In Situ Growth of Columnar PEG on PEDOT and Its Antifouling Properties.

The antifouling properties of conductive polymers have received extensive attention for biosensor and bioelectronic applications. Polyethylene glycol (PEG) is a well-known antifouling material, but the controlled regulation of the surface topography of PEG without a template remains a challenge. Here, we show a columnar structure antifouling conductive polymer brush with enhanced antifouling properties and considerable conductivity. The method involves synthesizing the 3,4-ethylenedioxythiophene monomer modified with azide (EDOT-N3), the electropolymerization of PEDOT-N3, and the in situ growth of PEG polymer brushes on PEDOT through double-click reactions. The resultant columnar structure polymer brush exhibits high electrical conductivity (3.5 Ω·cm2), ultrahigh antifouling property, electrochemical stability (capacitance retention was 93.8% after 2000 cycles of CV scans in serum), and biocompatibility.

Exploring the Performance Improvement for CO2 Chemical Fixation in Zn/ZnMg-MOFs.

A new 3D zinc-based metal-organic framework {[Zn7L2(DMF)3(H2O)(OH)2]·5DMF}n (1) (H6L = 5,5',5″-(methylsilanetriyl) triisophthalic acid) was constructed with an organosilicon-based linker, where H6L is a tetrahedral structure furnished with rich -COO- chelating sites for Zn(II) immobilization. Compound 1 exhibited two types of irregular one-dimensional channels and a three-dimensional skeleton with large specific surface area, making it a promising catalytic platform. Moreover, by incorporation of the second metal ion into the inorganic node of framework 1, isomorphic bimetallic MOF ZnMg-1 was successfully synthesized. ZnMg-1 demonstrated enhanced catalytic activity compared to 1 under identical conditions. Contrast experiments and theoretical calculations indicate that bimetallic active sites play a facilitating role in the chemical fixation of epoxides and CO2. It indicated that efficient chemical fixation of CO2 to cyclic carbonates was obtained over isomorphic MOF catalysts 1 and ZnMg-1.

Polyoxometalate functionalized magnetic metal-organic framework with multi-affinity sites for efficient enrichment of phosphopeptides.

The reasonable design of metal-organic framework (MOF)-derived nanomaterial has important meaning in increasing the enrichment efficiency in the study of protein phosphorylation. In this work, a polyoxometalate (POM) functionalized magnetic MOF nanomaterial (Fe3O4@MIL-125-POM) was designed and fabricated. The nanomaterial with multi-affinity sites (unsaturated metal sites and metal oxide clusters) was used for the enrichment of phosphopeptides. Fe3O4@MIL-125-POM had high-efficient enrichment performance towards phosphopeptides (selectivity, a mass ratio of bovine serum albumin/α-casein/ß-casein at 5000:1:1; sensitivity, 0.1 fmol; satisfactory repeatability, ten times). Furthermore, Fe3O4@MIL-125-POM was employed to enrich phosphopeptides from non-fat milk digests, saliva, serum, and A549 cell lysate. The enrichment results illustrated the great potential of Fe3O4@MIL-125-POM for efficient identification of low-abundance phosphopeptides.

Cerium ions immobilized magnetic graphite nitride decorated with L-Alanyl-L-Glutamine as new chelator for enrichment of phosphopeptides.

Cerium ions immobilized magnetic graphite nitride material have been prepared using L-Alanyl-L-Glutamine as the new chelator. The resulting Fe3O4/g-C3N4-L-Ala-L-Gln-Ce4+, as an immobilized metal ion affinity chromatography (IMAC) sorbent, was reusable. This is due to the strong coordination interaction between L-Alanyl-L-Glutamine and cerium ions. After a series of characterizations, the magnetic nanocomposite showed high surface area, good hydrophilicity, positive electricity, and magnetic response. Fe3O4/g-C3N4-L-Ala-L-Gln-Ce4+ had high sensitivity (0.1 fmol), selectivity (α-/ß-casein/bovine serum albumin, 1:1:5000), and good recyclability (10 cycles). A total of 647 unique phosphopeptides mapped to 491 phosphoproteins were identified from A549 cell lysate by nano LC-MS analysis.

