Monitoring real-time curing of epoxies in situ using single-sided NMR

Adhesively bonded joints using epoxy are widely used in aircraft and aerospace structures. Quality control and defect detection during epoxy curing in such applications is critical. We used single-sided nuclear magnetic resonance (NMR) to nondestructively probe and spatially resolve the change in the characteristic NMR relaxation time (T₂) of epoxies during curing on a substrate. Time-dependent T₂ values were fit to a Weibull function to model temporal changes in the NMR measurables. Our results demonstrate that the reduction in molecular mobility of various epoxy/curing agent mixtures occurs more rapidly at the interface than in the bulk. Further use of single-sided NMR to acquire spatially resolved T₂ data will provide a route for elucidatory epoxy curing studies. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 616–623     

Extraction and Determination of Two Antidepressant Drugs in Human Plasma by Dispersive Liquid–Liquid Microextraction‒HPLC

In this study, an effective method of ultrasound-assisted ionic liquid based dispersive liquid–liquid microextraction (UA?IL?DLLME) coupled with HPLC was applied for extraction and determination of two antidepressant drugs: venlafaxine hydrochloride and amitriptyline hydrochloride from human plasma samples. Three ionic liquids were studied: 1-butyl-3-methyl imidazolium hexafluorophosphate, 1-hexyl-3- methyl imidazolium hexa-fluoro-phosphate, and 1-octyl-3-methyl imidazolium hexafluorophosphate [C8MIM][PF6]. Various factors affect the stages and efficiency of extraction, some of which are pH of sample solution, type and volume of ionic liquid, the time of ultrasonication, centrifuging time and rate, and the ionic strength of solution. In this research, optimum conditions were obtained as 55 μL of [C8MIM][PF6] selected as ionic liquid, pH 11, 2% NaCl, 4 min ultrasonication and 5 min centrifuging at 3500 rpm. Under the optimized conditions, the linearity was obtained in the range of 0.2 to 250 μg/L. The limits of detection were 0.5 μg/L for venlafaxine and 0.8 μg/L for amitriptyline. Pre-concentration factors were 1.3 × 10³ for venlafaxine and 1.2 × 10³ for amitriptyline. The UA?IL?DLLME method coupled with HPLC was successfully used for the determination of venlafaxine and amitriptyline spiked into the real samples of human plasma.     

The critical re-evaluation of the aromatic/antiaromatic nature of Ti3(CO)3: a missed opportunity?

The nature of bonding and aromaticity of Ti(3)(CO)(3), a mill-shaped metal-carbonyl complex, is studied carefully. A unique bonding mechanism between metal and carbonyl groups is found in this species. Ti(3)(CO)(3) is an example of a metal-carbonyl complex with prominent metal to carbonyl donation. Moreover, it is proven that not only is Ti(3)(CO)(3) not an antiaromatic complex but also it is the first synthesized example of d-block, σ+π aromatic species. A quick survey among the first row of transition metals in the periodic table shows that other local minima with similar structures and aromaticity are present and Ti(3)(CO)(3) is the first synthesized species of an unknown family.     

Determination of the formation constant for the inclusion complex between Lanthanide ions and Dansyl chloride derivative by fluorescence spectroscopy: Theoretical and experimental investigation

In this paper, a sensitive, easy, efficient, and suitable method for the calculation of K_f values of complexation between one derivative of Dansyl chloride [5-(dimethylamino) naphthalene-1-sulfonyl 4-phenylsemicarbazide] (DMNP) and Lanthanide(III) (Ln) ions is proposed, using both spectrofluorometric and spectrophotometric methods. Determination of K_f showed that DMNP was mostly selective towards the erbium (III) ion. The validity of the method was also confirmed calculating the Stern–Volmer fluorescence quenching constants (K_sv) that resulted in the same consequence, obtained by calculating the K_f of complexation values. In addition, the UV–vis spectroscopy was applied for the determination of K_f only for the Ln ions that had interactions with DMNP. Finally, the DFT studies were done on Er³⁺ and the DMNP complex for distinguishing the active sites and estimating the pair wise interaction energy. It can be concluded that this derivative of Dansyl chloride with inherent high fluorescence intensity is a suitable reagent for the selective determination of the Er³⁺ ion which can be used in constructing selective Er³⁺ sensors.     

Monitoring of Anti Cancer Drug Letrozole by Fast Fourier Transform Continuous Cyclic Voltammetry at Gold Microelectrode

A continuous cyclic voltammetric study of letrozole at gold microelectrode was carried out. The drug in phosphate buffer (pH 2.0) is adsorbed at ?200 mV, giving rise to change in the current of well‐defined oxidation peak of gold in the flow injection system. The proposed detection method has some of advantages, the greatest of which are as follows: first, it is no more necessary to remove oxygen from the analyte solution and second, this is a very fast and appropriate technique for determination of the drug compound in a wide variety of chromatographic analysis methods. Signal‐to‐noise ratio has significantly increased by application of discrete Fast Fourier Transform (FFT) method, background subtraction and two‐dimensional integration of the electrode response over a selected potential range and time window. Also in this work some parameters such as sweep rate, eluent pH, and accumulation time and potential were optimized. The linear concentration range was of 1.0×10^?7?1.0×10^?10 mol/L (r=0.9975) with a limit of detection and quantitation 0.08 nmol/L and 0.15 nmol/L, respectively. The method has the requisite accuracy, sensitivity, precision and selectivity to assay letrozol in tablets. The influences of pH of eluent, accumulation potential, sweep rate, and accumulation time on the determination of the letrozol were considered.     

