The Utility of Isothiocyanato Thiophenes in the Synthesis of Thieno[2,3-d]pyrimidine Derivatives as Possible Radioprotective and Anticancer Agents

The synthesis of novel thioureido derivatives 3, 8, and 10; biscompounds 7, 9, and 11; and tetracyclic compounds 5, 6, and 16 utilizing 5-isothiocyanato-3-methyl-thiophene-2,4-dicarboxylic acid diethyl ester 2 are reported. The structures of these compounds were confirmed by microanalyses and IR, ¹H NMR, and mass spectroscopy. Preliminary biological studies of some of the synthesized compounds showed promising radioprotective and anticancer activities.     

Catalytic Synthesis of 2-Methyl-1,4-Naphthoquinone (Vitamin K3) Over Silica-Supported Aminomethyl Phosphine-Ru(II), Pd(II), and Co(II) Complexes

Ru(II), Pd(II), and Co(II) complexes of the free ditertiary aminomethylphosphine ligand, N,N-bis(diphenylphosphinomethyl)aminopropyltriethoxysilane [(EtO)₃Si(CH₂)₃ N(CH₂PPh₂)₂] (DIPAPTES), and its SiO₂-DIPAPES have been synthesized under a nitrogen atmosphere using Schlenk techniques. All the complexes were used as catalysts for the oxidation of 2-methyl naphthalene (2MN) to give 2-methyl-1,4-naphthoquinone (vitamin K₃, menadione, 2MNQ) in the presence of hydrogen peroxide as a clean and cheap oxidant. The catalytic synthesis of vitamin K₃ was investigated using both homogeneous catalysis with free complexes and heterogeneous catalysis with silica-supported complexes. [(DIPAPTES)PdCl₂] and its silica-supported form showed the best catalytic activity for the selective oxidation of 2-methyl naphthalene to 2-methyl-1,4-naphtoquinone compared to the other metal complexes. 2MNQ yield reached 52.26% with the 2MN conversion of 90.52% using complex [(DIPAPTES)PdCl₂] and 58.59% with the 2MN conversion of 99.56% using the silica supported [SiO₂(DIPAPES)PdCl₂] complex for 1 h. Recycling was investigated for the silica-supported Pd(II) complex and compared with the classical production of vitamin K₃.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Spectrophotometric studies on the interactions of C.I. Basic Red 9 and C.I. Acid Blue 25 with hexadecyltrimethylammonium bromide in cationic surfactant micelles

Interactions between cationic dye-cationic surfactant and anionic dye-cationic surfactant systems were investigated in aqueous solutions using spectrophotometric method at 288.15, 298.15, 308.15 and 318.15 K. C.I. Basic Red 9 (BR9) and C.I. Acid Blue 25 (AB25) were used as cationic and anionic dyes, respectively, and hexadecyltrimethylammonium bromide (HDTMABr) was selected as cationic surfactant in this study. Although there was an interaction between the AB25 and the HDTMABr molecules, an interaction between the BR9 and HDTMABr did not occur due to the electrostatic repulsion forces. Binding constants and partition coefficients between the micellar and the bulk water phases for the AB25-HDTMABr system were calculated from the changes in absorbance values and the critical micelle concentrations at different temperatures. It was found that the values of binding constant and partition coefficient decreased with increasing temperature. Thermodynamic parameters (ΔG⁰, ΔH⁰ and ΔS⁰) were determined for the binding and partition processes of AB25-HDTMABr system. It was concluded from ΔG⁰ values that the binding of AB25 to HDTMABr occurred spontaneously. In addition, the binding and partition processes were exothermic.     

Laser Ablation Molecular Isotopic Spectrometry

A new method of performing optical isotopic analysis of condensed samples in ambient air and at ambient pressure has been developed: Laser Ablation Molecular Isotopic Spectrometry (LAMIS). The technique uses radiative transitions from molecular species either directly vaporized from a sample or formed by associative mechanisms of atoms or ions in a laser ablation plume. This method is an advanced modification of a known atomic emission technique called laser-induced breakdown spectroscopy (LIBS). The new method — LAMIS — can determine not only chemical composition but also isotopic ratios of elements in the sample. Isotopic measurements are enabled by significantly larger isotopic shifts found in molecular spectra relative to atomic spectra. Analysis can be performed from a distance and in real time. No sample preparation or pre-treatment is required. Detection of the isotopes of hydrogen, boron, carbon, and oxygen are discussed to illustrate the technique.     

