Evaluating a four-directional benzene-centered aliphatic polyamine curing agent for epoxy resins

A four-directional benzene-centered aliphatic polyamine, MXBDP, with high functionality and low volatility, is used to cure epoxy resin (DGEBA). Herein we originally report the isothermal cure kinetics and dynamic mechanical properties of DGEBA/MXBDP. Differential scanning calorimetry confirms that MXDBP is more reactive than commercial linear metaxylenediamine and branched Jeffamine T-403 and the isothermal curing reaction is autocatalytic. The Kamal model is found to be able to well describe the curing rate up to the onset of diffusion control, and the excellent match over the whole conversion range is achieved using the extended Kamal model. Interestingly, the isoconversional kinetic analysis indicates that the effective reaction activation energy (E _α ) changes substantially with conversion, and ultimately decreases to a very small value (<10 kJ mol^?1) because of the diffusion-controlled reaction kinetics. Then, dynamic mechanical analysis reveals that DGEBA/MXBDP exhibits the higher α- and β-relaxation temperatures and the much higher crosslink density than DGEBA/metaxylenediamine. Our experiment results support that MXBDP has the high reactivity and improved thermal resistance in combination with the advantages of the high functionality, low volatility and decreased CO₂ absorption. Therefore, MXBDP may be especially suitable for room temperature-cure epoxy coatings and adhesives.     

Electrodeposited nanogold decorated graphene modified carbon ionic liquid electrode for the electrochemical myoglobin biosensor

In this paper, a carbon ionic liquid electrode (CILE) was fabricated using ionic liquid 1-hexylpyridinium hexafluorophosphate as modifier, which was further in situ electrodeposited with graphene (GR) and gold nanoparticles step by step to get an Au/GR nanocomposite modified CILE. Myoglobin (Mb) was further immobilized on the Au/GR/CILE surface with Nafion film to get the modified electrode denoted as Nafion/Mb/Au/GR/CILE. Cyclic voltammetric experiments indicated that a pair of well-defined quasi-reversible redox peaks appeared in pH 3.0 phosphate buffer solution with the formal potential (E ^0′) located at ?0.197 V (vs. saturated calomel electrode), which was the typical characteristics of Mb heme Fe(III)/Fe(II) redox couples. Thus, the direct electron transfer rate between Mb and the modified electrode was promoted due to the high conductivity and increased surface area of Au/GR nanocomposite present on electrode surface. Based on the cyclic voltammetric data, the electrochemical parameters of Mb on the modified electrode were calculated. The Mb-modified electrode showed excellent electrocatalytic activities towards the reduction of trichloroacetic acid and H₂O₂ with wider linear range and lower detection limit. Using GR and Au nanoparticles modified CILE, a new third-generation electrochemical Mb biosensor was constructed with good stability and reproducibility.     

Improved electrochemical performance of nano-crystalline Li2FeSiO4/C cathode material prepared by the optimization of sintering temperature

Li₂FeSiO₄/C cathode materials have been prepared using the conventional solid-state method by varying the sintering temperature (650 °C, 700 °C and 750 °C), and the structure and electrochemical performance of Li₂FeSiO₄/C materials are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge–discharge tests, respectively. The results show that Li₂FeSiO₄ nano-crystals with a diameter of about 6–8 nm are inbedded in the amorphous carbon, and the Li₂FeSiO₄/C material obtained at 700 °C exhibits an initial discharge capacity of 195 mA?h g^?1 at 1/16 C in the potential range of 1.5–4.8 V. The excellent electrochemical performance of Li₂FeSiO₄/C attributes to the improvement of conductivity and reduction of impurity by the optimization of the sintering temperature.     