Dispersive liquid-liquid microextraction followed by spectrofluorimetry as a simple and accurate technique for determination of thiamine (vitamin B1)

Dispersive liquid-liquid microextraction (DLLME) combined with spectrofluorimetry was applied to the extraction, pre-concentration and analysis of thiamine (vitamin B₁). The procedure is based on (a) the oxidation of thiamine with ferricyanide to form fluorescent thiochrome (TC), (b) the trapping of TC into a microextraction solvent, and (c) spectrofluorometric determination. Microextraction solvent and disperser solvent are directly injected into an aqueous solution containing TC. After centrifuging, phase separation is performed by sedimenting the fine droplets of the microextraction solvent on the bottom of a test tube. The settled phase is transferred into a fluorometer for the determination of thiamine at excitation/emission wavelengths of 375/438 nm. Under the optimized experimental conditions, the method provides a linear dynamic range of 0.2–100 ng mL^?1, a detection limit of 0.06 ng mL^?1, and a relative standard deviation of 3.0%. The method was successfully applied to pharmaceutical formulations and human urine. The results were validated by recovery test and by comparison with other methods, and were found to be highly satisfactory.     

Spectral,crystallographic, theoretical and antibacterial studies of palladium(II)/platinum(II) complexes with unsymmetric diphosphine ylides

The reaction of α‐keto‐stabilized diphosphine ylides [Ph₂P(CH₂)_nPPh₂═C(H)C(O)C₆H₄‐p‐CN] (n = 1 (Y¹); n = 2 (Y²)) with dibromo(1,5‐cyclooctadiene) palladium(II)/platinum(II) complexes, [Pd/PtBr₂(cod)], in equimolar ratio gave the new cyclometalated Pd(II) and Pt(II) complexes [Br₂Pd(κ²‐Y¹)] ( 1 ), [Br₂Pt(κ²‐Y¹)] ( 2 ), [Br₂Pd(κ²‐Y²)] ( 3 ) and [Br₂Pt(κ²‐Y²)] ( 4 ). These compounds were screened in a search for novel antibacterial agents and characterized successfully using Fourier transfer infrared and NMR (¹H, ¹³C and ³¹P) spectroscopic methods. Also, the structures of complexes 1 and 2 were characterized using X‐ray crystallography. The results showed that the P,C‐chelated complexes 1 and 2 have structures consisting of five‐membered rings, while 3 and 4 have six‐membered rings, formed by coordination of the ligand through the phosphine group and the ylidic carbon atom to the metal centre. Also, a theoretical study of the structures of complexes 1 – 4 was conducted at the BP86/def2‐SVP level of theory. The nature of metal–ligand bonds in the complexes was investigated using energy decomposition analyses (EDA) and extended transition state combined with natural orbitals for chemical valence analyses. The results of EDA confirmed that the main portions of ΔE_int, about 57–58%, in the complexes are allocated to ΔE_elstat.     

Adsorption properties of H2O2 trapped inside a boron phosphide nanotube

Abstract  

The behavior of H₂O₂ adsorbed inside a [4,4] armchair boron phosphide nanotube (BPNT) was studied by using density functional calculations. Geometry optimizations were carried out at the B3LYP/6-31G* level of theory using the Gaussian 03 suite of programs. We present the nature of the H₂O₂ interactions inside the nanotube. The interaction between the guest species (H₂O₂) and the nanotube and the dipole moments of the different geometries are discussed. The results show that the binding energies and the dipole moments of the nanotube depend on the orientation and location of the H₂O₂ inside the tube. Among the parallel orientation (AT) and perpendicular orientations (PTA and PTP), the PTA and PTP geometries of the H₂O₂ are unstable whereas the AT-state geometries show stabilization of the guest species inside the BPNT. For AT orientations, the value of the dihedral angle of the H₂O₂ trapped inside the BPNT in the most stable conformation displays a notable change with respect to free H₂O₂. Also, with change of tube type, more efficient binding could not be achieved, and only the orientation and location of the H₂O₂ inside the tube play an important role in determining the binding energy. The polarization of the BPNT in the presence of the guest species in the PT state is higher than that of the AT state. Adsorption of H₂O₂ in the AT state slightly reduces the energy gap of the pristine BPNTs and slightly increases their electrical conductance.     

OXIDATIVE DEPROTECTION OF TRIMETHYLSILYL ETHERS WITH HEXAMETHYLENETETRAMINEBROMINE SUPPORTED ONTO SILICA GEL UNDER MICROWAVE IRRADIATION IN SOLVENTLESS SYSTEM

Hexamethylenetetramine-bromine supported onto[3pc] silica gel rapidly converts trimethylsilyl ethers to their corresponding carbonyl compounds under microwave irradiation in solventless system.     

Numerical Simulation of Mixing in a Micro-well Scale Bioreactor by Computational Fluid Dynamics

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