Covalent and ionic Cu(II) complexes with cyclam and substituted benzoato ligands: structural,thermal, redox and mesomorphic properties

A covalent mononuclear complex, [Cu(p–HOC₆H₄COO)₂(cyclam)] (1), and two ionic mononuclear complexes, [Cu(cyclam)(H₂O)₂](p–CH₃OC₆H₄COO)₂ (2) and [Cu(cyclam)(H₂O)₂](p–CH₃(CH₂)₁₅OC₆H₄COO)₂·H₂O (3), were formed from reaction of cyclam with [Cu₂(p–HOC₆H₄COO)₄(H₂O)₂], [Cu₂(p–CH₃OC₆H₄COO)₄(H₂O)₂] and [Cu₂(p-CH₃(CH₂)₁₅OC₆H₄COO)₄(H₂O)₂], respectively. These complexes were isolated as purple crystals with molecular structures showing distorted octahedral N₄O₂ geometry. Complexes 1 and 2 were irreversibly reduced to Cu(I) and oxidized to Cu(III), while 3 was redox inactive. Complex 2 reacted with N-(hexadecyl)isonicotinamide (L) to form [Cu(cyclam)(L)₂](p–CH₃OC₆H₄COO)₂ (4). These complexes were thermally stable (T_dec > 200 °C for 1–3 and 174 °C for 4). Complexes 3 and 4 behaved as ionic liquids (melting temperatures lower than 100 °C) and exhibited mesomorphism.     

Investigation of the synthesis of poly-D,L-lactide-co-poly(ethylene glycol) flexible thermoplastic

A series of biodegradable poly(D,L-lactide)-poly(ethylene glycol) multiblock poly(ether-ester-urethane)s with various lactide-to-poly(ethylene glycol) (LA/PEG) mole ratios has been successfully synthesized by ring-opening polymerization (ROP) followed by chain extension reaction through formation of urethane linkage. Resulting FT-IR spectra indicate complete polymerization of lactide monomers, while NMR analysis quantitatively marks the chain length of polymer blocks. The molecular weight and dispersion index of copolymers were investigated by GPC analysis. DSC thermogram and XRD diffractogram of the prepared copolymers were studied as well for revealing the thermal and crystallinity behavior of the copolymer as LA/PEG mole ratios varied.     

The Specific Heat Capacity,Effective Thermal Conductivity,Density, and Viscosity of Coolants Containing Carboxylic Acid Functionalized Multi-Walled Carbon Nanotubes

Obviously, the behavior of thermophysical properties of covalently functionalized CNT-based water and -based ethylene glycol (EG) nanofluids cannot be predicted from the predicted models. We present a study of the specific heat capacity, effective thermal conductivity, density, and viscosity of coolants containing functionalized multi-walled carbon nanotubes (CNT-COOH) with carboxylic acid groups at different temperatures. After synthesizing of CNT-COOH-based water and CNT-COOH-based EG nanofluids, measurements on the prepared coolant were made at various concentrations by different experimental methods. While the thermal conductivity of both nanofluids illustrated a significant increase, the specific heat capacity of both samples showed a downward behavior with increasing temperature. Although the thermal conductivity of CNT-COOH-based water nanofluids is bigger than CNT-COOH-based EG nanofluids, CNT-COOH-based water has weaker temperature dependence than that of the CNT-COOH-based EG nanofluids. The viscosity was investigated in different shear rates and temperatures. It is noteworthy that CNT-COOH-based EG nanofluids show relatively a non-Newtonian behavior. Interestingly, specific heat capacities of both prepared nanofluids were decreased with increasing concentration. Also, the density of the CNT-COOH-based water and -based EG nanofluids increased and decreased smoothly with increasing CNT-COOH concentration and temperature, respectively.     

Effects of substituents and charge on the RCHO⋯X–Y {X = Cl,Br, I; Y = –CF3, –CF2H, –CFH2, –CN, –CCH, –CCCN; R = –OH, –OCH3, –NH2, –O−} halogen-bonded complexes

Structural Chemistry - Noncovalent interactions involving halogen bonding interactions, one of the emerging interactions due to its directionality, have been a subject of interest for various...     

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.     

Two-Dimensional Liquid Chromatography (2D-LC) in Pharmaceutical Analysis: Applications Beyond Increasing Peak Capacity

One-dimensional liquid chromatography (1D-LC) is not always capable of efficiently separating complex samples. This drawback is not solely due to the lack of column efficiency, but is mainly due to insufficient selectivity and the need to separate the analytes of interest with orthogonal retention mechanisms. In this regard, two-dimensional liquid chromatography (2D-LC) is currently attracting much interest for its markedly higher resolving power compared to one-dimensional separation. In this work, three applications of 2D-LC from the pharmaceutical industry are presented with the goal not only to increase peak capacity, but also to support investigations. In the first application, the retention times of peaks of interest are matched under different mobile phase conditions for the purpose of transferring the method from a mass spectrometry (MS) incompatible buffer to an MS compatible buffer. The second application includes developing a method for simultaneous detection and quantitation of degradants and aggregates in a biologics and small molecule combination product. The third application supports method development by confirming the purity of separated peaks using orthogonal separation conditions in the first and second dimensions and to investigate mass balance issues where some peaks are expected to elute in the solvent front.     

Electrochemical behavior of superoxide anion radical towards quinones: a mechanistic approach

Research on Chemical Intermediates - Among the reactive oxygen species, the superoxide anion radical (O 2 ·? ) has a fundamental role in several biological functions. Consequently, its...     

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.     

Rapid development in two-dimensional layered perovskite materials and their application in solar cells

This review summarized recent research progresses of two-dimensional layered organic-inorganic hybrid perovskite materials and their photovoltaic performances in 2D perovskite solar cells.     

Room temperature LPG resistive sensor based on the use of a few-layer graphene/SnO<Subscript>2</Subscript> nanocomposite

A nanocomposite consisting of a few layers of graphene (FLG) and tin dioxide (SnO₂) was prepared by ultrasound-assisted synthesis. The uniform SnO₂ nanoparticles (NPs) on the FLG were characterized by X-ray diffraction in terms of lattice and phase structure. The functional groups present in the composite were analyzed by FTIR. Electron microscopy (HR-TEM and FE-SEM) was used to study the morphology. The effect of the fraction of FLG present in the nanocomposite was investigated. Sensitivity, selectivity and reproducibility towards resistive sensing of liquid propane gas (LPG) was characterized by the I-V method. The sensor with 1% of FLG on SnO₂ operated at a typical voltage of 1 V performs best in giving a rapid and sensitive response even at 27 °C. This proves that the operating temperature of such sensors can be drastically decreased which is in contrast to conventional metal oxide LPG sensors.

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Graphical abstract Schematic of a room temperature gas sensor for liquefied petroleum gas (LPG). It is based on the use of a few-layered graphene (1 wt%)/SnO₂ nanocomposite that was deposited on an interdigitated electrode (IDEs). A sensing mechanism for LPG detection has been established.