Effect of bication (Cu-Cr) substitution on the structure and electrochemical performance of LiMn2O4 spinel cathodes at low and high current rates

This report describes the detailed structural and electrochemical characterization of a series of low content (0.01 to 0.05) Cu-Cr bi-metal doped LiMn₂O₄ cathode material synthesized by sol–gel method. The structural and morphological features were described using XRD, SEM, TEM, EDAX and FTIR techniques. The electron transfer and its feasibility were discussed through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The charge–discharge studies were performed to evaluate the capacity fading and rate capability. It was found that the electrochemical performance is very much dependent on the amount of Cu-Cr bi-metal doping and interestingly decreased the capacity fading with high cycleability. The sample with the least amount of dopants (i.e., LiCu_0.01Cr_0.01Mn_1.98O₄) demonstrated much improved capacity, cycleability and high rate capability. The LiCu_0.01Cr_0.01Mn_1.98O₄ cathode exhibited a discharge capacity of 112 mA h g^?1 at very first cycle and retained 93 mA h g^?1 after 100 cycles at a C rate of 0.3. Further, the same material at very high current density (5 C) retained 83% of the initial discharge capacity. The Cu-Cr doping stabilized the spinel structure by suppressing the Jahn-Teller distortion effect and Mn dissolution and the resultant material showed the workability of the cathodes for devices which work at substantially high C-rate of 5C.     

Analysis of Solvent Effect on Mechanical Properties of Poly(ether ether ketone) Using Nano-indentation

Poly (ether ether ketone)(PEEK) is a high-performance semi-crystalline thermoplastic polymer.Exposure of the polymeric surface to solvents can have a strong effect like softening/swelling of polymeric network or dissolution.In this study, nano-indentation analysis was performed to study the effect of acetone on the surface mechanical properties of PEEK using different exposure time.The experiments were performed with a constant loading rate (10 nm/s) to a maximum indentation displacement (1000 nm).A 30-second hold segment was included at the maximum load to account for any creep effects followed by an unloading segment to 80% unloading.The indentation hardness and the elastic modulus were computed as a continuous function of the penetration displacement in the continuous stiffness mode (CSM) indentation.The experimental data showed that the peak load decreased from ~5.2 mN to ~1.7 mN as exposure time in solvent environment increased from 0 to 18 days.The elastic modulus and the hardness of PEEK samples also displayed a decreasing trend as a function of exposure time in the solvent environment.Two empirical models were used to fit the experimental data of hardness as a function of exposure time which showed a good agreement with the experimental values.     

Enhancing single-molecule magnet behavior of linear Co<Superscript>II</Superscript>-Dy<Superscript>III</Superscript>Co<Superscript>II</Superscript> complex by introducing bulky diamagnetic moiety

Single-molecule magnets (SMMs) are regarded as promising candidates for ultrahigh-density storage, quantum information processing and molecular spintronics. It is a crucial challenge for chemists to modulate magnetic dynamics of SMMs. Here, we successfully synthesized two 3d-4f polynuclear compounds [Co₂Dy(TTTT^Cl)₂(MeOH)]NO₃·3MeOH (1) and [Co₂Dy(TTTT^Cl)₂ (MeOH)][Co(HTTTT^Cl)](NO₃)₂·2.5MeOH·2H₂O (2), where H₃TTTT^Cl=2,2′,2′′-(((nitrilotris(ethane-2,1-diyl)) tris(azanediyl)) tris(methylene))tris-(4-chlorophenol). On applying the approach by co-crystallization of bulky diamagnetic moiety, the effective energy barrier enhances from 401 K (1) to 536 K (2), which are both among the highest d-f heterometallic SMMs.     

A Norm Minimization-Based Convex Vector Optimization Algorithm

Journal of Optimization Theory and Applications - We propose an algorithm to generate inner and outer polyhedral approximations to the upper image of a bounded convex vector optimization problem....     

