as instalações comunitárias afetam a direção do desenvolvimento do comportamento de exercício físico dos adolescentes. Conclusões: Somente considerando de forma abrangente a relação entre vários fatores relacionados podemos entender melhor as características do desenvolvimento de exercícios físicos em adolescentes, propor estratégias de intervenção complementar e promover hábitos de exercícios físicos de forma eficaz. Nível de evidência II; Estudos terapêuticos: investigação dos resultados do tratamento.

RESUMEN Antecedentes: La generación del comportamiento individual está íntimamente relacionada con el entorno en el que se ubica y es fácilmente afectado por factores ambientales. Objetivo: La tesis toma como punto de partida la teoría del modelo de ecología social, aplica los cinco niveles diferentes de factores de influencia en el modelo teórico al campo de la conducta de ejercicio físico juvenil y busca la interrelación entre los diversos factores de influencia. Métodos: Mediante cuestionarios, entrevistas y otros métodos de investigación, el trabajo realiza un simple peinado y análisis teórico del modelo de ecología del comportamiento saludable, busca la interrelación entre los factores influyentes, propone estrategias de intervención complementarias y promueve el desarrollo de la física de los adolescentes. Hábitos de ejercicio de forma eficaz. Resultados: La motivación de la participación deportiva, la protección de la salud física, la conciencia de la salud familiar, el entorno económico y educativo, la calidad profesional de los profesores de educación física y el entorno de ejercicio escolar y las instalaciones comunitarias afectan la dirección del desarrollo de la conducta de ejercicio físico de los adolescentes. Conclusiones: Solo considerando de manera integral la relación entre varios factores relacionados podemos comprender mejor las características del desarrollo del ejercicio físico en los adolescentes, proponer estrategias de intervención complementarias y promover los hábitos de ejercicio físico de manera efectiva. Nivel de evidencia II; Estudios terapéuticos: investigación de los resultados del tratamiento.

Highly efficient electrochemiluminescence resonance energy transfer material constructed from an AIEgen-based 2D ultrathin metal-organic layer for thrombin detection.

A facile strategy to design a highly efficient electrochemiluminescence resonance energy transfer (ECL-RET) system was proposed by using an AIEgen-based 2D ultrathin metal-organic layer (MOL) to coordinatively immobilize energy donors and acceptors simultaneously, in which the distance between adjacent donor-acceptor pairs was precise and short for obtaining high ECL-RET efficiency.

Highly Stable Covalent Organic Framework Nanosheets as a New Generation of Electrochemiluminescence Emitters for Ultrasensitive MicroRNA Detection.

A pyrene-based sp2 carbon-conjugated covalent organic framework (COF) nanosheet (Py-sp2c-CON) with strong and stable electrochemiluminescence (ECL) emission was constructed by C═C polycondensation of tetrakis(4-formylphenyl)pyrene (TFPPy) and 2,2'-(1,4-phenylene)diacetonitrile, which was employed as a highly efficient ECL emitter to fabricate an ECL biosensor for the first time. The Py-sp2c-CON exhibited higher ECL intensity and efficiency than those of TFPPy, bulk Py-sp2c-COF, and imine-linked pyrene COF, not only because the pyrene luminophores and aggregation-induced emissive luminogens (cyano-substituted phenylenevinylene) were topologically linked into Py-sp2c-CON, which greatly increased the immobilization amount of luminophores and decreased the aggregation-caused quenching effect and nonradiative transition but also because the porous ultrathin structure of Py-sp2c-CON effectively shortened transport distances of an electron, ion, and co-reactant (S2O82-), which made more ECL luminophores be activated and thus efficiently increased the utilization ratio of luminophores. More interestingly, when Bu4NPF6 was introduced into the Py-sp2c-CON/S2O82- system as a co-reaction accelerator, the ECL signal of Py-sp2c-CON was further amplified. As expected, the average ECL intensity of the Py-sp2c-CON/S2O82-/Bu4NPF6 system was about 2.03, 5.76, 24.31, and 190.33-fold higher than those of Py-sp2c-CON/S2O82-, Py-sp2c-COF/S2O82-, TFPPy/S2O82,- and imine-linked pyrene COF/S2O82- systems. Considering these advantages, the Py-sp2c-CON/S2O82-/Bu4NPF6 system was employed to prepare an ECL biosensor for microRNA-21 detection, which exhibited a broad linear response (100 aM to 1 nM) and a low detection limit (46 aM). Overall, this work demonstrated that sp2 carbon CONs can be directly used as a high-performance ECL emitter, thus expanding the application scope of COFs and opening a new horizon to develop new types of ECL emitters.

