A novel pencil graphite electrode modified with an iron-based conductive metal-organic framework exhibited good ability in simultaneous sensing bisphenol A and bisphenol S.

Bisphenol A (BPA) and its substitute bisphenol S (BPS) are desirable materials widely used in manufacturing plastic products but can pose carcinogenic risks to humans. A new conductive iron-based metal-organic framework (Fe-HHTP)-modified pencil graphite electrode (PGE) for electrochemically sensing BPA and BPS was prepared and fully characterized by SEM, TEM, FT-IR, XRD, and XPS. Results showed that the optimal conditions for preparing Fe-HHTP/PGE were a pH of 6.5, a Fe-HHTP concentration of 2 mg·mL-1, a deposition potential of 0 V, and a deposition time of 100 s. The Fe-HHTP/PGE prepared under such conditions harbored a significant electrocatalytic activity with a detection limit of 0.8 nM for BPA and 1.7 nM for BPS (S/N = 3). Correspondingly, the electrochemical response current was linearly correlated to BPA and BPS, ranging from 0.01 to 100 µM. Fe-HHTP/PGE also obtained satisfactory recoveries by 93.8-102.1% and 96.0-101.3% for detecting BPA and BPS in plastic food packaging samples. Our work has provided a novel electrochemical tool to simultaneously detect BPA and BPS in food packaging samples and environmental matrixes.

Theoretical and Experimental Study of Different Side Chains on 3,4-Ethylenedioxythiophene and Diketopyrrolopyrrole-Derived Polymers: Towards Organic Transistors.

In this research, two polymers of P1 and P2 based on monomers consisting of thiophene, 3,4-Ethylenedioxythiophene (EDOT) and diketopyrrolopyrrole (DPP) are designed and obtained via Stille coupling polycondensation. The material shows excellent coplanarity and structural regularity due to the fine planarity of DPP itself and the weak non-covalent bonding interactions existing between the three units. Two different lengths of non-conjugated side chains are introduced and this has an effect on the intermolecular chain stacking, causing the film absorption to display different characteristic properties. On the other hand, the difference in the side chains does not have a significant effect on the thermal stability and the energy levels of the frontier orbitals of the materials, which is related to the fact that the materials both feature extremely high conjugation lengths and specific molecular compositions. Microscopic investigations targeting the side chains provide a contribution to the further design of organic semiconductor materials that meet device requirements. Tests based on organic transistors show a slight difference in conductivity between the two polymers, with P2 having better hole mobility than P1. This study highlights the importance of the impact of side chains on device performance, especially in the field of organic electronics.

Organic Transistors Based on Highly Crystalline Donor-Acceptor π-Conjugated Polymer of Pentathiophene and Diketopyrrolopyrrole.

Oligomers and polymers consisting of multiple thiophenes are widely used in organic electronics such as organic transistors and sensors because of their strong electron-donating ability. In this study, a solution to the problem of the poor solubility of polythiophene systems was developed. A novel π-conjugated polymer material, PDPP-5Th, was synthesized by adding the electron acceptor unit, DPP, to the polythiophene system with a long alkyl side chain, which facilitated the solution processing of the material for the preparation of devices. Meanwhile, the presence of the multicarbonyl groups within the DPP molecule facilitated donor-acceptor interactions in the internal chain, which further improved the hole-transport properties of the polythiophene-based material. The weak forces present within the molecules that promoted structural coplanarity were analyzed using theoretical simulations. Furthermore, the grazing incidence wide-angle X-ray scanning (GIWAXS) results indicated that PDPP-5Th features high crystallinity, which is favorable for efficient carrier migration within and between polymer chains. The material showed hole transport properties as high as 0.44 cm2 V-1 s-1 in conductivity testing. Our investigations demonstrate the great potential of this polymer material in the field of optoelectronics.

Incorporation of Diketopyrrolopyrrole into Polythiophene for the Preparation of Organic Polymer Transistors.

Polythiophene, as a class of potential electron donor units, is widely used in organic electronics such as transistors. In this work, a novel polymeric material, PDPPTT-FT, was prepared by incorporating the electron acceptor unit into the polythiophene system. The incorporation of the DPP molecule assists in improving the solubility of the material and provides a convenient method for the preparation of field effect transistors via subsequent solution processing. The introduction of fluorine atoms forms a good intramolecular conformational lock, and theoretical calculations show that the structure displays excellent co-planarity and regularity. Grazing incidence wide-angle X-ray (GIWAXS) results indicate that the PDPPTT-FT is highly crystalline, which facilitates carrier migration within and between polymer chains. The hole mobility of this π-conjugated material is as high as 0.30 cm2 V-1 s-1 in organic transistor measurements, demonstrating the great potential of this polymer material in the field of optoelectronics.