Determination of Cadmium in Human Serum and Blood Samples after Dispersive Liquid–Liquid Microextraction Using a Task-Specific Ionic Liquid

Task-specific ionic liquid dispersive liquid–liquid microextraction (TSIL-DLLME) is a simple and rapid preconcentration approach for the measurement of cadmium in serum and blood samples of human subjects. In this method a novel task-specific ionic liquid, trioctylmethyl ammonium thiosalicylate (TOMATS), which has dual characteristics as a chelating agent and extractive solvent, was investigated. TOMATS complexes with Cd due to the chelating effect of the ortho-positioned carboxylate relative to the thiol functionality. The assessment of the optimum values of variables including the pH, amount of reagents (TOMATS, diluents, Triton X114, and back extracting acid solution), temperature, and incubation time, which affect the recoveries of analyte by TSIL-DLLME method were studied. After enrichment experiments, acidic solution was used to back extract the metal ions from the ionic liquid rich phase and with determination by electrothermal atomic absorption spectrometry. Using the optimal experimental conditions, the limit of detection (3?s), precision (relative standard deviation), preconcentration, and enhancement factors of developed method for Cd were found to be 0.05?µg/L, greater than 5%, 62.5, and 52.8, respectively. To check the accuracy of the developed method, certified reference material of serum and blood were analyzed by the developed method, and the measured values of Cd were in good agreement with the certified values. The developed method was applied successfully to determine Cd in blood and serum samples of lymphatic cancer patients relative to healthy controls.     

Method Development for Determination of Antibiotic Drugs Using Newly Prepared <Emphasis Type="Italic">p</Emphasis>-Morpholinomethylcalix[4]arene Mesoporous Silica-Based HPLC Column

Mesoporous materials are described by their relatively high surface areas and pore volumes. They possess uniform channels within nanometer range. These materials have numerous applications in catalysis, separation and many other fields. The qualitative and quantitative determination of antibiotic drugs, i.e., ciprofloxacin and cefixime has clinical and analytical importance due to their broad spectrum of antimicrobial activity and stability. Both antibiotic drugs are orally active and have excellent activity against different pathogens. It is for the first time that we have developed an analytical method for the simultaneous analyses of both drugs using a newly developed p-morpholinomethylcalix[4]arene (p-MC4) mesoporous silica-based HPLC column (15?×?3 mm I.D.). Furthermore, separation of these two components was carried out using isocratic elution of methanol and 0.1% aqueous formic acid (70:30 v/v) with flow rate of 1 ml min^?1 at retention time of 2.71 and 4.21 min and retention factor 1.85 and 1.19 for ciprofloxacin and cefixime, respectively; while total run time was 5 min. The developed method was repeatable with a relative standard deviation (RSD) of 0.90–2.08% for antibiotic drugs. The limits of detection and quantification of ciprofloxacin and cefixime were obtained within the range of 0.152–0.801 and 0.40–1.23 µg mL^?1, respectively. The method is highly applicable, rapid, simple, very reproducible and accurate for the separation and determination of antibiotic drugs.     

Asymmetric Oxygen Bridged Copper(II) Carboxylate: Synthesis,Complete Characterization,and Crystal Structure

Binuclear centrosymmetric copper(II) complex of the formula bipyCu(L)₄Cubipy, where bipy = 2,2′- bipyridine and L = 4-methoxy-2-phenyl acetate, is synthesized and characterized by FT-IR, UV-Visible, ESR and mass spectroscopy, electrochemical, thermogravimetric, and single crystal XRD techniques. The complex contains two differently oriented molecules per unit cell stabilized via intermolecular interactions. Geometry around each Cu(II) was found to be square pyramidal affected by asymmetrically bridging oxygen atoms occupying the apical position of one square pyramid and the axial position of another in the same binuclear molecule. The square base is formed by two oxygen atoms from two carboxylate ligands and two nitrogen atoms from the bipyridine moiety. TGA shows that the complex is stable up to 170 °C followed by stepwise loss of coordinated ligands, which was supported by GC-MS data as well. A broad absorption spectrum indicated ²B_1g as the ground state and single electron occupancy of the dx²–y² orbital, which was confirmed by the ESR spectrum. The electrochemical study gives two oxidation curves corresponding to Cu(II)/Cu(III) and Cu(I)/Cu(II) and a reduction signal corresponding to the Cu(II)/Cu(I) process. The robust complex represents an interesting contribution to the understanding of coordination chemistry.     

