Activity

Rechargeable Zn-MnO2 batteries with mild and nearly neutral aqueous electrolytes have shown great potential for large-scale energy storage because of their high safety, low cost, environmental friendliness and high energy density. However, MnO2 cathode materials usually have disadvantages such as low capacity and poor cycling stability, which limit the development of Zn-MnO2 batteries. In this study, mesoporous MnO2 nanospheres were prepared by in situ Mg ion pre-intercalation via a simple chemical method. The prepared MnO2 shows a high reversible capacity (247 mA h g-1 at 0.3 A g-1), excellent cycling stability (a capacity retention of 93% over 800 cycles at 0.8 A g-1) and good rate performance. The GITT, in situ EIS, ex situ XRD, ex situ XPS and ex situ SEM show that the zinc storage mechanism of MnO2 should be H+/Zn2+ co-intercalation/de-intercalation. This research could provide specific inspiration and promotion for the development and mechanism research of high-performance rechargeable Zn-MnO2 batteries.Knoevenagel condensation reaction counts as a vital condensation in organic chemistry due to the synthesis of valuable intermediates, heterocycles, and fine chemicals from commercially available reactants through forming new CC bonds between an aldehyde or ketone and active methylene compounds. Therefore, the catalytic Knoevenagel condensation reaction has continuously received significant interest in different aspects, i.e., investigating the catalytic efficiency of new heterogeneous and homogeneous catalysts. Furthermore, metal-free catalysis has recently attracted considerable attention because of environmental concerns. This review summarizes the most recent studies on utilizing metal-free nitrogen-based catalysts in the Knoevenagel condensation reaction, including organocatalysts, polymers, ionic liquids, and bio- and carbon-based catalysts. The substrate scope, the optimal reaction conditions, selectivity, the desired product yield, merits, and limitations of each method are discussed. In addition, the recyclability, biocompatibility, and biodegradability of catalysts are reported. This review also covers the approaches that influence the selectivity of the Knoevenagel products.Thin films of two ambipolar lithium-organic electrode materials, Li2DHTP and Li4DHTP, are grown from gaseous precursors, Li(thd) (tetramethyl heptanedione) and DHTP (dihydroxyterephthalic acid). These precursors are pulsed into the reactor in a sequential manner like in atomic/molecular layer deposition, but the reaction product, i.e. the di- or the tetra-lithium salt, is controlled by adjusting the precursor pulse lengths.The anion recognition properties of six synthetic acyclic and macrocyclic carbazole-based receptors have been studied by 1H-NMR as well as with COSMO-RS calculations towards acetate, benzoate, lactate, sorbate and formate. The receptors differed by the number and geometry of hydrogen-bond donor (HBD) sites, the nature and length of the linker(s) between the HBD sites and the cyclic or non-cyclic nature. The binding ability of the receptors is strongly influenced by the structure and steric variables of the receptors and anions. It was found that when urea was replaced with the flexible diglycolyl as the connecting linker between carbazole subunits, the carboxylate binding affinity of the receptor decreased significantly. The effects of the receptors’ structure on anion binding have been investigated and several intriguing cases have been identified and analysed. The current findings shed light on carboxylate anion binding and contribute to the systematic synthesis of receptors with beneficial functional selectivity for carboxylate anions.A DNA origami nanocaliper is employed as a shape-resolved nanomechanical device, with pH-responsive triplex DNA integrated into the two arms. The shape transition of the nanocaliper results in a subtle difference depending on the local pH that is visible via TEM imaging, demonstrating the potential of these nanocalipers to act as a universal platform for pH sensing at the nanoscale.Examination of a series of naturally-occurring trypsin inhibitor proteins, led to identification of a set of three residues (which we call the “interface triplet”) to be determinant of trypsin binding affinity, hence excellent templates for small molecule mimicry. Consequently, we attempted to use the Exploring Key Orientation (EKO) strategy developed in our lab to evaluate small molecules that mimic the interface triplet regions of natural trypsin inhibitors, and hence potentially might bind and inhibit the catalytic activity of trypsin. A bis-triazole scaffold (“TT-mer”) was the most promising of the molecules evaluated in silico. Twelve such compounds were synthesized and assayed against trypsin, among which the best showed a Kd of 2.1 μM. X-ray crystallography revealed a high degree of matching between an illustrative TT-mer’s actual binding mode and that of the mimics that overlaid the interface triplet in the crystal structure. Deviation of the third side chain from the PPI structure seems to be due to alleviation of an unfavorable dipole-dipole interaction in the small molecule’s actual bound conformation.Meso-Tetrakis-(3,4,5-tris2-[2-(2-methoxyethoxy)ethoxy]ethoxyphenyl)porphyrin TEG12PH2 is reported as an ‘omnisoluble’ reference for singlet oxygen (1O2) generation quantum yield (ΦSO) estimation. TEG12PH2 is a highly soluble, nonionic compound possessing excellent 1O2 QY in a wide variety of common solvents, including water. TEG12PH2 was prepared on multigram scale by the 12-way O-alkylation of tetrakis(3,4,5-trihydroxyphenyl)porphyrin using 2-(2-(2-methoxyethoxy)ethoxy)ethyl 4-toluenesulfonate