Enrichment of Phosphopeptides Based on Zirconium Phthalocyanine-Modified Magnetic Nanoparticles.

Highly selective extraction of phosphopeptides is necessary before mass spectrometry (MS) analysis. Herein, zirconium phthalocyanine-modified magnetic nanoparticles were prepared through a simple method. The Fe-O groups on Fe3O4 and the zirconium ions on phthalocyanine had a strong affinity for phosphopeptides based on immobilized metal ion affinity chromatography (IMAC). The enrichment platform exhibited low detection limit (0.01 fmol), high selectivity (α-/ß-casein/bovine serum albumin, 1/1/5000), good reusability (10 circles), and recovery (91.1 ± 1.1%) toward phosphopeptides. Nonfat milk, human serum, saliva, and A549 cell lysate were employed as actual samples to assess the applicability of the enrichment protocol. Metallo-phthalocyanine will be a competitive compound for designing highly efficient adsorbents and offers a new approach to phosphopeptide analysis.

Zirconium-rich magnetic polyoxometalate-based metal-organic framework: Tailored for phosphopeptide analysis from lung cancer A549 cells.

Polyoxometalate-based metal-organic frameworks (POMOFs) have become a promising affinity material for separation and enrichment. The analysis of protein phosphorylation represents a challenge for the development of efficient enrichment materials. Here, a novel zirconium-rich magnetic POMOF was successfully designed and prepared for the enrichment of phosphopeptides. The binding affinity of the nanomaterial partly came from Fe-O clusters in the MOF. The Lewis acid-base interactions between V-O clusters and zirconium ions in V10O28-Zr4+ and phosphate groups in phosphopeptides further strengthened the enrichment ability. The zirconium-rich magnetic POMOF was employed to capture phosphopeptides from non-fat milk, human saliva, and serum. Additionally, 748 unique phosphopeptide peaks were detected from the tryptic digests of lung cancer A549 cell proteins with a high specificity (86.9 %). POMOFs will become an active competitor for the design of protein affinity materials and will provide a new approach for phosphopeptide analysis.

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.

Preparation of high-efficiency titanium ion immobilized magnetic graphite nitride nanocomposite for phosphopeptide enrichment.

BACKGROUND: Protein phosphorylation has been implicated in life processes including molecular interaction, protein structure transformation, and malignant disease. An in-depth study of protein phosphorylation may provide vital information for the discovery of early biomarkers. Mass spectrometry (MS)-based techniques have become an important method for phosphopeptide identification. Nevertheless, direct detection remains challenging because of the low ionization efficiency of phosphopeptides and serious interference from non-phosphopeptides. There is a great need for an efficient enrichment strategy to analyze protein phosphorylation prior to MS analysis. RESULTS: In this study, a novel nanocomposite was prepared by introducing titanium ions into two-dimensional magnetic graphite nitride. The nanocomposite was combined with immobilized metal ion affinity chromatography (IMAC) and anion-exchange chromatography mechanisms for phosphoproteome research. The nanocomposite had the advantages of a large specific surface (412.9 m2 g-1), positive electricity (175.44 mV), and excellent magnetic property (35.7 emu g-1). Moreover, it presented satisfactory selectivity (α-casein:ß-casein:bovine serum albumin = 1:1:5000), a low detection limit (0.02 fmol), great recyclability (10 cycles), and high recovery (92.8%). The nanocomposite demonstrated great practicability for phosphopeptides from non-fat milk, human serum, and saliva. Further, the nanocomposite was applied to enrich phosphopeptides from a more complicated specimen, A549 cell lysate. A total of 890 phosphopeptides mapping to 564 phosphoproteins were successfully detected with nano LC-MS. SIGNIFICANCE: We successfully designed and developed an efficient analysis platform for phosphopeptides, which includes protein digestion, phosphopeptide enrichment, and MS detection. The MS-based enrichment platform was further used to analyze phosphopeptides from complicated bio-samples. This work paves the way for the design and preparation of graphite nitride-based IMAC materials for phosphoproteome analysis.

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.

Effective Enrichment of Phosphopeptides Using Magnetic Polyoxometalate-Based Metal-Organic Frameworks.

In this study, magnetic polyoxometalate-based metal-organic frameworks (Fe3O4-POMOFs) were designed and applied to the enrichment of phosphopeptides. Thanks to the abundant metal oxide and metal ion sites, the material had a strong affinity for phosphopeptides. Simultaneously, the high amount of amino and guanidyl groups provided hydrophilicity and positive charge for phosphopeptide capture. By coupling with MS detection, the established platform possessed good reusability, high sensitivity (0.01 fmol), and high selectivity (α-casein/ß-casein/bovine serum albumin = 1:1:5000). Furthermore, the method was successfully used for the detection of phosphopeptides in nonfat milk, human serum, saliva, and A549 cell lysate, showing great potential for practical application.