Phase Stability and Elastic Properties of Chromium Borides with Various Stoichiometries

Phase stability is important to the application of materials. By first‐principles calculations, we establish the phase stability of chromium borides with various stoichiometries. Moreover, the phases of CrB₃ and CrB₄ have been predicted by using a newly developed particle swarm optimization (PSO) algorithm. Formation enthalpy–pressure diagrams reveal that the MoB‐type structure is more energetically favorable than the TiI‐type structure for CrB. For CrB₂, the WB₂‐type structure is preferred at zero pressure. The predicted new phase of CrB₃ belongs to the hexagonal P‐6m2 space group and it transforms into an orthorhombic phase as the pressure exceeds 93 GPa. The predicted CrB₄ (space group: Pnnm) phase is more energetically favorable than the previously proposed Immm structure. The mechanical and thermodynamic stabilities of predicted CrB₃ and CrB₄ are verified by the calculated elastic constants and formation enthalpies. The full phonon dispersion calculations confirm the dynamic stability of WB₂‐type CrB₂ and predicted CrB₃. The large shear moduli, large Young’s moduli, low Poisson ratios, and low bulk and shear modulus ratios of CrB₄? PS_C and CrB₄? PS_D indicate that they are potential hard materials. Analyses of Debye temperature, electronic localization function, and electronic structure provide further understanding of the chemical and physical properties of these borides.     

Visible‐Light‐Active Elemental Photocatalysts

Seeking visible‐light‐active photocatalysts for efficient solar‐energy conversion has become an intensifying endeavor worldwide. In this concept paper, general requirements for finding new visible‐light‐active photocatalysts are briefly introduced, and recent progress in exploring elemental photocatalysts for clean‐energy generation and environmental remediation are reviewed. Finally, opportunities and challenges facing elemental photocatalysts are discussed.     

Ion mobility-mass correlation trend line separation of glycoprotein digests without deglycosylation

A high-throughput ion mobility mass spectrometer (IMMS) was used to rapidly separate and analyze peptides and glycopeptides derived from glycoproteins. Two glycoproteins, human α-1-acid glycoprotein and antithrombin III were digested with trypsin and subjected to electro-spray traveling wave IMMS analysis. No deglycosylation steps were performed; samples were complex mixtures of peptides and glycopeptides. Peptides and glycosylated peptides with different charge states (up to 4 charges) were observed and fell on distinguishable trend lines in 2-D IMMS spectra in both positive and negative modes. The trend line separation patterns matched between both modes. Peptide sequence was identified based on the corresponding extracted mass spectra and collision induced dissociation (CID) experiments were performed for selected compounds to prove class identification. The signal-to-noise ratio of the glycopeptides was increased dramatically with ion mobility trend line separation compared to non-trend line separation, primarily due to selection of precursor ion subsets within specific mobility windows. In addition, isomeric mobility peaks were detected for specific glycopeptides. IMMS demonstrated unique capabilities and advantages for investigating and separating glycoprotein digests in this study and suggests a novel strategy for rapid glycoproteomics studies in the future.     

Self‐Assembly of Anionic Porphyrins and Alkaline or Alkaline Earth Metal Ions Mediated by Cucurbit[7,8]uril

Nanoscaled coordination polymers based on biologically prevalent ions have potential applications in drug delivery and biomedical imaging. Herein, coordination polymer nanoparticles of anionic porphyrins, including meso‐tetra(4‐carboxyphenyl)‐porphyrin (H₂TCPP^4?) and meso‐tetra(4‐sulfonatophenyl)‐porphyrin (H₂TPPS^4?), and alkaline or alkaline earth metal cations, such as K⁺ and Ca²⁺, were constructed in aqueous solution in the presence of cucurbit[7]uril (CB7) or cucurbit[8]uril (CB8). UV/Vis absorption and fluorescence spectroscopy, dynamic light scattering (DLS), scanning electron spectroscopy (SEM), and atomic force microscopy (AFM) were applied to explore the assembly and particle formation of porphyrin anions and metal cations mediated by CBn. The particle size depends on the kinds of CBn and metal cations and their concentrations. The uptake of H₂TPPS^4? particles by tumor cells (A549 cells) was found to be more efficient than H₂TPPS^4? at 37 °C, showing the application potential of such assembled particles in biology and medicine.     

Copper-and Silver-Mediated Cyanation of Aryl Iodides Using DDQ as Cyanide Source

A new copper and silver‐mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, providing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles.