A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection

In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL^?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd.     

A concise route to 4-aminomethylpyrazoles and 4-aminomethylisoxazoles from acetylacetone-derived hexahydropyrimidines under mild conditions

Acetylacetone was successfully used as a precursor of 4-aminomethylpyrazoles and 4-aminomethylisoxazoles in a two step process at ambient temperature. In the first step, acetylacetone was transformed to the corresponding hexahydropyrimidines (1,3-diazinanes) via two consecutive one-pot Mannich aminomethylations. Hexahydropyrimidines were then treated with hydrazine, phenylhydrazine, and hydroxylamine, respectively, to obtain the corresponding 4-aminomethylpyrazoles and 4-aminomethylisoxazoles in good yields. The hexahydropyrimidine ring decomposed providing the title compounds and a reasonable mechanism has been proposed.     

Synthesis and design of polyurethane and its nanocomposites derived from canola-castor oil: Mechanical,thermal and shape memory properties

The recent global pandemic and its tremendous effect on the price fluctuations of crude oil illustrates the side effects of petroleum dependency more evident than ever. Over the past decades, both academic and industrial communities spared endless efforts in order to replace petroleum-based materials with bio-derived resources. In the current study, a series of shape memory polymer composites (SMPC's) was synthesized from epoxidized vegetable oils, namely canola oil and castor oil fatty acids (COFA's) as a 100% bio-based polyol and isophorone diisocyanate (IPDI) as an isocyanate using a solvent/catalyst-free method in order to eventuate polyurethanes (PU's). Thereafter, graphene oxide (GO) nanoplatelets were synthesized and embedded in the neat PU in order to overcome the thermomechanical drawbacks of the neat matrix. The chemical structure of the synthesized components, as well as the dispersion and distribution levels of the nanoparticles, was characterized. In the following, thermal and mechanical properties as well as shape memory behavior of the specimens were comprehensively investigated. Likewise, the thermal conductivity was determined. This study proves that synthesized PU's based on vegetable oil polyols, including graphene nanoparticles, exhibit proper thermal and mechanical properties, which make them stand as a potential candidate to compete with traditional petroleum-based SMPC's.     

Monoterpene Glycosides from the Aerial Part of Centaurea aucheriana and their Antioxidant and Antifungal Activities

Chemistry of Natural Compounds -     

Gaps in the number of generators of monomial Togliatti systems

Let $I_{d,n}?k[x_0,?,x_n]$ be a minimal monomial Togliatti system of forms of degree d. In [4], Mezzetti and Miró-Roig proved that the minimal number of generators $\mu (I_{d,n})$ of $I_{d,n}$ lies in the interval $[2n+1,\left(\begin{array}{c}n+d?1\\ n?1\end{array}\right)]$. In this paper, we prove that for $n\ge 4$ and $d\ge 3$, the integer values in $[2n+3,3n?1]$ cannot be realized as the number of minimal generators of a minimal monomial Togliatti system. We classify minimal monomial Togliatti systems $I_{d,n}?k[x_0,?,x_n]$ of forms of degree d with $\mu (I_{d,n})=2n+2$ or 3n (i.e. with the minimal number of generators reaching the border of the non-existence interval). Finally, we prove that for $n=4$, $d\ge 3$ and $\mu \in [9,\left(\begin{array}{c}d+3\\ 3\end{array}\right)]?\{11\}$ there exists a minimal monomial Togliatti system $I_{d,n}?k[x_0,?,x_n]$ of forms of degree d with $\mu (I_{n,d})=\mu$.     

Binder-less and free-standing Co–Fe metal nanoparticles-decorated PVdF-HFP nanofiber membrane as an electrochemical probe for enzyme-less glucose sensors

Co–Fe bimetallic nanoparticles-affixed polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP) nanofiber membrane is fabricated using the electrospinning and chemical reduction techniques. The semicrystalline polymeric backbone decorated with the highly crystalline Co–Fe bimetallic nanoparticles enunciates the mechanical integrity, while the incessant and swift electron mobility is articulated with the consistent dissemination of bimetallic nanoparticles on the intersected and multi-layered polymeric nanofibers. The diffusion and adsorption of glucose are expedited in the extended cavities and porosities of as-formulated polymeric nanofibers, maximizing the glucose utilization efficacy, while the uniformly implanted Co⁴⁺/Fe³⁺ active centers on PVdF-HFP nanofibers maximize the electrocatalytic activity toward glucose oxidation under alkaline regimes. Thus, the combinative sorts including nanofiber and nanocomposite strategies of PVdF-HFP/Co–Fe membrane assimilate the enzyme-less electrochemical glucose detection concerts of high sensitivity (375.01 μA mM^?1 cm^?2), low limit of detection (0.65 μm), and wide linear range (0.001 to 8 mM), outfitting the erstwhile enzyme-less glucose detection reports. Additionally, the endowments of high selectivity and real sample glucose-sensing analyses of PVdF-HFP/Co–Fe along with the binder-less and free-standing characteristics construct the state-of-the-art paradigm for the evolution of affordable enzyme-less electrochemical glucose sensors.

     

Head-to-head bisbenzazole derivatives as antiproliferative agents: design,synthesis, in vitro activity,and SAR analysis

Molecular Diversity - In the present work, a series of bisbenzazole derivatives were designed and synthesized as antiproliferative agents. The antiproliferative activity of these compounds was...     

MXene-based composite electrodes for efficient electrochemical sensing of glucose by non-enzymatic method

A recently discovered 2D transition titanium metal carbides also called as MXenes (Ti₃C₂T_x)-based nanocomposite was prepared with Cu₂O through wet precipitation technique, and these materials were further developed as the electrode for sensing glucose by chronoamperometry technique. The prepared MXene-Cu₂O (Ti₃C₂T_x-Cu₂O) nanocomposite was characterized by XRD, FTIR, UV–Vis spectroscopy, FE-SEM, EDAX, and Raman spectroscopy. Morphological studies of the composites revealed that the micro-octahedral shape of Cu₂O is distributed on the surface of MXene with size larger than bare Cu₂O. Further, the prepared composite material was fabricated as a sensing probe, and the electrochemical activities were examined by cyclic voltammetric analysis (CV) and chronoamperometric (CA) methods. From the CV and CA investigation, the current response was higher for the composite than the bare material (Cu₂O & MXene) in the presence of glucose. The amperometric investigation of MXene-Cu₂O composite for the detection of glucose shows a broad linear range (0.01–30 mM) with a sensitivity of 11.061/μAmM cm^?2 and a detection limit of 2.83 μM. Further, the fabricated sensor exhibits good selectivity with interfering species like NaCl, fructose, sucrose, urea, ascorbic acid, lactose, short response time, stability, good reproducibility, and compatibility with human serum sample. From the investigation, the prepared MXene-Cu₂O composite is a good candidate for the direct detection of glucose molecules and is also well suitable for clinical diagnosis.