NiCoP/g-C3N4 Nanocomposites-Based Electrochemical Immunosensor for Sensitive Detection of Procalcitonin.

Herein, an ultra-sensitive and facile electrochemical biosensor for procalcitonin (PCT) detection was developed based on NiCoP/g-C3N4 nanocomposites. Firstly, NiCoP/g-C3N4 nanocomposites were synthesized using hydrothermal methods and then functionalized on the electrode surface by π-π stacking. Afterward, the monoclonal antibody that can specifically capture the PCT was successfully linked onto the surface of the nanocomposites with a 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-Hydroxysuccinimide (NHS) condensation reaction. Finally, the modified sensor was employed for the electrochemical analysis of PCT using differential Pulse Voltammetry(DPV). Notably, the larger surface area of g-C3N4 and the higher electron transfer capacity of NiCoP/g-C3N4 endow this sensor with a wider detection range (1 ag/mL to 10 ng/mL) and an ultra-low limit of detection (0.6 ag/mL, S/N = 3). In addition, this strategy was also successfully applied to the detection of PCT in the diluted human serum sample, demonstrating that the developed immunosensors have the potential for application in clinical testing.

Synthesis of Tetrahydrocarbazol-4-ones via Rh(III)-Catalyzed C-H Activation/Annulation of Arylhydrazines with Iodonium Ylides.

The rhodium(III)-catalyzed C-H activation followed by intramolecular annulation reactions between arylhydrazines and iodonium ylides under suitable conditions has been described. Tetrahydrocarbazol-4-ones are readily achieved with moderate to excellent yields. The synthetic protocol features a wide range of substrates with high functional group tolerance. The gram-scale reaction and derivatization of the product demonstrate the synthetic practicality and utilization of this method.

Layer-by-layer assembly of multilayered double hydroxides/polyoxometalate-coated magnetic nanoparticles for highly efficient phosphopeptide enrichment.

A layer-by-layer (LbL) assembly strategy was developed to prepare multilayered double hydroxide/polyoxometalate shell-coated magnetic nanoparticles. The introduction of functional shells not only offered abundant affinity sites of metal oxide and metal ions but also increased the surface area for the contact with targets. By combining the enrichment strategies of immobilized metal ion affinity chromatography and metal oxide affinity chromatography, the nanomaterial can capture phosphopeptides via a synergistic effect. The method presented a low detection limit of 0.1 fmol in combination with matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) analysis. The nanomaterial showed satisfactory selectivity (1:1:5000 M ratio of α-/ß-casein/bovine serum albumin), good recovery (92.07%), high adsorption capacity (117.6 mg g-1), and ten times reusability for capturing phosphopeptides.

Rare-Earth-Based Metal-Organic Frameworks as Multifunctional Platforms for Catalytic Conversion.

The development of catalytic conversion is very important for human society. In the catalytic process, metal-organic frameworks (MOFs) can be utilized to obtain effective catalysts for their porous structures and adjustable properties. In addition, the introduction of rare-earth (RE) elements with unique properties for catalysts can realize good catalytic performances. Thus, the RE-MOF related catalysts for catalytic conversion are summarized. Due to the cooperation of RE elements and porous MOF structures, the RE-based MOFs can be used as promising catalysts or precursors/supports for other catalysts in the areas of energy conversion, environmental governance, and organic synthesis. These aggregated studies highlight the RE-MOFs as promising candidates for catalytic conversion.

Strong adsorption, catalysis and lithiophilic modulation of carbon nitride for lithium/sulfur battery.