Understanding run-in behavior of diamond-like carbon friction and preventing diamond-like carbon wear in humid air

The friction behavior of diamond-like carbon (DLC) is very sensitive to the test environment. For hydrogen-rich DLC tested in dry argon and hydrogen, there was always an induction period, so-called "run-in" period, during which the friction coefficient was high and gradually decreased before DLC showed an ultralow friction coefficient (less than 0.01) behavior. Regardless of friction coefficients and hydrogen contents, small amounts of wear were observed in dry argon, hydrogen, oxygen, and humid argon environments. Surprisingly, there were no wear or rubbing scar on DLC surfaces tested in n-pentanol vapor conditions, although the friction coefficient was relatively high among the five test environments. Ex situ X-ray photoelectron and near-edge X-ray absorption fine-structure spectroscopy analyses failed to reveal any differences in chemical composition attributable to the environment dependence of DLC friction and wear. The failure of getting chemical information of oxygenated surface species from the ex situ analysis was found to be due to facile oxidation of the DLC surface upon exposure to air. The removal or wear of this surface oxide layer is responsible for the run-in behavior of DLC. It was discovered that the alcohol vapor can also prevent the oxidized DLC surface from wear in humid air conditions.     

<Emphasis Type="Italic">I</Emphasis>–<Emphasis Type="Italic">V</Emphasis>–<Emphasis Type="Italic">T</Emphasis> analysing an inhomogeneous Au/Poly(4-vinyl phenol)/p-Si structure with a double Gaussian distribution of barrier heights

In this study, the current–voltage (I–V) characteristics of Au/Poly(4-vinyl phenol)/p-Si structures have been measured over a wide temperature range (100–300 K). These structures have been analyzed according to thermionic emission (TE) theory, as a result of which an abnormal decrease occurred in the zero-bias barrier height (f_b0 \phi_{b0} ) and an increase in the ideality factor (n) was observed with temperature decrease and nonlinearity in the activation energy plot. By assuming a Gaussian distribution (GD) of barrier heights of the Au/Poly(4-vinyl phenol)/p-Si structures, barrier inhomogeneities are believed to responsible for this behavior. Evidence is given for the existence of a double GD with mean barrier heights ([`(f)]<sub>b0</sub> \bar{\phi }_{b0} ) of 1.042 and 0.623 eV, standard deviations of 0.138 and 0.081 V, and ideality factors 2.76 and 7.26, which remain effective in the temperature ranges of 180–300 and 100–160 K, respectively. As a result, without using the temperature coefficient of the barrier height, the modified ln(I <sub>o</sub> /T <sup>2</sup>) − q <sup>2</sup> σ <sub>o</sub> <sup>2</sup>/2(kT)<sup>2</sup> vs. q/kT plot gives [`(f)]_b0 \bar{\phi }_{b0} values and Richardson constants (A ^* ) as 1.036 and 0.623 eV, and 36.20 and 19.99 A/cm² K², respectively. The effective Richardson constant value of 36.20 A/cm² K² is very similar to the theoretical value of 32 A/cm²K² for p-Si. Consequently, the temperature dependence of the forward bias I–V characteristics of Au/Poly(4-vinyl phenol)//p-Si (MIS) structure could be attributed to the thermionic emission (TE) mechanism with double GD of the barrier heights.     