Closed Cyclic DNA Machine for Sensitive Logic Operation and APE1 Detection.

DNA self-assembly has been developed as a kind of robust signal amplification strategy, but most of reported assembly pathways are programmed to amplify signal in one direction. Herein, based on mutual-activated cascade cycle of hybridization chain reaction (HCR) and catalytic hairpin assembly (CHA), a closed cycle circuit (CCC) based DNA machine is developed for sensitive logic operation and molecular recognition. Benefiting from the synergistically accelerated signal amplification, the closed cyclic DNA machine enabled the logic computing with strong and significant output signals even at weak input signals. The typical logic operations such as OR, YES, AND, INHIBIT, NOR, and NAND gate, are conveniently and clearly executed with this DNA machine through rational design of the input and computing elements. Moreover, by integrating the target recognition module with the CCC module, the proposed DNA machine is further employed in the homogeneous detection of apurinic/apyrimidinic endonuclease 1 (APE1). The precise recognition and exponential signal amplification facilitated the highly selective and sensitive detection of APE1 with limit of detection (LOD) of 7.8 × 10-5 U mL-1 . Besides, the normal cells and tumor cells are distinguished unambiguously by this method according to the detected concentration difference of cellular APE1, which indicates the robustness and practicability of this method.

Photosynthesis of 3-Alkylated Coumarins from Carboxylic Acids Catalyzed by a Na2S-Based Electron Donor-Acceptor Complex.

A simple and practical electron donor-acceptor (EDA) strategy to synthesize various 3-alkylated coumarins from easily available coumarins and naturally abundant carboxylic acids under photocatalyst-, oxidant-, and additive-free and mild conditions is reported. Using Na2S as the catalytic electron donor, a series of primary, secondary, and tertiary carbon radicals can be efficiently generated, and the EDA complex can be regenerated without an alkaline additive.

Visible-Light-Induced Annulation of Iodonium Ylides and 2-Isocyanobiaryls to Access 6-Arylated Phenanthridines.

A 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4-CzIPN)-photocatalyzed cascade arylation/cyclization reaction of 2-isocyanobiaryls and iodonium ylides was established for the synthesis of 6-arylated phenanthridines. This is the first example of employing iodonium ylides as aryl radical sources in a visible-light-induced radical cascade cyclization reaction.

Visible-Light-Mediated Annulation/Thiolation of 2-Isocyanobiaryls with Disulfides to Organoylthiophenanthridines Derivatives.

A visible-light-induced annulation/thiolation of 2-isocyanobiaryls with dialkyl(aryl)disulfides has been established, delivering a sustainable and atom-economic route to 6-organoylthiophenanthridines with wild functional group tolerance and good to excellent yields under oxidant-, base-, and transition-metal-free conditions.

A ratiometric SERS sensor with one signal probe for ultrasensitive and quantitative monitoring of serum xanthine.

Xanthine can be converted into uric acid, and a high concentration of xanthine in the human body can cause many diseases. Therefore, it is important to develop a sensitive, simple, and reliable approach for measuring xanthine in biological liquids. Hence, a ratiometric surface-enhanced Raman spectroscopy (SERS) sensing strategy with one signal probe was exploited for reliable, sensitive, and quantitative monitoring of serum xanthine. 3-Mercaptophenylboronic acid (3-MPBA) was used as a typical reference with a Raman peak at 996 cm-1. First, 3-MPBA was bound to gold nanoflowers@silica (GNFs@Si) through Au-S bonds. Xanthine oxidase (XOD) catalyzed the oxidation of xanthine into H2O2 on GNFs@Si. Afterward, the obtained H2O2 further reduced 3-MPBA to 3-hydroxythiophenol (3-HTP) accompanied by the emergence of a new Raman peak at 883 cm-1. Meanwhile, the Raman intensity at 996 cm-1 remained constant. Therefore, the ratio of I883/I996 increased with the increasing of xanthine concentration, thus realizing quantitative detection of xanthine. As a result, a ratiometric SERS sensor for the detection of xanthine was proposed with a detection limit of 5.7 nM for xanthine. The novel ratiometric SERS sensor provides a new direction for analyzing other biomolecules with high sensitivity and reliability.

