Controlling the Degree of Interpenetration in Chiral Three-Dimensional Covalent Organic Frameworks via Steric Tuning.

Network interpenetration plays a crucial role in functionalizing porous framework materials. However, controlling the degree of interpenetration in covalent organic frameworks (COFs) to influence their pore sizes, shapes, and functionalities still remains a significant challenge. Here, we demonstrate a steric tuning strategy to control the degree of COF interpenetration and modulate their physicochemical properties. By imine condensations of 1,1'-bi-2-naphthol-derived tetraaldehydes bearing different alkyl substituents with the monomer tetra(p-aminophenyl)-methane, we synthesized and characterized a family of two-component and three-component chiral COFs with different interpenetrated dia networks. The alkyl groups are periodically appended on the pore walls, and their types/contents that can be synthetically tuned control the interpenetration degree of COFs by minimizing repulsive interactions between the alkyl groups. Specifically, the COF with -OH groups adopts an interpenetrated dia-c5 topology, those with -OMe/-OEt groups take an interpenetrated dia-c4 topology, whereas those with the bulky -OnPr/-OnBu groups exhibit a noninterpenetrated dia-c1 topology. The multivariate COFs with both -OH and -OnBu groups display either a noninterpenetrated or dia-c5 topology, depending on the proportion of -OnBu groups. The extent of interpenetration in COFs significantly affects their porosity, thermal stability, and chemical stability, resulting in varying selective performances in the adsorption and separation of dyes and asymmetric catalysis. This work highlights the potential of using steric hindrance to tune and control interpenetration, porosity, stability, and functionalities of COFs materials, broadening the range of their applications.

Highly Flexible K-Intercalated MnO2 /Carbon Membrane for High-Performance Aqueous Zinc-Ion Battery Cathode.

The layered MnO2 is intensively investigated as one of the most promising cathode materials for aqueous zinc-ion batteries (AZIBs), but its commercialization is severely impeded by the challenging issues of the inferior intrinsic electronic conductivity and undesirable structural stability during the charge-discharge cycles. Herein, the lab-prepared flexible carbon membrane with highly electrical conductivity is first used as the matrix to generate ultrathin δ-MnO2 with an enlarged interlayer spacing induced by the K+ -intercalation to potentially alleviate the structural damage caused by H+ /Zn2+ co-intercalation, resulting in a high reversible capacity of 190 mAh g-1 at 3 A g-1 over 1000 cycles. The in situ/ex-situ characterizations and electrochemical analysis confirm that the enlarged interlayer spacing can provide free space for the reversible deintercalation/intercalation of H+ /Zn2+ in the structure of δ-MnO2 , and H+ /Zn2+ co-intercalation mechanism contributes to the enhanced charge storage in the layered K+ -intercalated δ-MnO2 . This work provides a plausible way to construct a flexible carbon membrane-based cathode for high-performance AZIBs.

Surface Reconstruction of Co4N Coupled with CeO2 toward Enhanced Alkaline Oxygen Evolution Reaction.

Constructing the active interface in a heterojunction electrocatalyst is critical for the electron transfer and intermediate adsorption (O*, OH*, and HOO*) in alkaline oxygen evolution reaction (OER) but still remains challenging. Herein, a CeO2/Co4N heterostructure is rationally synthesized through the direct calcination of Ce[Co(CN)6], followed by thermal nitridation. The in situ electrochemically generated CoOOH on the surface of Co4N serves as the active site for the OER, and the coupled CeO2 with oxygen vacancy can optimize the energy barrier of intermediate reactions of the OER, which simultaneously boosts the OER performance. Besides, electrochemical measurement results demonstrate that oxygen vacancies in CeO2 and optimized absorption free energy originating from the electron transfer between CeO2 and CoOOH contribute to enhanced OER kinetics. This work provides new insight into regulating the interface heterostructure to rationally design efficient OER electrocatalysts under alkaline conditions.

A two-dimensional zinc(II)-based metal-organic framework for fluorometric determination of ascorbic acid, chloramphenicol and ceftriaxone.