Two Birds with One Stone: Surface Functionalization and Delamination of Multilayered Ti3C2Tx MXene by Grafting a Ruthenium(II) Complex to Achieve Conductivity-Enhanced Electrochemiluminescence.

Two-dimensional (2D) nanosheets have captured significant attention in constructing highly efficient electrochemiluminescent (ECL) materials because their high surface area and fully exposed postmodification sites could greatly increase the loading amount of luminophores. However, traditional 2D nanosheets as carriers exhibited natively poor electrical conductivity that restricted the electrochemical activation and the utilization ratio of ECL luminophores. Herein, to overcome this drawback, we utilized conductive 2D Ti3C2Tx MXene nanosheets as carriers to graft Ru(bpy)2(mcpbpy)2+ (bpy = 2,2'-bipyridine, mcpbpy = 4-(4'-methyl-[2,2'-bipyridin]-4-yl) butanoic acid) via a dehydrative condensation reaction and electrostatic interaction. Interestingly, Ru(bpy)2(mcpbpy)2+ played the role of "two birds with one stone", where Ru(bpy)2(mcpbpy)2+ acted as both an ECL luminophore and an intercalation molecule to achieve surface functionalization and delamination of multilayered Ti3C2Tx successfully, obtaining 2D ultrathin Ru-complex-grafted MXene nanosheets (Ru@MXene). Owing to the high load capacity and superior electrical conductivity of an ultrathin 2D MXene nanosheet, the obtained Ru@MXene exhibited a superb ECL emission. As expected, compared with the nonconductive 2D ultrathin metal-organic layers (MOLs) as carriers to graft Ru(bpy)2(mcpbpy)2+, the ECL intensity and ECL efficiency of Ru@MXene presented about 5-fold and 1.7-fold enhancement, respectively. Considering these advantages, Ru@MXene was applied to construct an ECL sensor for ultrasensitive determination of mucin 1 (MUC1), which displayed superb sensitivity (100 ag/mL to 10 ng/mL) with a low detection limit of 26.9 ag/mL. Overall, the conductivity-enhanced ECL based on Ru@MXene opened a fire-new chapter to develop splendent performance ECL emitters and shed new light on the application potential of conductive materials in the bioanalysis field.

An AIEgen-based 2D ultrathin metal-organic layer as an electrochemiluminescence platform for ultrasensitive biosensing of carcinoembryonic antigen.

In this work, a novel two-dimensional (2D) ultrathin metal-organic layer (MOL) based on the aggregation-induced emission (AIE) ligand H4ETTC (H4ETTC = 4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1'-biphenyl]-4-carboxylic acid))) was developed and used to construct a novel electrochemiluminescence (ECL) aptasensor for ultrasensitive detection of carcinoembryonic antigen (CEA). The newly synthesized AIE luminogen (AIEgen)-based MOL (Hf-ETTC-MOL) yielded a higher ECL intensity and efficiency than did H4ETTC monomers, H4ETTC aggregates and 3D bulk Hf-ETTC-MOF. This improvement occurred not only because the ETTC ligands were coordinatively immobilized in a rigid MOL matrix, which restricted the intramolecular free rotation and vibration of these ligands and then reduced the non-radiative transition, but also because the porous ultrathin 2D MOL greatly shortened the transport distances of ions, electrons, coreactant (triethylamine, TEA) and coreactant intermediates (TEA˙ and TEA˙+), which made more ETTC luminophores able to be excited and yielded a high ECL efficiency. On the basis of using the Hf-ETTC-MOL as a novel ECL emitter and rolling circle amplification (RCA) as a signal amplification strategy, the constructed ECL aptasensor exhibited a linear range from 1 fg mL-1 to 1 ng mL-1 with a detection limit of 0.63 fg mL-1. This work has opened up new prospects for developing novel ECL materials and is expected to lead to increased interest in using AIEgen-based MOLs for ECL sensing.

Restriction of intramolecular motions (RIM) by metal-organic frameworks for electrochemiluminescence enhancement:2D Zr12-adb nanoplate as a novel ECL tag for the construction of biosensing platform.

