Synthesis,XRD, spectral (IR,UV–Vis,NMR) characterization and quantum chemical exploration of benzoimidazole‐based hydrazones: A synergistic experimental‐computational analysis

Present study advocates the joint experimental and computational studies of two potent benzoimidazole‐based hydrazones with chemical formula C₂₃H₁₈F₂N₄O ( 5a ) and C₂₅H₂₂FN₅O₃ ( 5b ). Both 5a and 5b were synthesized and resolved into their crystal structures using SC‐XRD for the assessment of bond lengths, bond angles, unit cells and space groups. The structures of 5a and 5b were chemically characterized using infrared (FT‐IR), UV–Visible, nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR), EIMS and elemental analysis. DFT at M06‐2X/6‐31G(d,p) level of theory was performed to get optimized structures and countercheck the experimental findings. Overall, DFT findings show excellent concurrence with the experimental data which confirms the purity of both compounds. FMO, NBO analysis, MEP surfaces and nonlinear optical (NLO) properties were explored at same level of theory. UV–Vis analysis at TDDFT/M06‐2X/6‐31G(d,p) level of theory showed that 5b is red shifted with λ_max 331.69 nm as compared to 5a with λ_max 240.25 nm. Global reactivity parameters were estimated using energy of FMOs indicated the greater harness value than the softness values of 5a and 5b . NBO analysis confirmed that the presence of non‐covalent interactions, hydrogen bonding and hyper conjugative interactions are pivotal cause for the existence of 5a and 5b in the solid‐state. NLO results of 5a and 5b were observed better than standard molecule recommended the NLO activity of said molecules for optoelectronic applications.     

Full control of polymer properties during the two‐stage on‐demand free‐radical photopolymerization of fiber‐reinforced polymers

The effect of a two‐step free‐radical photopolymerization of an acrylate resin on the polymer properties in the presence of glass fibers is studied. It is found that a first irradiation leading to a partial conversion is effective for the fabrication of a preimpregnated glass‐fiber composite, which can be further processed and fully polymerized through a second irradiation. DMA analysis evidences the formation of a first relatively soft polymer embedding unreacted double bonds during the preirradiation. Further process allows the completion of the photopolymerization together with a reinforcement of the polymer network. This obviously affects the final mechanical properties of the photocomposite. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1440–1447     

Kinetics of silver nanoparticle growth in aqueous polymer solutions: 1st Nano Update

In this paper we report the effect of poly(vinyl alcohol) (PVA) on the silver nanoparticles formation of different morphologies by using silver nitrate and citric acid as the oxidant and reductant, respectively, for the first time. Our transmission electron microscopy (TEM) results suggest that the presence of PVA has significant impact on the size, shape, and the size distribution of the silver nanoparticles. The reaction follows a zero-order kinetics in [citric acid] as well as in [silver(I)] in the absence and presence of PVA. It was found that PVA and cetyltrimethylammonium bromide (CTAB) concentrations show no significant effects on the rate of CTAB-stabilized silver nanoparticles formation, whereas in presence of PVA, the reaction rate increases with (CTAB). Both spectrophotometric and TEM measurement demonstrated that the orange silver sol consists of aggregates, whereas the purple sol does not contain the aggregated arrangement. On the basis of various observations, the most plausible mechanism has been envisaged.     

Molecular dynamics study of the mechanical characteristics of Ni/Cu bilayer using nanoindentation

<正>In the present work,a three-dimensional molecular dynamics simulation is carried out to perform the nanoindentation experiment on Ni single crystal.The substrate indenter system is modeled using hybrid interatomic potentials including the many-body potential embedded atom method(EAM),and two-body morse potential.To simulate the indentation process,a spherical indenter(diameter = 80 A,1 A=0.1 nm) is chosen.The results show that the mechanical behaviour of a monolithic Ni is not affected by crystalline orientation.To elucidate the effect of a heterogeneous interface, three bilayer interface systems are constructed,namely Ni(100)/Cu(111),Ni(110)/Cu(111),and Ni(111)/Cu(111).The simulations along these systems clearly describe that mechanical behaviour directly depends on the lattice mismatch. The interface with the smaller mismatch between the specified crystal planes is proved to be harder and vice versa.To describe the relationship between film thickness and interface effect,we choose various values of film thickness ranging from 20 A to 50 A to perform the nanoindentation experiment.It is observed that the interface is significant only for the relatively small thickness of film and the separation between interface and the indenter tip.It is shown that with the increase in film thickness,the mechanical behaviour of the film shifts more toward that of monolithic material.     