Lithium/sulfur (Li/S) batteries have emerged as one of the most promising next-generation energy storage systems with advantages of high theoretical energy density, low cost and environmental friendliness. However, problems regarding to severe shuttle effect of soluble polysulfide, poor electronic/ionic conductor of solid charged/discharged products (S8 and Li2S), and fatal swell of volume along with the growth of Li dendrites greatly deteriorate the sulfur utilization and capacity retention during extended charge-discharge cycles. With advantages of high nitrogen content, lithiophilic modulation and tunable charge density and charge transfer, carbon nitride (g-C3N4) has played a positive role in restricting the shuttle effects and dendrite formation. This minireview mainly discusses these research achievements of g-C3N4 in Li/S batteries, aiming to provide a basic understanding and direct guidance for further research and development of functionalized g-C3N4 materials in electrical energy storage. The two-dimensional (2D) structure of g-C3N4 with abundant hierarchical pores improves its accommodation capacity for sulfur by effectively confining the lithium polysulfides (LiPSs) into the pores, and provides favorable channels for ion diffusion. The rich nitrogen and carbon defects further offer more active sites for strongly adsorbing LiPSs and bridge electron transfer pathway at atomic scale for catalytic reactions to accelerate redox kinetics of Li/S conversion chemistry. Moreover, the features of lithiophilic wettability, high adsorption energy and densely distributed lithiophilic N of g-C3N4 provide a large number of adhesive sites for lithium cation (Li+) and disperse the nucleation sites to enable uniform nucleation and deposition of Li on the anode surface and to suppress formation and growth of Li dendrites. Finally, the g-C3N4 also effectively regulates the wettability between Li anode and solid inorganic electrolyte, and reduces the crystallinity of solid polymer electrolyte to enhance the Li+ migration ability and ionic conductivity.

Photocatalytic selective H2release from formic acid enabled by CO2captured carbon nitride.

The selective decomposition of formic acid (FA) traditionally needs to be carried out under high temperature with the noble metal-based catalysts. Meanwhile, it also encounters a separation of H2and CO2for pure H2production. The photocatalytic FA dehydrogenation under mild conditions can meet a growing demand for sustainable H2generation. Here, we reported a photocatalytic selective H2release from FA decomposition at low temperature for pure H2production by Pt/g-C3N4. Low-cost and easy-to-obtained urea was utilized to produce carbon nitride as the metal-free semiconductor photocatalyst, along with a photodeposition to obtain Pt/g-C3N4. The electrochemical evidences clearly demonstrate the photocatalytic activity of Pt/g-C3N4to produce H2and CO2in one-step FA decomposition. And, the impedance is the lowest under simulated solar light of 70 mW cm-2with a faster electron transfer kinetic. Under simulated solar light, H2production rate is up to 1.59 mmol · h-1· g-1for FA with concentration at 2.65 mol l-1, 1700 000 times larger than that under visible light and 1928 times under ultraviolet (UV) light. DFT calculations further elucidate that nitrogen (N) active site at the g-C3N4has an excellent adsorption towards CO2molecule capture. Then, H2molecules are selectively released to simultaneously separate H2and CO2in solution. Platinum (Pt) at Pt/g-C3N4as the catalytic site contributes into the acceleration of H2production.

Ternary flower-sphere-like MnO2-graphite/reduced graphene oxide nanocomposites for supercapacitor.

Chemical fabrication of a nanocomposite structure for electrode materials to regulate the ion diffusion channels and charge transfer resistances and Faradaic active sites is a versatile strategy towards building a high-performance supercapacitor. Here, a new ternary flower-sphere-like nanocomposite MnO2-graphite (MG)/reduced graphene oxide (RGO) was designed using the RGO as a coating for the MG. MnO2-graphite (MnO2-4) was obtained by KMnO4 oxidizing the pretreated graphite in an acidic medium (pH = 4). The GO coating was finally reduced by the NaBH4 to prepare the ternary nanocomposite MG. The microstructures and pore sizes were investigated by x-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and nitrogen adsorption/desorption. The electrochemical properties of MG were systematically investigated by the cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy in Na2SO4 solution. The MG as an electrode material for supercapacitor exhibits a specific capacitance of 478.2 and 454.6 F g-1 at a current density of 1.0 and 10.0 A g-1, respectively. In addition, the capacitance retention was 90% after 8,000 cycles. The ternary nanocomposite enhanced electrochemical performance originates from the specific flower-sphere-like morphology and coating architecture bringing higher specific surface area and lower charge transfer resistance (Rct).