A two-dimensional zinc(II)-based metal-organic framework [Zn • (BA) • (BBI)] was synthesized from 1,2-benzenediacetic acid and 1,1'-(1,4-butanediyl) bis(imidazole) via a solvothermal reaction. The crystal exhibits good chemical stability in the pH range from 2 to 12, and strong fluorescence with excitation/emission maxima of 270/290 nm. The crystal is shown to by a viable fluorescent probe for the detection of ascorbic acid (AA) and the antibiotics chloramphenicol (CHL) and ceftriaxone (CRO). Fluorescence intensity of crystal dispersion is significantly quenched with increasing concentrations of AA/CHL/CRO. Quenching occurs even in the presence of other substances. The assay is fast (5 s) and has a low detection limit (1.6 ppb for AA, 12 ppb for CHL and 3.9 ppb for CRO). The crystal still has a good quenching effect on AA/CHL/CRO after washing and using for five times. The response of the probe is related to the interplay between the MOF and analytes via energy absorption competition. Graphical abstractSchematic diagram of preparing Zn • (BA) • (BBI) and responding to target analytes. BA: 1,2-phenyldiacetic acid; BBI: 1,1'-(1,4-butanediyl)bis(imidazole); Zn • (BA) • (BBI): Crystal chemical formula.

Electrochemiluminescence immunoassay for the prostate-specific antigen by using a CdS/chitosan/g-C3N4 nanocomposite.

An electrochemiluminescence (ECL) biosensor was fabricated for the evaluation of prostate specific antigen (PSA). The sensor was developed by successively modifying glassy carbon electrode (GCE) electrodes with CdS/Chito/g-C3N4 nanocomposites and DNA1 was labeled at the 5' end with thiol. The aptamer DNA was labeled at the 3' end with a quencher ferrocene (Fc) was ligated to DNA1 by the principle of complementary base pairing. In the absence of PSA, the ECL intensity signal is effectively quenches through the energy transfer and photoexcitation electron transfer between CdS/Chito/g-C3N4 emitter and quencher Fc. After incubation with target PSA, the aptamer DNA interacts with PSA and then moved away from the electrode surface together, which will recover the ECL intensity. Under the optimal conditions, the ECL intensity increases linearly with the logarithm of PSA concentration in the range of 1 pg·mL-1 to 100 ng·mL-1, and the detection limit is 0.14 pg·mL-1 (S/N = 3). The biosensor has been successfully applied to the determination of PSA in serum sample. Graphical abstractSchematic representation of the electrochemiluminescence sensor based on a CdS/chitosan/g-C3N4 nanocomposite, which can be applied to the determination of prostate specific antigen in serum.

A Cd-MOF as a fluorescent probe for highly selective, sensitive and stable detection of antibiotics in water.

Recently, the pollution and damage caused by antibiotics in water have aroused serious concerns. In this situation, it is extremely important to develop a highly effective approach to detect antibiotics in water. In this contribution, we built a Cd-MOF material with stable fluorescence properties, using bbi = 1,4-bis(2-methyl-imidazol-1-yl)butane and H2L = 1,2-phenylenediacetic acid as organic ligands and Cd(NO3)2·4H2O as the metal node. The highly selective response of this MOF probe to ceftriaxone sodium (an antibiotic) can reach up to the ppb level in water, along with a fast response time, acid and alkali resistance, and anti-interference ability.

Bottom-Up Assembly of a Highly Efficient Metal-Organic Framework for Cooperative Catalysis.

In this study, we demonstrate a bottom-up assembly of a monomeric copper complex and a two-dimensional (2-D) heterometallic metal-organic framework (MOF) from a carboxylate-functionalized tridentate Schiff base ligand and metal ions. The obtained 2-D MOF features a unique bimetallic copper center which is different from its monometallic precursor and acts as an efficient heterogeneous catalyst for the Friedel-Crafts reaction and Henry reaction. The MOF catalyst shows a remarkably superior activity compared to its homogeneous counterparts in a wide range of substrates. It is presumably ascribed to the dual activation of the substrates by the active bimetallic copper center confined in the MOF network, which is supported by the significant changes in catalytic activity at low catalyst/substrates ratios when using the 2-D MOF and its precursor as catalysts, respectively. Moreover, the MOF catalyst also shows an excellent stability and recyclability. Our work, therefore, provides a stepwise strategy to design a heterogeneous cooperative catalyst, by taking advantage of the modulated structure of MOF and tunable functionality of the tridentate Schiff base, with high performance in a variety of organic synthesis.

Photoelectrochemical immunoassay for human interleukin 6 based on the use of perovskite-type LaFeO3 nanoparticles on fluorine-doped tin oxide glass.