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.

Activating Octahedral Center in Co-Doped NiFe2 O4 via Bridging Amorphous MoSx for Electrocatalytic Water Oxidation: A Case for eg Orbital Regulation in Spinel Oxide.

Moderate eg filling for octahedral metal cations (MOh ) is strongly correlated with the electrocatalytic water oxidation performance in the oxides system. Here, the eg fillings of NiOh and FeOh in NiFe2 O4 -based spinel are controllably regulated by introducing an external radical of catalytically inactive MoSx as an electron acceptor via a novel ultrasonic anchored pyrolysis strategy. The electron occupied in eg orbit of MOh emigrates with the amount of MoS hanging on the apical of octahedral sites, and results in a salutary transition from high to medium eg occupancy state, as confirmed by the X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. In addition, benefiting from the abundant unsaturated S atoms in amorphous MoSx , the MOh at the surface furthest activates and consequently shows a superior water oxidation performance. Density functional theory also reveals that the eg fillings of Ni and Fe decrease to 1.4 and 1.2 after MoSx modification, which can effectively reduce the free energy of the OOH* intermediates in the oxygen evolution reaction process. This work opens an avenue for further releasing the electrocatalytic activity of octahedral sites through bridging external phases with rational electron-capturing/donating capability.

Unsupported nanoporous gold catalyst for highly selective hydroamination of alkynes.

An efficient and highly selective heterogeneous catalyst system for hydroamination of alkynes was developed using unsupported gold nanopores (AuNPore) for the first time. The AuNPore-catalyzed highly regioselective hydroamination of alkynes proceeded smoothly without any additive and solvent under mild conditions (rt-50 °C) to yield Markovnikov imines in satisfactory to excellent yields. No gold leached from AuNPore during the hydroamination of alkynes. Moreover, the catalyst was easily recovered and reused without any loss of catalytic activity. A one-pot, two-step procedure using a single AuNPore catalyst has been devised to produce secondary amines derived from readily available alkynes and anilines with high atom efficiency.

Design of two-dimensional molybdenum trioxide-immobilized magnetic graphite nitride nanocomposites with multiple affinity sites for phosphopeptide enrichment.

Here, two-dimensional magnetic graphite nitride nanosheets were synthesized, over which molybdenum trioxide was distributed evenly. The magnetic nanocomposite served as an enrichment platform for phosphopeptides based on metal oxide affinity chromatography and anion-exchange chromatography. Owing to the abundant affinity sites, positive electricity, and large surface area, the nanocomposite had high selectivity (α-casein/ß-casein/bovine serum albumin, 1:1:5000), sensitivity (0.1 fmol), quantitative recovery (91.3%), and good recyclability (10 cycles). The nanocomposite also showed good enrichment performance for phosphopeptides from non-fat milk, human serum, saliva, and A549 cell lysate. The results demonstrated the value of this material in phosphorylated proteomics.

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.

A Facile Fabrication of CdSe/ZnS QDs-Block Copolymer Brushes-Modified Graphene Oxide Nanohybrid with Temperature-Responsive Behavior.

In this paper, we described a straightforward one-step chemical method for the synthesis of semiconductor quantum dots(QDs)-block copolymer brushes functionalized graphene oxide(GO) fluorescence nanohybrids. The azobenzene-terminated block copolymer poly(N-isopropylacrylamid)-b-poly(styrene-co-5-(2-methacryoylethyloxymethyl)-8-quinolinol)(PNIPAM-b-P(St-co-MQ)) was modified on the surface of GO sheets via host-guest interactions between ß-cyclodextrin-modified GO and azobenzene moieties, and simultaneously CdSe/ZnS QDs were integrated on the block copolymer brushes through the coordination between 8-hydroxyquinoline units in the polymer brushes and CdSe/ZnS QDs. The resulting fluorescence nanohybrid exhibited dual photoluminescence at 620 nm and 526 nm, respectively, upon excitation at 380 nm and LCST-type thermo-responsive behavior which originated from the change in the PNIPAM conformation in the block copolymer brushes of GO sheets.

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.

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.

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.

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.

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.

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).

Enhancing Methane Aromatization Performance by Reducing the Particle Size of Molybdenum Oxide.

Efficient use of natural gas to produce aromatics is an attractive subject; the process requires catalysts that possess high-performance active sites to activate stable C-H bonds. Here, we report a facile synthetic strategy to modify HMCM-49 with small molybdenum oxide nanoparticles. Due to the higher sublimability of nano-MoO3 particles than commercial MoO3, they more easily enter into the channels of HMCM-49 and associate with Brønsted acid sites to form active MoCx-type species under calcination and reaction conditions. Compared with commercial MoO3 modified MCM-49, nano-MoO3 modified MCM-49 exhibits higher methane conversion (13.2%), higher aromatics yield (9.1%), and better stability for the methane aromatization reaction.