Application of bar adsorptive microextraction to determine trace organic micro-pollutants in environmental water matrices

The present work proposes the application of bar adsorptive micro-extraction (BAµE) coated with an N-vinylpyrrolidone polymer (NVP) combined with micro-liquid desorption (200 µL) followed by high-performance liquid chromatography with diode array detection (BAµE(NVP)-µLD/HPLC-DAD) for the determination of trace levels of emerging organic micro-pollutants in environmental water matrices. The model compounds selected include an antibacterial/antifungal agent (triclosan), two pharmaceuticals (carbamazepine and diclofenac) and two steroid hormones (17α-ethinylestradiol and 17β-estradiol), in which the latter three were recently included in the European Union watch list of substances to be monitored in the field of water policy. Assays performed on 25 mL of ultrapure water samples spiked at the 8.0 µg L^?1 level yielded average recoveries ranging from 81.9 to 102.4% for the compounds studied using optimised experimental conditions. The proposed analytical methodology demonstrated suitable detection limits (0.02–0.10 µg L^?1) and good linear dynamic ranges (0.1–20.0 µg L^?1) with determination coefficients higher than 0.9909. Using the standard addition method (SAM), the present analytical approach was applied on environmental water matrices, including surface, sea, river and groundwaters. The proposed method proved to be a suitable and alternative sorption-based static micro-extraction technique for monitoring trace levels of organic micro-pollutants in environmental water matrices.     

An organic‐inorganic heterogeneous catalyst based on Keplerate polyoxometalates for oxidation of dibenzothiophene derivatives with Hydrogen peroxide

An organic‐inorganic material (NH₄)₂(MimAM)₄₀[Mo₁₃₂O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] have been synthesized by reacting [(NH₄)₄₂[Mo^VI₇₂ Mo^V₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] with the ionic liquid 3‐Aminoethyl‐1‐methylimidazolium bromide. The catalyst showed remarkably a high catalytic performance in the oxidation of dibenzothiophene (DBT) derivatives with H₂O₂ 35% as a safe and green oxidant. The main parameters affecting the process including catalyst, acid additive, hydrogen peroxide amounts and temperature have been investigated in detail. Sulfur removal of DBT in n‐heptane reached to 98.3% yield at 40 °C using 2.5 mmol H₂O₂ and 100 mg of (NH₄)₂(MimAM)₄₀[Mo₁₃₂O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] after 90 min. Under the optimal conditions, BT (benzothiophene), DBT (dibenzothiophene) and 4,6‐DMDBT (4,6‐dimethyl‐dibenzothiophene) achieved high desulfurization efficiency. Our results showed that the reactivity order of different model sulfur compounds are thiophene <4,6‐dimethyl dibenzothiophene< dibenzothiophene. The catalysts could be easily separated from the reaction solution by simple filtration and recycled for several times without loss of activity.     

Passive Q-switching in an erbium-doped fiber laser using tungsten sulphoselenide as a saturable absorber

A highly stable Q-switched laser incorporating a mechanically exfoliated tungsten sulphoselenide (WSSe) thin sheet saturable absorber (SA) is proposed and demonstrated. The SA assembly, formed by sandwiching a thin WSSe sheet between two fiber ferrules within the erbium-doped fiber laser, is used to effectively modulate the laser cavity losses. The WSSe-based SA has a saturation intensity of ~0.006 MW∕cm~2 and a modulation depth of 7.8%, giving an optimum Q-switched laser output with a maximum repetition rate of 61.81 kHz and a minimum pulse width of 2.6 μs. The laser's highest output power of 0.45 mW and highest pulse energy of 7.31 nJ are achieved at the maximum pump power of 280.5 mW. The tunability of the cavity's output at the maximum pump power is analyzed with a C-band tunable bandpass filter, giving a broad tunable range of ~40 nm, from 1530 nm to 1570 nm. The output performance of the tunable Q-switched laser correlates well with the gain spectrum of erbium-doped fibers, with the shift in the gain profile as a result of the saturated SA.     

