Transamidation of Amides and Amidation of Esters by Selective N–C(O)/O–C(O) Cleavage Mediated by Air- and Moisture-Stable Half-Sandwich Nickel(II)–NHC Complexes

The formation of amide bonds represents one of the most fundamental processes in organic synthesis. Transition-metal-catalyzed activation of acyclic twisted amides has emerged as an increasingly powerful platform in synthesis. Herein, we report the transamidation of N-activated twisted amides by selective N–C(O) cleavage mediated by air- and moisture-stable half-sandwich Ni(II)–NHC (NHC = N-heterocyclic carbenes) complexes. We demonstrate that the readily available cyclopentadienyl complex, [CpNi(IPr)Cl] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), promotes highly selective transamidation of the N–C(O) bond in twisted N-Boc amides with non-nucleophilic anilines. The reaction provides access to secondary anilides via the non-conventional amide bond-forming pathway. Furthermore, the amidation of activated phenolic and unactivated methyl esters mediated by [CpNi(IPr)Cl] is reported. This study sets the stage for the broad utilization of well-defined, air- and moisture-stable Ni(II)–NHC complexes in catalytic amide bond-forming protocols by unconventional C(acyl)–N and C(acyl)–O bond cleavage reactions.     

Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates

This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH₄ + CO₂ hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH₄ + CO₂ hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.     

Preparation of a 99mTc-labeled graft polymer and its in vitro and in vivo evaluation

Journal of Radioanalytical and Nuclear Chemistry - The aim of this study is the synthesis of a novel 99mTc-labeld graft polymer and the biological evaluation of its in vitro and in vivo properties....     

One-pot synthesis of CoO–ZnO/rGO supported on Ni foam for high-performance hybrid supercapacitor with greatly enhanced cycling stability

The high specific capacitance along with good cycling stability are crucial for practical applications of supercapacitors,which always demands high-performance and stable electrode materials.In this work,we report a series of ternary composites of CoO-ZnO with different fractions of reduced graphene oxide(rGO) synthesized by in-situ growth on nickel foam,named as CZG-1,2 and 3,respectively.This sort of binder-free electrodes presents excellent electrochemical properties as well as large capacitance due to their low electrical resistance and high oxygen vacancies.Particularly,the sample of CZG-2(CoO-ZnO/rGO 20 mg) in a nanoreticular structure shows the best electrochemical performance with a maximum specific capacitance of 1951.8 F/g(216.9 mAh/g) at a current intensity of 1 A/g.The CZG-2-based hybrid supercapacitor delivers a high energy density up to 45.9 Wh/kg at a high power density of 800 W/kg,and kept the capacitance retention of 90.1% over 5000 charge-discharge cycles.     

Effect of organic dye on the performance of dye-sensitized solar cell utilizing TiO2 nanostructure films synthesized via CTAB-assisted liquid phase deposition technique

This work is concerned with the growth of TiO₂ nanostructures as photovoltaic materials of dyesensitized solar cell (DSSC) via phase liquid deposition technique treated with CTAB surfactant. This work investigates the influence of organic dyes, N719, N3 and Z907 as photosensitizer on the photovoltaic parameters of TiO₂ nanostructures dye-sensitized solar cells (DSSCs). It also highlights the effect of the concentration of the best dye, N719 on the performance of the cell. The platinum films as counter electrode of the DSSC were prepared by sputtering platinum pellet on ITO substrate. The redox couple of the electrolyte utilized in the DSSC was iodide/triiodide. The cell sensitized with N719 dye demonstrated the best performance compared with the cell sensitized with another two dyes, N3 and Z907. This is due to N719 dye possess the highest optical absorption in visible region. The cell sensitized with 0.8 mM N719 dye performs the highest short-circuit current density, J _sc and power conversion efficiency, η since it posses the highest absorption in visible region. The DSSC utilizing 0.8 mM N719 dye demonstrated the highest J _sc and η of 6.48 mA cm^?2 and 1.69%, respectively.     

Synthesis and complexation of a ‘mixed’-pyridine-naphthalene homooxacalixarene

A deep-cavity ‘mixed’ octahomotetraoxacalix[2]naphthalene[2]pyridine macrocycle has been synthesised and its single-crystal X-ray structure has been determined. Molecular modeling studies suggested that this macrocycle could be an effective host for guest aromatic diol(s) similar to Wang's methylazacalixpyridines. Binding constants were determined using ¹H NMR chemical shifts changes and comparisons were made between the diols which were tested.     

High Pressure Super-Heated Electrospray Ionization Mass Spectrometry for Sub-Critical Aqueous Solution

The heating of electrospray ion source under atmospheric pressure is limited to the normal boiling point of the solution. The boiling takes place when the vapor pressure of the liquid at a given temperature equals the ambient pressure. By using a high pressure ESI source, which has been developed previously in our laboratory, a stable electrospray ionization of super-heated aqueous solution is performed up to a solution temperature of 180°C. The ion source is pressurized with pure nitrogen to a maximum pressure of 11 atm, and it is coupled to a commercial mass spectrometer via a custom-made ion transport capillary. A booster pump with variable pumping speed is added to the pumping system to regulate the pressure in the first pumping stage at 1?~?1.3 Torr. High pressure mass spectrometry is performed on several peptides and proteins to demonstrate its application in the temperature-controlled thermally induced denaturation and dissociation. Graphical Abstract

?     

Halide ion effect on the chloroform chemical shift in supramolecular complexation studies with tetra-n-butylammonium salts: a 1H NMR and X-ray study

A ¹H NMR spectroscopic study of tetra-n-butylammonium halides (TBAX: X = Cl^? , Br^?  or I^? ) in CDCl₃ solutions was conducted. Complexation studies of TBAX salts with different host molecules using ¹H NMR in CDCl₃ have previously revealed that the reference residual CHCl₃ proton signal had been shifted downfield. The aim of the study was to quantify the extent of these chemical shift changes with TBAX salts. Linear concentration–chemical shift relationships in each case were obtained from the resulting titration plots obtained from the addition of the TBAX salts alone to CDCl₃. Interactions in the solid state as determined by X-ray crystallography support the solution-state investigations indicating halide ion–chloroform proton interactions.     

The effect of 3D printing on the morphological and mechanical properties of polycaprolactone filament and scaffold

Three‐dimensional (3D) printing becomes an attractive technique to fabricate tissue engineering scaffolds through its high control on fabrication and repeatability using the printing parameters. This technique can be combined by the finite element method (FEM), and tissue‐specific scaffolds with desirable morphological and mechanical properties can be designed and manufactured. In this study, the influential 3D printing parameters on the morphological and mechanical properties of polycaprolactone (PCL) filament and scaffold were studied experimentally and numerically. First, the effects of printing parameters and process on the properties of extruded PCL filament were investigated. Then, using FEM, the effects of filament specifications on the overall characteristics of the scaffold were evaluated. Results showed that both the printing process in terms of resting time and remaining time and the printing parameters like pressure, printing speed, and printing path length have influenced the filament properties. In addition, both the filament diameter and elastic modulus had significant effects on the properties of scaffold especially, a 20% increase in the filament diameter caused the scaffold compressive elastic modulus to rise by around 72%. It is concluded that the printing parameters and process must be tuned very well in fabricating scaffolds with the desired morphology and mechanical property.