Carbon nitride grafted waste-derived carbon as sustainable materials for lithium-sulfur batteries.

The synthesis of a sustainable material through carbon nitride (C3N4) chemically grafted on waste-derived carbon including carbonizing coals (PM), melamine-urea-formaldehyde resins (MUF-C-1100), and luffa cylindrical sponges (SG), respectively, and its application as sulfur cathode in lithium-sulfur (Li-S) batteries were demonstrated. The Li-S cell assembled by the sulfur (S) cathode with component from C3N4grafted coal-derived carbon (PM-CN) possesses a specific capacity of 1269.8 mA h g-1at 0.05 C. At 1 C, the initial specific capacity of PM cathode is only 380.0 mA h g-1, comparable to the PM-CN5 cathode of 681.9 mA h g-1, and PM-CN10 cathode of 580.7 mA h g-1, respectively. And, PM-CN 5 cathode presents the capacity retention of 75.9% with a coulomb efficiency (C.E.) of 97.3% after 200 cycles. The MUF-CN cathode gives a specific capacity of 1335.6 mA h g-1at 0.05 C, and the capacity retention of 66.7% with a C. E. of 93.6% after 300 cycles at 0.5 C. The SG-CN cathode had a specific capacity of 953.9 mA h g-1at 0.05 C, and capacity retention of 95.1% with a C. E. of 98.2% after 125 cycles at 1 C. The remarkable improved performances were mainly ascribed to the sustainable materials as S host with micro-meso pore and C3N4structure providing the strong affinity N sites to lithium polysulfides (LiPSs). This work provides an attractive approach for the preparation of sustainable materials by rational design of grafting C3N4to waste-derived carbons with functions as S cathode materials for high-performance Li-S batteries.

Design of Gd3+-immobilized two-dimensional magnetic magadiite nanosheets for highly selective enrichment of phosphopeptides.

Exfoliated magadiite nanosheets embedded with Fe3O4 were constructed. Advantage was taken of the strong coordination between the silanol groups in magadiite nanosheets and the Gd3+ ion to prepare the final adsorbent, Gd3+-immobilized magnetic magadiite nanosheets. The adsorbent with two-dimensional (2D) morphology offered high surface area and abundant Gd3+ contents for phosphopeptides enrichment, on which Fe3O4 with positive electricity incorporated the magnetic properties. Combining with matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI TOF-MS), the method showed low detection limit (0.05 fmol). The feasibility of using the 2D nanocomposite for phosphopeptides enrichment was demonstrated using mixtures of ß-casein and bovine serum albumin (1:5000). The standard deviation of captured phosphopeptides in three repeated experiments were in the range 0.15-0.42 (< 0.5% RSD). Further evaluation revealed that the nanocomposite was capable of enriching phosphopeptides from non-fat milk, human saliva, and serum. A novel Gd3+-immobilized two-dimensional magnetic magadiite nanosheets-based enrichment platform was designed. The developed material was employed as the adsorbent for the selective enrichment of phosphopeptides by coupling with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The material was successfully applied to enrich phosphopetides from standard peptide mixtures, nonfat milk, human saliva, and serum.

Multiresponsive Fluorescence "Turn ON-OFF" Switch on PB@EuW10/SiO2 Composite for Dual Spectral Detection of N2H4 and H2O2.