A film of perovskite-type LaFeO3 nanoparticles (NPs) was deposited on fluorine-doped tin oxide (FTO) conducting glass via dipping-lifting and calcination. Scanning electron microscopy shows that the NPs are evenly distributed on the surface of the glass. The modified glass was further coated with antibody against human interleukin 6 (IL-6) to result in a photoelectrochemical immunosensor for IL-6. The well-established photoelectrochemical immunoassay has a linear current response in the range of 0.1 pg·mL-1 to 0.1 µg·mL-1 and a detection limit as low as 33 fg·mL-1. Graphical abstract Schematic of a novel photoelectochemical immunoassay for the measurement of IL-6 based on perovskite-type LaFeO3 nanoparticles. The immunoassay had a higher sensitivity and may also be applied to other bioanalysis and environment monitoring.

Synthesis of TiO2-loaded Co0.85Se thin films with heterostructure and their enhanced catalytic activity for p-nitrophenol reduction and hydrazine hydrate decomposition.

P-nitrophenol (4-NP) and hydrazine hydrate are considered to be highly toxic pollutants in wastewater, and it is of great importance to remove them. Herein, TiO2-loaded Co0.85Se thin films with heterostructure were successfully synthesized by a hydrothermal route. The as-synthesized samples were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, transmission electron microscopy and selective-area electron diffraction. The results demonstrate that TiO2 nanoparticles with a size of about 10 nm are easily loaded on the surface of graphene-like Co0.85Se nanofilms, and the NH3 · H2O plays an important role in the generation and crystallization of TiO2 nanoparticles. Brunauer-Emmett-Teller measurement shows that the obtained nanocomposites have a larger specific surface area (199.3 m(2) g(-1)) than that of Co0.85Se nanofilms (55.17 m(2) g(-1)) and TiO2 nanoparticles (19.49 m(2) g(-1)). The catalytic tests indicate Co0.85Se-TiO2 nanofilms have the highest activity for 4-NP reduction and hydrazine hydrate decomposition within 10 min and 8 min, respectively, compared with the corresponding precursor Co0.85Se nanofilms and TiO2 nanoparticles. The enhanced catalytic performance can be attributed to the larger specific surface area and higher rate of interfacial charge transfer in the heterojunction than that of the single components. In addition, recycling tests show that the as-synthesized sample presents stable conversion efficiency for 4-NP reduction.

Self-catalytic polymerization of a water-soluble selenium/polypyrrole nanocomposite and its nonlinear optical properties.

A facile one-step method for the synthesis of a water-soluble selenium/polypyrrole (Se/PPy) nanocomposite was developed. In the aqueous synthesis process, the pyrrole acted as a reductant for the reduction of H2SeO3, and then the elemental Se formed in situ acted as a catalyst for the polymerization of pyrrole. The characterization results show that the as-obtained composite (Se/PPy) is a spherical (Φ80 nm) product that is made up of amorphous Se particles coated by PPy layers. The formation mechanism and influence factors of the products were discussed, based on a series of experiments. It is proposed that remainder H2SeO3 adsorbed on the PPy chains increased the water-solubility and conductivity of the Se/PPy nanocomposite. Significantly, relying on the synergistic effect of photo-conductive Se nanoparticles and electric-conductive PPy molecules, the Se/PPy nanocomposite possesses a large two-photon absorption (2PA) cross-section and good optical limiting properties, which were demonstrated by the Z-scan technique using a femtosecond laser. We believe that this work should be an interesting strategy for developing polymer composites with excellent optoelectrical properties.

Multicolor Fluorescent Inks Based on Lanthanide Hybrid Organogels for Anticounterfeiting and Logic Circuit Design.

With the rapid development of information technology, the encrypted storage of information is becoming increasingly important for human life. The luminescent materials with a color-changed response under physical or chemical stimuli are crucial for information coding and anticounterfeiting. However, traditional fluorescent materials usually face problems such as a lack of tunable fluorescence, insufficient surface-adaptive adhesion, and strict synthesis conditions, hindering their practical applications. Herein, a series of luminescent lanthanide hybrid organogels (Ln-MOGs) were rapidly synthesized using a simple method at room temperature through the coordination between lanthanide ions and 2,6-pyridinedicarboxylic acid and 5-aminoisophthalic acid. And the multicolor fluorescent inks were also prepared based on the Ln-MOG and hyaluronic acid, with the advantages of being easy to write, color-adjustable, and water-responsive discoloration, which has been applied to paper-based anticounterfeiting technology. Inspired by the responsiveness of the fluorescent inks to water, we designed a logic system that can realize single-input logic operations (NOT and PASS1) and double-input logic operations (NAND, AND, OR, NOR, XOR). The encryption of a binary code can be actualized utilizing different luminescent response modes based on the logic circuit system. By adjusting the energy sensitization and luminescence mechanism of lanthanide ions in the gel structure, the information reading and writing ability of the fluorescent inks were verified, which has great potential in the field of multicolor pattern anticounterfeiting and information encryption.