On dynamical behavior for optical solitons sustained by the perturbed Chen–Lee–Liu model

This study investigates the perturbed Chen–Lee–Liu model that represents the propagation of an optical pulse in plasma and optical fiber. The generalized exponential rational function method is used for this purpose. As a result, we obtain some non-trivial solutions such as the optical singular, periodic, hyperbolic, exponential, trigonometric soliton solutions. We aim to express the pulse propagation of the generated solutions, by taking specific values for the free parameters existed in the obtained solutions. The obtained results show that the generalized exponential rational function technique is applicable, simple and effective to get the solutions of nonlinear engineering and physical problems. Moreover, the acquired solutions display rich dynamical evolutions that are important in practical applications.     

Antifungal Activity of Soft Tissue Extract from the Garden Snail Helix aspersa (Gastropoda,Mollusca)

Gastropods comprise approximately 80% of molluscans, of which land snails are used variably as food and traditional medicines due to their high protein content. Moreover, different components from land snails exhibit antimicrobial activities. In this study, we evaluated the antifungal activity of soft tissue extracts from Helix aspersa against Candida albicans, Aspergillus flavus, and Aspergillus brasiliensis by identifying extract components using liquid chromatography-tandem mass spectrometry (LC-MS-MS). Two concentrations of three extracts (methanol, acetone, and acetic acid) showed antifungal activity. Both acetone (1 g/3 mL) and acetic acid extracts (1 g/mL) significantly inhibited C. albicans growth (p = 0.0001, 5.2 ± 0.2 mm and p = 0.02, 69.7 ± 0.6 mm, respectively). A. flavus and A. brasiliensis growth were inhibited by all extracts at 1 g/mL, while inhibition was observed for acetic acid extracts against A. brasiliensis (p = 0.02, 50.3 ± 3.5 mm). The highest growth inhibition was observed for A. flavus using acetic acid and acetone extracts (inhibition zones = 38 ± 1.7 mm and 3.1 ± 0.7 mm, respectively). LC-MS-MS studies on methanol and acetone extracts identified 11-α-acetoxyprogesterone with a parent mass of 372.50800 m/z and 287.43500 m/z for luteolin. Methanol extracts contained hesperidin with a parent mass of 611.25400 m/z, whereas linoleic acid and genistein (parent mass = 280.4 and 271.48900 m/z, respectively) were the main metabolites.     

High‐Density Polyethylene Micro‐ and Nanocomposites: Effect of Particle Shape,Size and Surface Treatment on Polymer Crystallinity and Gas Permeability

Summary: High‐density polyethylene (HDPE) micro‐ and nanocomposites with spherical and platelike inclusions were prepared and the effect of filler particles on polymer crystallinity and gas permeability was investigated. Platelike inclusions strongly reduce the polymer permeability coefficient, while spherical ones have no influence on it, irrespective of their size. The reduction in gas permeability depends on the average aspect ratio of the inclusions, which in turn depends on the exfoliation of the organo‐montmorillonites (OM) and consequently on its surface treatment.

A TEM micrograph of 3 vol.‐% 2C18 · M‐HDPE nanocomposite, showing partial exfoliation of the organo‐montmorillonite.     

Self-reported Side-effects of Ultraviolet-C Disinfection Devices

The COVID-19 pandemic increased sales of portable UV-C devices as a means of inactivating the SARS-CoV-2 virus. Research suggests that excessive UV-C exposure to the eyes and skin can lead to side-effects, primarily photokeratitis and erythema, but these findings are limited to case studies. This study explores self-reported side-effects of UV-C devices by collating five waves of UK consumer survey data from April 2020–December 2021 (N = 26 864). 30%–46% of owners report a side-effect after using a device claiming to emit UV-C. However, detailed analysis of Wave 4 data (N = 309) highlights inconsistencies between reported and plausible side-effect(s) associated with skin or eye exposure from UV-C devices. Alternative explanations are considered, namely that the reported side-effect(s) were psychosomatic or misattributed to direct exposure of UV-C radiation. Data regarding awareness of warnings about device side-effect(s) supports the misattribution explanation. For risk assessment purposes, limited reliable information about specific irritation or injury to the eye and skin was found from self-reporting surveys. To optimize future data collection, we recommend addressing recall errors by: reducing the period under investigation, supplementing responses with empirical measures, and incentivizing respondents to provide accurate information about the make and model of the UV-C device.