Design and identification of nano-Mg-[4-methoxy phenyl-salicylaldimine–methyl-pyranopyrzole] Cl2 and its catalytic application on the preparation of 1-(α-aminoalkyl)-2-naphthols

Nano-Mg- [4-methoxy phenylsalicylaldiminemethylpyranopyrazole]Cl₂ (nano-[Mg-4MSMP]Cl₂) as a nano-Schiff base complex was prepared and fully characterized using some various techniques including fourier transform infrared spectroscopy (FT-IR), energy-dispersive x-ray spectroscopy (EDS), X-ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric analysis (DTA), mass spectroscopy (MS) and scanning electron microscopy (SEM). Nano-[Mg-4MSMP]Cl₂ was successfully used as an efficient catalyst for the preparation of some 1-(α-aminoalkyl) -2 -naphthols.     

A Chiral Lanthanide Tag for Stable and Rigid Attachment to Single Cysteine Residues in Proteins for NMR,EPR and Time-Resolved Luminescence Studies

A lanthanide-binding tag site-specifically attached to a protein presents a tool to probe the protein by multiple spectroscopic techniques, including nuclear magnetic resonance, electron paramagnetic resonance and time-resolved luminescence spectroscopy. Here a new stable chiral Ln^III tag, referred to as C12 , is presented for spontaneous and quantitative reaction with a cysteine residue to generate a stable thioether bond. The synthetic protocol of the tag is relatively straightforward, and the tag is stable for storage and shipping. It displays greatly enhanced reactivity towards selenocysteine, opening a route towards selective tagging of selenocysteine in proteins containing cysteine residues. Loaded with Tb^III or Tm^III ions, the C12 tag readily generates pseudocontact shifts (PCS) in protein NMR spectra. It produces a relatively rigid tether between lanthanide and protein, which is beneficial for interpretation of the PCSs by single magnetic susceptibility anisotropy tensors, and it is suitable for measuring distance distributions in double electron–electron resonance experiments. Upon reaction with cysteine or other thiol compounds, the Tb^III complex exhibits a 100-fold enhancement in luminescence quantum yield, affording a highly sensitive turn-on luminescence probe for time-resolved FRET assays and enzyme reaction monitoring.     

Copper,gold, and silver decorated magnetic core–polymeric shell nanostructures for destruction of pathogenic bacteria

Fe₃O₄ magnetic nanoparticles (MNPs) were prepared by co-precipitation method. The nanoparticles were silica coated using TEOS, and then modified by the polymeric layers of polypropylene glycol (PPG) and polyethylene glycol (PEG). Finally, the core-shell samples were decorated with Ag, Au, and Cu nanoparticles. The products were characterized by vibrating sample magnetometry (VSM), TGA, SEM, XRD, and FTIR methods. The antibacterial activity of the prepared samples was evaluated in inactivation of E. coli and S. aureus microorganisms, representing the Gram-negative and Gram-positive species, respectively. The effect of solid dosage, bacteria concentration and type of polymeric modifier on the antibacterial activity was investigated. TEM images of the bacteria were recorded after the treatment time and according to the observed changes in the cell wall, the mechanism of antibacterial action was discussed. The prepared nanostructures showed high antibacterial activity against both Gram-negative and Gram-positive bacteria. This was due to the leaching of metal ions which subsequently led to the lysis of bacteria. A theoretical investigation was also done by studying the interaction of loaded metals with the nucleotide components of the microorganism DNA, and the obtained results were used to explain the experimental data. Finally, based on the observed inactivation curves, we explain the antibacterial behavior of the prepared nanostructures mathematically.