Rapid synthesis and electrochemiluminescence behavior of CdTe nanoribbons.

A rapid chemical method has been developed for the synthesis of the CdTe nanoribbons with cubic crystalline phase. The method is based on the template-engaged synthesis in which the Te nanowires were used as template reagents. On the basis of a series of experiments and characterizations, the electrochemical property of CdTe nanoribbons was determined by the voltammetric technique. Furthermore, electrochemiluminescence property of CdTe nanoribbons was investigated. The results show that CdTe nanoribbons are helpful to obtain stable electrochemiluminescence emission for 1200 seconds.

Nonsteroidal anti-inflammatory drug monitoring in serum: a Tb-MOF-based luminescent mixed matrix membrane detector with high sensitivity and reliability.

The identification of drugs or biomolecules for public health monitoring requires facile analytical technologies with excellent sensitivity, portability and reliability. In the past decades, different sensing materials have inspired the development of various bioanalytical strategies. However, sensing platforms based on powder materials are not suitable for medical diagnosis, which limits further exploration and application of biosensors. Herein, a point-of-care testing (POCT) membrane was designed from an energy competition mechanism and achieved the detection of the nonsteroidal antiphlogistic diclofenac, and exhibited remarkable testing efficacy at the ppb level. The mixed matrix membrane (MMM) sensor consists of electrospun polyacrylonitrile nanofibers and luminescent Tb-MOFs and possess the advantages of high stability, outstanding anti-interference ability, efficient detection (LOD = 98.5 ppb) and easy visual recognition. Furthermore, this MMM sensor exhibits excellent recyclability in serum, which is beneficial for developing a portable and convenient device to distinguish diclofenac in practical sensing applications. Meanwhile, the feasibility and mechanism of this recyclable sensor were verified by theory and experiments, indicating that it is a promising device for diclofenac detection in biological environments to evaluate the toxic effect caused by the accumulation of nonsteroidal drugs.

Direct electrochemistry and electrocatalytic behavior of hemoglobin entrapped in Ag@C nanocables/gold nanoparticles nanocomposites film.

Direct electrochemistry of hemoglobin (Hb) was successfully fabricated by immobilizing Hb on the nanocomposites containing of Ag@C nanocables and Au nanoparticles (AuNPs) modified glassy carbon electrode (GCE). The immobilized Hb retained its biological activity and shown high catalytic activities to the reduction of H2O2 by circular dicroism (CD) spectrum, fourier transform infrared (FT-IR) spectrum and cyclic voltammetry (CV). Experimental conditions such as scan rate and pH Value were studied and optimized. The results indicated that the resulting biosensor are linear to the concentrations of H2O2 in the ranges of 6.67 x 10(-7)-2.40 x 10(5) M, and the detection limit is 2.02 x 10(-7) M. The electrochemical biosensor has also high stability and good reproducibility.

Synthesis and electrochemical property of Bi2Se3 nanotubes with laminar surface.

A novel hydrothermal method has been developed for the preparation of Bi2Se3 nanotubes with the laminar surface. The method is based on the template-engaged synthesis in which the as-prepared Se nanotubes were used as template reagent. The morphology, constitution and crystalline phase of the products as-obtained were characterized by SEM, XRD and XPS. On the basis of a series of experiments and characterizations, the effect factors (such as the reaction temperature and the atom ratio of Bi and Se in the precursors) and the formation mechanism of the Bi2Se3 nanotubes were discussed. Furthermore, the electrochemical property of the Bi2Se3 nanotubes was determined by the voltammetric technique, and the significant results were obtained.

Coordination-induced spontaneous resolution of a TPPE-based MOF and its use as a crystalline sponge in guest determination.

In this work, by virtue of a coordination-induced fixation of the propeller-like conformation of the tetraphenylethylene (TPE) backbone, we achieved a spontaneous resolution of conglomerate-forming enantiomers of [Co(TPPE)Cl2]·4DMF (1M and 1P), as unambiguously probed by single-crystal X-ray crystallography. Benefitting from the robust, accessible, and electron-rich 1D channels, the chiral MOF turned out to be a good 'crystalline sponge' to adsorb and determine six liquid guests, of which two (2-butanol and 2-butylamine) are crystallized in an enantiospecific manner.

A mild reduction of Co-doped MnO2 to create abundant oxygen vacancies and active sites for enhanced oxygen evolution reaction.