Herein, a new phenomenon of enhanced electrochemiluminescence (ECL) emission by restricting intramolecular motion in the 2D ultra-thin Zr12-adb (adb = 9,10-anthracene dibenzoate) metal-organic framework (MOF) nanoplate was discovered for the first time. The coordination immobilization of adb in porous ultra-thin Zr12-adb nanoplate endowed the Zr12-adb excellent ECL performance, including stronger ECL signal and higher ECL efficiency relative to those of H2adb monomers and H2adb aggregates. In the 2D Zr12-adb nanoplate, the bridging ligand adb was stretched and fixed between two Zr12 clusters, which restricted intramolecular rotations and suppressed unnecessary energy loss caused by self-rotation, thereby remarkably improved the ECL intensity and efficiency. More importantly, the porous ultra-thin structure of Zr12-adb MOF nanoplate not only allowed the coreactants to diffuse into the MOF interior, making both internal and external adb be excited, but also shortened the migration distance of electrons, ions, coreactants and coreactant intermediates, which further improved the ECL efficiency of Zr12-adb and overcame the shortcoming of H2adb aggregates in which the internal luminophores were not easily excited. Regarding the excellent ECL properties above, Zr12-adb nanoplate was selected as a new ECL emitter incorporated with the bipedal walking molecular machine together to fabricate a biosensor for sensitive detection of mucin 1. The enhanced ECL by restriction of intramolecular motions in MOFs provided a new pathway to improve ECL intensity and efficiency, which lighted up a lamp for the design and manufacture of high-performance ECL materials based on MOFs, thus offering new opportunities to develop ultrasensitive ECL biosensors.

Matrix Coordination-Induced Electrochemiluminescence Enhancement of Tetraphenylethylene-Based Hafnium Metal-Organic Framework: An Electrochemiluminescence Chromophore for Ultrasensitive Electrochemiluminescence Sensor Construction.

Here, we discovered that rigidifying the tetraphenylethylene (TPE)-based ligand H4TCBPE (H4TCBPE = 1,1,2,2-tetra(4-carboxylbiphenyl)ethylene) into Hf-based metal-organic framework (Hf-TCBPE) could lead to a stronger electrochemiluminescence (ECL) emission in comparison to H4TCBPE aggregates and H4TCBPE monomers. Due to the lack of close-packed TCBPE chromophores in Hf-TCBPE, which was required for aggregation-induced ECL (AI-ECL) enhancement, we defined this unprecedented phenomenon as matrix coordination-induced ECL (MCI-ECL) enhancement. The strong ECL intensity of Hf-TCBPE not only originated from the fixation of the TCBPE ligand between Hf6 clusters that restricted the intramolecular free motions of TCBPE and suppressed the nonradiative relaxation but also stemmed from the high porosity of Hf-TCBPE that rendered both internal and external TCBPE chromophores able to be excited. Considering the unique ECL characteristic of Hf-TCBPE, we combined the new ECL indicator of Hf-TCBPE as well as the phosphate-terminal ferrocene (Fc)-labeled hairpin DNA (Fc-HP3) aptamer together as a signal probe (Hf-TCBPE/Fc-HP3), which was employed to construct a novel "off-on" ECL sensor for ultrasensitive mucin 1 (MUC1) detection with the assistance of the exonuclease III (Exo III)-assisted recycling amplification strategy. As expected, the ECL sensor displayed a desirable linear response range from 1 fg/mL to 1 ng/mL and the detection limit down to 0.49 fg/mL. The MCI-ECL enhancement demonstrated by the Hf-TCBPE developed a new and promising strategy to design and synthesize high-performance metal-organic framework (MOF)-based ECL materials for constructing ultrasensitive ECL sensors.

A highly sensitive self-enhanced aptasensor based on a stable ultrathin 2D metal-organic layer with outstanding electrochemiluminescence property.