Herein, a fluorescence "turn ON-OFF" switch model PB@EuW10/SiO2 core@shell composite is designed and fabricated by coating EuW10-containing silica layer on Prussian blue (PB) nanoparticles via a facile method. It is found that the presence of PB can quench the photoluminescence of the composite which arises from EuW10. When hydrazine is mixed with the composite dispersion, PB can be reduced to Prussian white (PW), resulting in the decrease of UV absorption and the appearance of photoluminescence (turn ON). In addition, PW can also be converted back to PB, which is achieved by adding hydrogen peroxide, and the photoluminescence of the composite is quenched again (turn OFF). Thus, the composite is applied for N2H4 and H2O2 detection by fluorescence spectroscopy and UV-vis absorption spectroscopy. Wide linear ranges for N2H4 and H2O2 detection with low detection limits are found for both detection methods on the PB@EuW10/SiO2 core@shell composite. Besides, the color from light blue to colorless of the detection dispersion can also indicate the turn ON-OFF switch for fluorescence. Furthermore, the proposed model can also be extended to other composites.

Poly(3,4-ethylenedioxythiophene) Bearing Pyridylboronic Acid Group for Specific Recognition of Sialic Acid.

Conducting polymers tethered with molecular recognition elements are good candidates for biosensing applications such as detecting a target molecule with selectivity. We develop a new monomer, namely, 3,4-ethylenedioxythiophene bearing a pyridylboronic acid moiety (EDOT-PyBA), for label-free detection of sialic acid as a cancer biomarker. PyBA, which is known to show specific binding to sialic acid in acid conditions is used as a synthetic ligand instead of lectins. PyBA confirms the enhanced binding affinity for sialic acid at pH 5.0-6.0 compared with traditional phenylboronic acid. Poly(EDOT-PyBA) is electrodeposited on a planar glassy carbon electrode and the obtained film is successfully characterized by X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, water contact angle measurements, and electrochemical impedance spectroscopy. The specific interaction of PyBA with sialic acid at the solution/electrode interface is detected by differential pulse voltammetry in a dynamic range 0.1-3.0 mM with a detection limit of 0.1 mM for a detection time of 3 min. The sensitivity covers the total level of free sialic acid in human serum and the assay time is the shorter than that of other methods. The poly(EDOT-PyBA) electrode successfully detects spiked sialic acid in human serum samples. Owing to its processability, mass productivity, and robustness, polythiophene conjugated with "boronolectin" is a candidate material for developing point-of-care and wearable biosensors.

Selective Oxidation of Benzylic C-H Bonds Catalyzed by Cu(II)/{PMo12}.

Precise catalytic regulation of carbon radical generation by a highly active oxygen radical to abstract the H atom in a C-H bond is an effective method for the selective activation of C-H synthetic chemistry. Herein, we report a facile catalyst system with commercially available copper(II)/{PMo12} to form a tert-butanol radical intermediate for the selective oxidation of benzylic C-H bonds. The reaction shows a broad range of substrates (benzyl methylene, benzyl alcohols) with good functional group tolerance and chemical selectivity. The corresponding carbonyl compounds were synthesized with good yields under mild conditions. DFT calculations and experimental analysis further demonstrated a reasonable carbon radical mechanism for this type of organic transformation reaction.

pH-Zone-refining counter-current chromatography for two new lipo-alkaloids separated from refined alkaline extraction of Kusnezoff monkshood root.

An efficient and refined method for the separation of six aconitine-type alkaloids from the alkaline prepared "Kusnezoff monkshood root" was established. It is the first study that two new lipo-alkaloids were successfully isolated from refined sample by pH-zone-refining counter-current chromatography rather than synthetic method. It was of interest that a great deal of lipo-alkaloids was produced in crude extract from the alkalization of "Kusnezoff monkshood root." A refined sample method was proposed to enrich two types of alkaloids by liquid-liquid extraction, i.e. lipo-alkaloids and monoester-diterpenoid alkaloids. The pH-zone-refining counter-current chromatography was performed with an optimized two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (3:5:4:5, v/v), where upper organic phase was added to 3 mmol/L triethylamine as a retainer and lower aqueous mobile phase was added to 3 mmol/L hydrochloric acid as an eluter. As a result, six aconitum alkaloids, including two lipo-alkaloids (8-lino-14-benzoylaconine, 8-pal-14-benzoylaconine), three monoester-diterpenoid alkaloids (14-benzoylmesaconine, 14-benzoylaconine, beyzoyldeoxyaconine), and one aconine alkaloid (neoline) were acquired from the plant at the same time. The anti-inflammatory activities of the two new lipo-alkaloids were compared to the six alkaloids in vitro, in cyclo-oxygen-ase-2 inhibition assays. The separation mechanism of six alkaloids by pH-zone-refining counter-current chromatography was illustrated.