Efficient and non-precious-metal-based catalysts (e.g., manganese-based oxides) for the oxygen evolution reaction (OER) remain a substantial challenge. Creation of oxygen vacancies of manganese-based oxides with the aim to enhance their intrinsic activities is rarely reported, and there is a critical requirement for a mild and facile synthesis strategy to create abundant oxygen vacancies on manganese-based oxides. Herein, Co-doped MnO2 nanowires were reduced by NaBH4 solution at room temperature; then, MnCo2O4.5 nanosheets with abundant oxygen vacancies and active sites were formed on the surface of Co-doped MnO2 nanowires. Benefiting from the reduction strategy, the fabricated hierarchical Co-doped-MnO2@MnCo2O4.5 nanowire/nanosheet nanocomposites exhibit higher catalytic activity (an overpotential of 250 mV at a current density of 10 mA cm-2 in 1.0 M KOH solution) than pristine Co-doped MnO2 nanowires. The calculated TOF of Co-doped-MnO2@MnCo2O4.5 is 0.034 s-1 at the overpotential of 300 mV, which is 136-fold higher than that of Co-doped-MnO2. The excellent OER performance was attributed to the synergistic advantages of abundant oxygen vacancies and active sites over the hierarchical nanowire-nanosheet architectures.

A novel self-assembled-derived 1D MnO2@Co3O4 composite as a high-performance Li-ion storage anode material.

Manganese dioxide (MnO2) is a high-performance anodic material and applied widely in lithium-ion batteries (LIBs). However, some intrinsic limitations originate from the low ionic conductivity, high polarization, and severe volume expansion of this type of material. In this work, we generated a one-dimensional porous MnO2@Co3O4 composite from a MnOOH@ZIF-67 precursor, which is synthesized via a self-assembly strategy. The one-dimensional porous structure provided more active sites and shorter-ion/electron-diffusion distance, thereby enabling higher Li+ storage capacity and better rate capability than a transition metal oxide alone. The Co3O4 coating buffered the volume change during Li+ insertion/extraction, leading to increased cycling stability of the electrode. When evaluated as the anode of LIBs, MnO2@Co3O4 exhibited a reversible capacity of 647 mA h g-1 at 2000 mA g-1 after 400 cycles. This excellent performance indicated that the MnO2@Co3O4 material could be an attractive potential candidate for Li+ storage.

Synthesis of novel C-doped g-C3N4 nanosheets coupled with CdIn2S4 for enhanced photocatalytic hydrogen evolution.

Photocatalytic hydrogen generation from water splitting has become a favorable route for the utilization of solar energy. An effective strategy, the combination of C-doping with nanocomposite semiconductors, is presented in this work. C-doped g-C3N4 (CCN) was prepared by supramolecular self-assembly and subsequently a number of CdIn2S4/CCN composite photocatalysts were designed and fabricated though in situ decoration of CdIn2S4 crystals on the surface of CCN nanosheets via a hydrothermal method. This unique architecture was able to efficiently promote the transfer and separation of photon-generated charges, enhance light absorption, and significantly increase photocatalytic H2 production. Detailed characterization was performed to analyze the crystal structure, morphology, elementary composition, optical properties and catalytic mechanism. The CdIn2S4/CCN nanocomposites with optimal CdIn2S4 content exhibited a maximum H2 production rate of 2985 µmol h-1 g-1, almost 15 times more than that obtained using pure g-C3N4 (205 µmol h-1 g-1). In addition, the hybrid photocatalysts display good recycling stability under visible-light irradiation. This research may provide promising information for the preparation of more efficient multifunctional hybrid photocatalysts with excellent stability in fine chemical engineering.

Electrochemiluminescent biosensor with DNA link for selective detection of human IgG based on steric hindrance.

A highly selective DNA-based electrochemiluminescence (ECL) based biosensor is described for the detection of human IgG. It is exploiting the effect of steric hindrance that affects the strength of the ECL signal in the presence of IgG. Digoxin-linked signaling DNA was specifically bound to IgG, and this causes steric hindrance which limits the ability of DNA to hybridize with capturing DNA attached to a gold electrode. Europium (II) doped CdSe quantum dots were covalently linked to the DNA in order to generate the ECL signal. Using this steric hindrance hybridization method, the ECL signal of the biosensor were proportional to the concentration of IgG with a wide linear range and a 14 pM detection limit. Conceivably, the method can be expanded to the detection of a wide range of proteins for which homologous recognition elements are available.