as a reaction solvent. The corresponding Zn(II) complex TEG12PZn was also prepared and studied. The 1O2 QYs of TEG12PH2 in the different solvents studied were found to be 0.86 (acetone), 0.59 (acetonitrile), 0.66 (chloroform), 0.85 (methanol), 0.45 (toluene) and 0.51 (water). TEG12PH2 can be considered a reliable and easy to implement omnisoluble reference compound for the estimation of the 1O2 generating activities of new materials, especially new porphyrinic compounds.2D carbides and nitrides of transition metals, also known as MXenes, are an emerging class of 2D nanomaterials that have shown excellent performances and broad application prospects in the fields of energy storage, catalysis, sensing, electromagnetic shielding, electronics and photonics, and life sciences. Colivelin This unusual diversity of applications is due to their superior hydrophilicity and conductivity, high carrier concentration, ultra-high volumetric capacitance, rich surface chemistry, and large specific surface area. However, it is difficult to make MXenes with the desired surface functional groups that deliver high reactivity and high stability, because most MXenes are extracted from ceramics (MAX phase) by an etching process, where a large number of metal atoms are inevitably exposed on the surface, with other anions and cations embedded uncontrollably. The exposed metal atoms and implanted ions are thermodynamically unstable and readily react with trace oxygen or oxygen-containing groups to form the corresponding metal oxides or degrade chemically, resulting in a sharp decline in activity and loss of excellent physicochemical properties. The addition of certain synergistic additives during the intercalation and chemical modification of surface functional groups under non-hazardous conditions can result in stable and efficient MXene-based materials with exceptional optical, electrical, and magnetic properties. This review discusses several such methods, mainly additive-mediated intercalation and chemical modification of the surface functional groups of MXene-based materials, followed by their potential applications. Finally, perspectives are given to discuss the future challenges and promising opportunities of this exciting field.Sulphonamides are a group of synthetic antibiotics used specially in veterinary medicine. Among the procedures employed in the sample preparation for sulphonamide determination are liquid-liquid extraction (LLE) and solid-phase extraction (SPE) that use large volumes of organic solvents. Hence, a clean procedure was developed based on preconcentration and cloud point extraction (CPE) without using organic solvents to quantify total sulphonamides in bovine milk. The procedure was optimized as follows 2 mL of pre-cleaned milk sample, 2 mL of reagent solution and 1 mL of Triton X-114 7% (m/v) were added to a tube, heated in a water bath at 40 °C for 10 minutes and centrifuged at 2950 rcf for 20 minutes. Digital image acquisition was employed directly at the tube without removing the supernatant/aqueous phase. The linear response was observed between 10 and 400 μg L-1 of total sulphonamides and described by the following equation S = 2.50 + 0.0514C (μg L-1) and R = 0.999. The LOD and the CV (n = 11) were estimated to be 10 μg L-1 and 1.3%, respectively. The main interferents present at their usual concentrations in the sample did not interfere with the results. Spike and recovery tests of total sulphonamides were carried out in UHT and pasteurized milk with recovery values between 73 and 106% and the results obtained for this kind of sample were in agreement with those achieved by a high performance liquid chromatography (HPLC) procedure at the 95% confidence level. The analytical procedure presents an adequate sensitivity to determine total sulphonamides in bovine milk and does not require organic solvents, being aligned to the principles of green chemistry.The generation of Mn4+ in α-Al2O3Mn3+ by soft X-ray exposure is demonstrated with a large dynamic range of the X-ray generated Mn4+ luminescence signal, indicating the potential use of α-Al2O3Mn3+ for multilevel optical data storage. Samples with a range of Mn concentrations (0.05, 0.1, 0.2, 0.4, 0.6 and 1.2 atom%) were prepared via a facile combustion method and the sample with 0.4 atom% was found to display the highest luminescence intensity. The stored information can be read out via the R-lines (2E → 4A2) under ∼470 nm (4A2 → 4T2), or ∼630 nm (4A2 → 2T1) excitation with the latter being preferred since photobleaching is minimized. Interestingly, the Mn4+ valence state can be fully switched back to Mn3+ by blue light exposure (e.g., 462 nm laser diode). The stored information could be repeatedly written and erased, showing no significant deterioration over five consecutive cycles, with less than 5% uncertainty.Cation-π interactions in aqueous media are known to play critical roles in various biological activities. However, quantitative experimental information, such as the binding ratio of metal ions to aromatic groups, is hardly available due to the lack of a suitable test system and method. Herein, we proposed a hydrogel Donnan potential method to determine the binding ratio of metal ions to aromatic groups on polymer networks in aqueous media. In this method, we adopted recently developed poly(cation-π) hydrogels with a rich adjacent sequence of the cationic group and the aromatic group on the polymer network. A microelectrode technique (MET) is used to measure the Donnan potential of the poly(cation-π) hydrogels. From the Donnan potential, the binding ratios of various metal ions to aromatic groups are quantitatively determined for the first time.