Optogenetic engineered umbilical cord MSC-derived exosomes for remodeling of the immune microenvironment in diabetic wounds and the promotion of tissue repair.

BACKGROUND: Angiogenesis and tissue repair in chronic non-healing diabetic wounds remain critical clinical problems. Engineered MSC-derived exosomes have significant potential for the promotion of wound healing. Here, we discuss the effects and mechanisms of eNOS-rich umbilical cord MSC exosomes (UCMSC-exo/eNOS) modified by genetic engineering and optogenetic techniques on diabetic chronic wound repair. METHODS: Umbilical cord mesenchymal stem cells were engineered to express two recombinant proteins. Large amounts of eNOS were loaded into UCMSC-exo using the EXPLOR system under blue light irradiation. The effects of UCMSC-exo/eNOS on the biological functions of fibroblasts and vascular endothelial cells in vitro were evaluated. Full-thickness skin wounds were constructed on the backs of diabetic mice to assess the role of UCMSC-exo/eNOS in vascular neogenesis and the immune microenvironment, and to explore the related molecular mechanisms. RESULTS: eNOS was substantially enriched in UCMSCs-exo by endogenous cellular activities under blue light irradiation. UCMSC-exo/eNOS significantly improved the biological functions of cells after high-glucose treatment and reduced the expression of inflammatory factors and apoptosis induced by oxidative stress. In vivo, UCMSC-exo/eNOS significantly improved the rate of wound closure and enhanced vascular neogenesis and matrix remodeling in diabetic mice. UCMSC-exo/eNOS also improved the inflammatory profile at the wound site and modulated the associated immune microenvironment, thus significantly promoting tissue repair. CONCLUSION: This study provides a novel therapeutic strategy based on engineered stem cell-derived exosomes for the promotion of angiogenesis and tissue repair in chronic diabetic wounds.

Super-enhancer mediated regulation of adult ß-globin gene expression: the role of eRNA and Integrator.

Super-enhancers (SEs) mediate high transcription levels of target genes. Previous studies have shown that SEs recruit transcription complexes and generate enhancer RNAs (eRNAs). We characterized transcription at the human and murine ß-globin locus control region (LCR) SE. We found that the human LCR is capable of recruiting transcription complexes independently from linked globin genes in transgenic mice. Furthermore, LCR hypersensitive site 2 (HS2) initiates the formation of bidirectional transcripts in transgenic mice and in the endogenous ß-globin gene locus in murine erythroleukemia (MEL) cells. HS2 3'eRNA is relatively unstable and remains in close proximity to the globin gene locus. Reducing the abundance of HS2 3'eRNA leads to a reduction in ß-globin gene transcription and compromises RNA polymerase II (Pol II) recruitment at the promoter. The Integrator complex has been shown to terminate eRNA transcription. We demonstrate that Integrator interacts downstream of LCR HS2. Inducible ablation of Integrator function in MEL or differentiating primary human CD34+ cells causes a decrease in expression of the adult ß-globin gene and accumulation of Pol II and eRNA at the LCR. The data suggest that transcription complexes are assembled at the LCR and transferred to the globin genes by mechanisms that involve Integrator mediated release of Pol II and eRNA from the LCR.

Modification of Pillared Intercalated Montmorillonite Clay as Heterogeneous Pd Catalyst Supports.

Montmorillonite clay was modified by pillaring with AlMn oxides in different Al/Mn ratios and intercalation of two kinds of N-containing polymers (i.e., chitosan (CS) and polyvinyl pyrrolidinone (PVP)) chains. The modified pillared montmorillonite clay (PM) showed a rich two-dimensional layered porous structure with tunable parameters, such as large interlayer spacing, high specific area, and large porous volume. They were then used as supports for Pd nanoparticles. As applied in coupling reactions of aryl halides with terminal alkynes, Pd@CS/AlMn-PM showed better comprehensive catalytic performance than Pd@PVP/AlMn-PM. This was mainly attributed to its higher specific area, stronger chelation to Pd species, and better solvent resistance.

Preparation of Dye Semiconductors via Coupling Polymerization Catalyzed by Two Catalysts and Application to Transistor.

Organic dye semiconductors have received increasing attention as the next generation of semiconductors, and one of their potential applications is as a core component of organic transistors. In this study, two novel diketopyrrolopyrrole (DPP) dye core-based materials were designed and separately prepared using Stille coupling reactions under different palladium catalyst conditions. The molecular weights and elemental compositions were tested to demonstrate that both catalysts could be used to successfully prepare materials of this structure, with the main differences being the weight-average molecular weight and the dispersion index. PDPP-2Py-2Tz I with a longer conjugation length exhibited better thermodynamic stability than the counterpart polymer PDPP-2Py-2Tz II. The intrinsic optical properties of the polymers were relatively similar, while the electrochemical tests showed small differences in their energy levels. The polymers obtained with different catalysts displayed similar and moderate electron mobility in transistor devices, while PDPP-2Py-2Tz I possessed a higher switching ratio. Our study provides a comparison of such dye materials under different catalytic conditions and also demonstrates the great potential of dye materials for optoelectronic applications.

Electrocatalytic three-component synthesis of 4-halopyrazoles with sodium halide as the halogen source.

The first example of the electrocatalytic multicomponent synthesis of 4-chloro/bromo/iodopyrazoles from hydrazines, acetylacetones and sodium halides under chemical oxidant- and external electrolyte-free conditions has been developed. Sodium halides played a dual role as a halogenation reagent and a supporting electrolyte. Mechanism studies revealed that the bromination reaction proceeded via an ionic pathway, whereas both chlorination and iodination proceeded via a radical pathway.

Real-Time Φ-OTDR Vibration Event Recognition Based on Image Target Detection.

Accurate and fast identification of vibration signals detected based on the phase-sensitive optical time-domain reflectometer (Φ-OTDR) is crucial in reducing the false-alarm rate of the long-distance distributed vibration warning system. This study proposes a computer vision-based Φ-OTDR multi-vibration events detection method in real-time, which can effectively detect perimeter intrusion events and reduce personnel patrol costs. Pulse accumulation, pulse cancellers, median filter, and pseudo-color processing are employed for vibration signal feature enhancement to generate vibration spatio-temporal images and form a customized dataset. This dataset is used to train and evaluate an improved YOLO-A30 based on the YOLO target detection meta-architecture to improve system performance. Experiments show that using this method to process 8069 vibration data images generated from 5 abnormal vibration activities for two types of fiber optic laying scenarios, buried underground or hung on razor barbed wire at the perimeter of high-speed rail, the system mAP@.5 is 99.5%, 555 frames per second (FPS), and can detect a theoretical maximum distance of 135.1 km per second. It can quickly and effectively identify abnormal vibration activities, reduce the false-alarm rate of the system for long-distance multi-vibration along high-speed rail lines, and significantly reduce the computational cost while maintaining accuracy.

Fabrication of novel electrochemical sensor based on bimetallic Ce-Ni-MOF for sensitive detection of bisphenol A.

In this paper, a novel bimetallic Ce-Ni metal-organic frameworks (Ce-Ni-MOF) are synthesized by hydrothermal reaction, using 1,3,5-benzenetricarboxylic acid as a ligand. In particular, the bimetallic Ce-Ni-MOF with the largest specific surface area and catalytic sites was synthesized when the molar ratio of Ce3+ to Ni2+ was 3:7. Bimetallic Ce-Ni-MOF is added to the traditional conductive material of multiwall carbon nanotubes (MWCNTs) to play their synergistic effect, improve the conductivity, specific surface area, and catalytic site of the MWCNTs. A novel bisphenol A (BPA) sensor was successfully prepared by a self-assembled multilayer strategy of Ce-Ni-MOF/MWCNTs modified glassy carbon electrodes (GCE). Field emission scanning electron microscopy, powder X-ray diffraction, and transmission electron microscope were carried out to characterize the Ce-Ni-MOF/MWCNTs. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used as a sensitive analytical method for the determination of BPA, and a wider linear dynamic range of BPA determination in 0.1 µmol·L-1 to 100 µmol·L-1 with a detection limit of 7.8 nmol·L-1 (S/N = 3). The proposed method was applied to measure the content of BPA in different brands of drinking water with satisfying recovery from 97.4 to 102.4%. Graphical abstract.

Recent advances in the use of microcarriers for cell cultures and their ex vivo and in vivo applications.

Microcarriers are 100- to 300-micron support matrices that permit the growth of adherent cells in bioreactor systems. They have a larger surface area to volume ratio in comparison to single cell monolayers, enabling cost-effective cell production and expansion. Microcarriers are composed of a solid matrix that must be separated from expanded cells during downstream processing stages. The detachment method is chosen on the basis of several factors like cell type, microcarrier surface chemistry, cell confluency and degree of aggregation. The development of microcarriers with a range of physiochemical properties permit controlled cell and protein associations that hold utility for novel therapeutics. In this review, we provide an overview of the recent advances in microcarrier cell culture technology. We also discuss its significance as an ex vivo research tool and the therapeutic potential of newly designed microcarrier systems in vivo.

CRISPR/Cas9 facilitates genomic editing for large-scale functional studies in pluripotent stem cell cultures.

Pluripotent stem cell (PSC) cultures form an integral part of biomedical and medical research due to their capacity to rapidly proliferate and differentiate into hundreds of highly specialized cell types. This makes them a highly useful tool in exploring human physiology and disease. Genomic editing of PSC cultures is an essential method of attaining answers to basic physiological functions, developing in vitro models of human disease, and exploring potential therapeutic strategies and the identification of drug targets. Achieving reliable and efficient genomic editing is an important aspect of using large-scale PSC cultures. The CRISPR/Cas9 genomic editing tool has facilitated highly efficient gene knockout, gene correction, or gene modifications through the design and use of single-guide RNAs which are delivered to the target DNA via Cas9. CRISPR/Cas9 modification of PSCs has furthered the understanding of basic physiology and has been utilized to develop in vitro disease models, to test therapeutic strategies, and to facilitate regenerative or tissue repair approaches. In this review, we discuss the benefits of the CRISPR/Cas9 system in large-scale PSC cultures.

One-step rapid synthesis of fluorescent silicon nanodots for a hydrogen peroxide-related sensitive and versatile assay based on the inner filter effect.

In this work, a kind of environment-friendly and water-dispersible silicon nanodot (SiND) was rapidly synthesized by using the mild reagents (3-aminopropyl)triethoxysilane (APTES) and glucose. It was found that the fluorescence of the as-prepared SiNDs can be quenched obviously by permanganate due to the inner filter effect. Inspired by this finding, a novel fluorescent sensor for sensitive detection of hydrogen peroxide (H2O2) was developed through the oxidation-reduction reaction between permanganate and H2O2. The detection limit of H2O2 is down to 2.8 nM. Since H2O2 is an important molecule and involved in various studies, this sensor could be applied in various H2O2-related biological analyses. As a proof-of-application demonstration, a sensitive biosensor for glucose detection was constructed through the catalytic oxidation of glucose to generate H2O2. The as-constructed sensor showed good linear response to glucose over the range from 0.16 to 16 µM with a detection limit of 0.11 µM. Moreover, the biosensor can be readily extended to other sensors for different targets, which indicates the broad applications of the proposed sensing strategy in biomedical analysis.

Rational Design of Yolk-Shell CuO/Silicalite-1@mSiO2 Composites for a High-Performance Nonenzymatic Glucose Biosensor.

In this study, an interface coassembly strategy is employed to rationally synthesize a yolk-shell CuO/silicalite-1@void@mSiO2 composite consisting of silicalite-1 supported CuO nanoparticles confined in the hollow space of mesoporous silica, and the obtained composite materials were used as a novel nonenzymatic biosensor for highly sensitive and selective detecting glucose with excellent anti-interference ability. The synthesis of CuO/silicalite-1@mSiO2 includes four steps: coating silicalite-1 particles with resorcinol-formaldehyde polymer (RF), immobilization of copper species, interface deposition of a mesoporous silica layer, and final calcination in air to decompose RF and form CuO nanoparticles. The unique hierarchical porous structure with mesopores and micropores is beneficial to selectively enrich glucose for fast oxidation into gluconic acid. Besides, the mesopores in the silica shell can effectively inhibit the large interfering substances or biomacromolecules diffusing into the void as well as the loss of CuO nanoparticles. The hollow chamber inside serves as a nanoreactor for glucose oxidation catalyzed by the active CuO nanoparticles, which are spatially accessible for glucose molecules. The nonenzymatic glucose biosensors based on CuO/silicalite-1@mSiO2 materials show excellent electrocatalytic sensing performance with a wide linear range (5-500 µM), high sensitivity (5.5 µA·mM-1·cm-2), low detection limit (0.17 µM), and high selectivity against interfering species. Furthermore, the unique sensors even display a good capability in the determination of glucose in real blood serum samples.