3D bulk metal-organic frameworks (MOFs) have received growing interest in electrochemiluminescence (ECL) assays because they can provide a high specific surface for loading a large quantity of ECL luminophores, but the ECL efficiency of bulk MOFs is still low since some interior luminophores are difficult to be excited. Herein, an ultrathin 2D metal-organic layer (MOL) for grafting self-enhanced ruthenium complexes (Ru-l-Lys) was first synthesized to greatly increase the utilization ratio of luminophores. Compared with 3D bulk MOFs, ultrathin 2D MOL could provide more accessible postmodification sites for grafting the Ru-l-Lys complexes; the self-enhanced Ru-l-Lys complexes on MOL were easily excited by electrons due to the shortened ion/electron-transport distance and the removal of diffusion barriers. Furthermore, the electron transfer path between the Ru(ii) luminophore and coreactant (l-Lys) was shortened and the energy loss of the luminophores decreased, which significantly improved the ECL efficiency. As expected, our work manifested that the Zr-MOL's loading amount of Ru-l-Lys was about 1.23-fold higher than that of a 3D bulk Zr-MOF, and the ECL intensity and efficiency of Ru-l-Lys-Zr-MOL were around 93.45-fold and 1.64-fold higher than those of control Ru-l-Lys-Zr-MOF, respectively. Considering all of these merits, in this work, we utilized the prepared Ru-l-Lys-Zr-MOL as a highly efficient ECL indicator for the first time to fabricate a highly sensitive self-enhanced aptasensor for mucin 1 (MUC1) determination. The proposed aptasensor showed high sensitivity with a linear range from 1 fg mL-1 to 100 pg mL-1 with a detection limit of 0.72 fg mL-1; it also exhibited excellent specificity and stability. It is noteworthy that this work not only provides a new strategy to design and synthesize high-performance ECL materials, but also opens a new way to develop ultrasensitive ECL sensors for bioanalysis.

Highly stable Ru-complex-grafted 2D metal-organic layer with superior electrochemiluminescent efficiency as a sensing platform for simple and ultrasensitive detection of mucin 1.

This work utilized ultrathin metal-organic layer (MOL) to immobilize luminophores for effectively shortening the ion/electron-transport distance and relieving the diffusional constraints of ion/electron, which greatly enhanced the ECL efficiency and intensity. Moreover, the MOL's immobilization amount of luminophores should be higher than these of bulk MOFs because MOLs possess more accessible postmodification sites for the luminophores with minimal diffusion barriers. As expected, our proof-of-concept experiment indicated that the Hf-MOL's loading number of Ru(bpy)2(mcpbpy)2+ was about 1.74 times that of a 3D mesoporous MOF (PCN-777), and the ECL efficiency and intensity of PEI@Ru-Hf-MOL were around 1.27 times and 14.5 times those of PEI@Ru-PCN-777, respectively. In view of these merits, this work utilized the prepared PEI@Ru-Hf-MOL as a highly efficient sensing platform for simple, rapid and sensitive detection of mucin 1, which exhibited a broad linearity from 1 fg/mL to 10 ng/mL and a low detection limit of 0.48 fg/mL. This work provided a practicable strategy to develop high-performance ECL materials, and therefore opened up a new avenue to design ultrasensitive ECL biosensors, which expanded the application potential of MOLs in ECL assays.

Highly Stable Mesoporous Luminescence-Functionalized MOF with Excellent Electrochemiluminescence Property for Ultrasensitive Immunosensor Construction.

In this work, a novel mesoporous luminescence-functionalized metal-organic framework (Ru-PCN-777) with high stability and excellent electrochemiluminescence (ECL) performance was synthesized by immobilizing Ru(bpy)2(mcpbpy)2+ on the Zr6 cluster of PCN-777 via a strong coordination bond between Zr4+ and -COO-. Consequently, the Ru(bpy)2(mcpbpy)2+ could not only cover the surface of PCN-777 but also graft into the interior of PCN-777, which greatly increased the loading amount of Ru(bpy)2(mcpbpy)2+ and effectively prevented the leaching of the Ru(bpy)2(mcpbpy)2+ resulting in a stable and high ECL response. Considering the above merits, we utilized the mesoporous Ru-PCN-777 to construct an ECL immunosensor to detect mucin 1 (MUC1) based on proximity-induced intramolecular DNA strand displacement (PiDSD). The ECL signal was further enhanced by the enzyme-assisted DNA recycling amplification strategy. As expected, the immunosensor had excellent sensitivity, specificity, and responded wide linearly to the concentration of MUC1 from 100 fg/mL to 100 ng/mL with a low detection limit of 33.3 fg/mL (S/N = 3). It is the first time that mesoporous Zr-MOF was introduced into ECL system to assay biomolecules, which might expand the application of mesoporous metal-organic frameworks (MOFs) in bioanalysis. This work indicates that the use of highly stable mesoporous luminescence-functionalized MOFs to enhance the ECL intensity and stability is a feasible strategy for designing and constructing high-performance ECL materials, and therefore may shed light on new ways to develop highly sensitive and selective ECL sensors.