Jahn-Teller Disproportionation Induced Exfoliation of Unit-Cell Scale ϵ-MnO2.

Exfoliation of non-layered (structurally) bulk materials at the nanoscale is challenging because of the strong chemical bonds in the lattice, as opposed to the weak van der Waals (vdW) interactions in layered materials. We propose a top-down method to exfoliate ϵ-MnO2 nanosheets in a family of charge-ordered La1-x AEx MnO3 (AE=Ca, Sr, Ba) perovskites, taking advantage of the Jahn-Teller disproportionation effect of Mn3+ and bond-strength differences. ϵ-MnO2 crystallized into a nickel arsenide (NiAs) structure, with a thickness of 0.91 nm, displays thermal metastability and superior water oxidation activity compared to other manganese oxides. The exfoliation mechanism involves a synergistic proton-induced Mn3+ disproportionation and structural reconstruction. The synthetic method could also be potentially extended to the exfoliation of other two-dimensional nanosheet materials with non-layered structures.

Carbon Nitride Supramolecular Hybrid Material Enabled High-Efficiency Photocatalytic Water Treatments.

Surface defects in relation to surface compositions, morphology, and active sites play crucial roles in photocatalytic activity of graphitic carbon nitride (g-C3N4) material for highly reactive oxygen radicals production. Here, we report a high-efficiency carbon nitride supramolecular hybrid material prepared by patching the surface defects with inorganic clusters. Fe (III) {PO4[WO(O2)2]4} clusters have been noncovalently integrated on surface of g-C3N4, where the surface defects provide accommodation sites for these clusters and driving forces for self-assembly. During photocatalytic process, the activity of supramolecular hybrid is 1.53 times than pure g-C3N4 for the degradation of Rhodamine B (RhB) and 2.26 times for Methyl Orange (MO) under the simulated solar light. Under the mediation of H2O2 (50 mmol L-1), the activity increases to 6.52 times for RhB and 28.3 times for MO. The solid cluster active sites with high specific surface area (SSA) defect surface promoting the kinetics of hydroxide radicals production give rise to the extremely high photocatalytic activity. It exhibits recyclable capability and works in large-scale demonstration under the natural sunlight as well and interestingly the environmental temperature has little effects on the photocatalytic activity.

A Graphene-like Oxygenated Carbon Nitride Material for Improved Cycle-Life Lithium/Sulfur Batteries.

Novel sulfur (S) anchoring materials and the corresponding mechanisms for suppressing capacity fading are urgently needed to advance the performance of Li/S batteries. Here, we designed and synthesized a graphene-like oxygenated carbon nitride (OCN) host material that contains tens of micrometer scaled two-dimensional (2D) rippled sheets, micromesopores, and oxygen heteroatoms. N content can reach as high as 20.49 wt %. A sustainable approach of one-step self-supporting solid-state pyrolysis (OSSP) was developed for the low-cost and large-scale production of OCN. The urea in solid sources not only provides self-supporting atmospheres but also produces graphitic carbon nitride (g-C3N4) working as 2D layered templates. The S/OCN cathode can deliver a high specific capacity of 1407.6 mA h g(-1) at C/20 rate with 84% S utilization and retain improved reversible capacity during long-term cycles at high current density. The increasing micropores, graphitic N, ether, and carboxylic O at the large sized OCN sheet favor S utilization and trapping for polysulfides.