Aptamer-based fluorescent platform for ultrasensitive adenosine detection utilizing Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles and silver nanoparticles

The authors describe an aptamer-based fluorescent assay for adenosine (Ade). It is based on the interaction between silver nanoparticles (AgNPs) and CdTe quantum dots (QDs). The beacon comprises a pair of aptamers, one conjugated to Fe₃O₄ magnetic nanoparticles, the other to AgNPs. In the presence of Ade, structural folding and sandwich association of the two attachments takes place. After magnetic separation, the associated sandwich structures are exposed to the QDs. The AgNPs in sandwich structures act as the signaling label of Ade by quenching the fluorescence of QDs (at excitation/emission wavelengths of 370/565 nm) via inner filter effect, electron transfer and trapping processes. As a result, the fluorescence of QDs drops with increasing Ade concentration. The assay has a linear response in the 0.1 nM to 30 nM Ade concentration range and a 60 pM limit of detection. The assay only takes 40 min which is the shortest among the aptamer-based methods ever reported. The method was successfully applied to the detection of Ade in spiked biological samples and satisfactory recoveries were obtained.

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Graphical abstract Schematic of a highly efficient and convenient adenosine (Ade) fluorometric assay. It is based on the interaction between Ag nanoparticles (NPs) and CdTe quantum dots (QDs). Ade aptamers (ABA1 and ABA2) are used as recognition unit and Fe₃O₄ magnetic nanoparticles act as magnetic separator. The assay exhibits superior sensitivity and speediness.

     

New analogs of temporin-LK1 as inhibitors of multidrug-resistant (MDR) bacterial pathogens

The peptide temporin-LK1 (1) was obtained from the skin secretion of frog Limnonectes kuhlii (Ranidae). It is a unique antimicrobial peptide with 17 residues, including four L-phenylalanines and single glycine. Mass spectrometry and Edmand degradation were used for the determination of sequence of amino acids in temporin-LK 1 (1), and confirmed by cDNA cloning. We report here the synthesis and structural studies of temporin-LK1 (1) and its analogs 2–4. Peptides 2–4 were prepared by substitution of achiral glycine residue of temporin-LK1 (1) with D-alanine, L-phenylglycine, and L-naphthylalanine, respectively. Peptides 1–4 were evaluated against multidrug-resistant (MDR) strains of Staphylococcus aureus and Pseudomonas aeruginosa. Analog 2 was found active against all MDR strains of S. aureus and P. aeruginosa at a much lower dose than the clinically used antibiotics.     

DABCO–PEG ionic liquid-based synthesis of acridine analogous and its inhibitory activity on alkaline phosphatase

In world, many people struggle with viral, parasitic, bacterial, cancer, and other diseases. Therefore, numerous chemists seek to develop less toxic, more selective, and effective medicines. Most therapeutic medicines are based on inhibition of specific enzymes. Acridines are interesting heterocyclic structures that are much sought after targets attributed to their wide biological activities and feature to display potent enzymes inhibitory effects. Their approach of action is owing to DNA interaction and subsequent effects on the biological functions linked to DNA and associated enzymes. In this regards, we synthesized acridine analogous through 1,4-diazabicyclo[2.2.2]octane (DABCO)–polyethylene glycol-400 (PEG-400) mediated ionic liquid approach. DABCO–PEG-400-mediated IL was prepared through the DABCO alkylation using 1-bromopentane followed by mixing with PEG-400. The synthesized analogous were investigated as inhibitors of alkaline phosphatase, which is a nonspecific phosphomonoester hydrolase that catalyzes the hydrolysis of broad spectrum of organic monophosphates. Analogue viz. 3,3,6,6-tetramethyl-9-(4-nitrophenyl)-2,3,4,5,6,7,9,10-octahydroacridine-1,8-dione was found to be potent alkaline phosphatase inhibitor.