Synthesis and Structures of Arene Ruthenium (II)–NHC Complexes: Efficient Catalytic α‐alkylation of ketones via Hydrogen Auto Transfer Reaction

A panel of six new arene Ru (II)‐NHC complexes 2a‐f , (NHC = 1,3‐diethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1a , 1,3‐dicyclohexylmethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1b and 1,3‐dibenzyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1c ) were synthesized from the transmetallation reaction of Ag‐NHC with [(η⁶‐arene)RuCl₂]₂ and characterized. The ruthenium (II)‐NHC complexes 2a‐f were developed as effective catalysts for α‐alkylation of ketones and synthesis of bioactive quinoline using primary/amino alcohols as coupling partners respectively. The reactions were performed with 0.5 mol% catalyst load in 8 h under aerobic condition and the maximum yield was up to 96%. Besides, the different alkyl wingtips on NHC and arene moieties were studied to differentiate the catalytic robustness of the complexes in the transformations.     

Carbon Paste Composite with Co3O4 as a New Electrochemical Sensor for the Detection of Allura Red by Reduction

The detection of Allura red (AR) by electrochemical reduction using a different electrode from the conventional mercury electrode is presented. A carbon paste with cobalt (II, III) oxide composite electrode (CoO_x/CPE) is reported for the first time for the detection of AR. Moreover, others dyes such as tartrazine (TZ), sunset yellow (SY), amaranth (AM), Ponceaut 4‐R (P‐4R), and Sudan (SD) as well as pharmaceutical agents such as paracetamol (PMC) that are present in samples that contained AR did not show a reduced signal between 0.0 and ?0.3 V, which is the potential range where AR reduction was observed. The surface electroactivity was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The presence of CoO_X increased the cathodic peak current for AR by more than 50 % and 65 % via CV and square wave voltammetry (SWV), respectively, compared with an unmodified carbon paste electrode. Under the optimal parameters, (pH=3.0, accumulation time (t_ACC)=60 s and accumulation potential (E_ACC)=0.50 V), the detection limit for AR was 0.05 μmol L^?1. The new sensor was sensitive and stable for the detection of AR. Moreover, it was easily manufactured and very convenient for food samples such as soft and isotonic drinks as well as chili sauce.     

Biological applications of amide and amino acid containing synthetic macrocycles

ABSTRACT

Amino acid derived macrocycles with elaborate well-defined stereochemistry are a unique class of compounds that have been isolated from natural sources. Macrocycles like cyclosporine, octreotide, and valinomycin have been used in multiple applications, like drugs or ion sensors. Chemists have long been fascinated by the unique molecular recognition capabilities of these macrocycles and tried to design synthetic analogs with similar functions. This article is focused on reviewing current research on amide and amino acid containing macrocycles that have been developed in research laboratories for biological recognition, specifically for anion sensing, ion transport, carbohydrate sensing, and peptide sensing.     

Properties of G-martingales with finite variation and the application to G-Sobolev spaces

As is known, if $B={\left(B_t\right)}_{t\in [0,T]}$ is a $G$-Brownian motion, a process of form ${\int }_0^t{\eta }_{s}d{〈B〉}_s?{\int }_0^{t}2G\left({\eta }_s\right)ds$, $\eta \in M_G^1(0,T)$, is a non-increasing $G$-martingale. In this paper, we shall show that a non-increasing $G$-martingale cannot be form of ${\int }_0^t{\eta }_{s}ds$ or ${\int }_0^t{\gamma }_{s}d{〈B〉}_s$, $\eta ,\gamma \in M_G^1(0,T)$, which implies that the decomposition for generalized $G$-Itô processes is unique: For arbitrary $\zeta \in H_G^1(0,T)$, $\eta \in M_G^1(0,T)$ and non-increasing $G$-martingales $K,L$, if ${\int }_0^t{\zeta }_{s}d{B}_s+{\int }_0^t{\eta }_{s}ds+K_t=L_t,t\in [0,T],$then we have $\eta \equiv 0$, $\zeta \equiv 0$ and$K_t=L_t$. As an application, we give a characterization to the $G$-Sobolev spaces introduced in Peng and Song (2015).     

Development and validation of an ultra‐high‐performance liquid chromatography–tandem mass spectrometry method to determine the bioavailability of warfarin and its major metabolite 7‐hydroxy warfarin in rats dosed with oral formulations containing different polymorphic forms

A simple, sensitive and rapid ultra‐high‐performance liquid chromatography–electrospray ionization–tandem mass spectrometry method was developed and validated for the quantification of warfarin and 7‐hydroxy warfarin in Sprague Dawley (SD) rats. Animals were administered a single dose of warfarin sodium formulations (crystalline and amorphous) at 12 mg/kg via oral gavage and blood was drawn over a 96‐h time course. Sample process recoveries, matrix effect and analyte stability were determined. The linearity for warfarin and 7‐hydroxy warfarin was from 5 to 2000 ng/mL in blank SD rat plasma. Correlation coefficients (r²) for standard calibration curves were >.98 and analytes quantified within ±15% of target at all calibrator concentrations. The average percent accuracy and precision for intra‐ and inter‐day were 93.7%–113.8% and ≤12.1%, respectively, for warfarin and 7‐hydroxy warfarin, across the quality control standards (5, 10, 500, 1800 and 2000 ng/mL). Acceptable analytical recovery (>55%) was achieved with process efficiencies >41.5% and matrix effects <139.9% over the analytical range. Both analytes were stable in stock solution, autosampler, benchtop and three cycles of freeze–thaw with percent accuracy ≥90.2% and precision (percent relative standard deviation) ≤14%. The validated method was successfully applied to a pre‐clinical bioavailability study of crystalline and amorphous warfarin sodium formulations in SD rats.     

On the Discrete Criteria and JØ rgensen Inequalities for SL(m,F((t)))

In this paper, the author gives the discrete criteria and J\o rgensen inequalities of subgroups for the special linear group on $\overline{\mathrm{F}}((t))$ in two and higher dimensions.     

Highly sensitive and selective detect of p‐arsanilic acid with a new water‐stable europium metal–organic framework

The p‐arsanilic acid (p‐ASA), as an aromatic organoarsenic compounds, had received considerable concerns for their potential toxicity and carcinogenic properties. It was essential to detect p‐ASA with a facile method. In this paper, an europium based fluorescent metal–organic framework (MOF) [Eu₂(clhex)·2H₂O)]·H₂O ( BUC‐69 ) was successfully prepared under hydrothermal conditions with 1,2,3,4,5,6‐cyclohexanehexacarboxylic acid (H₆clhex) as organic linker. BUC‐69 displayed superior fluorescence capability to achieve selective and sensitive detection toward p‐ASA in water, which presented the first example of a MOF‐based sensor to detect p‐ASA. BUC‐69 showed excellent chemical stability in solutions under pH ranging from 4 to 12, which makes it be a potential sensor both in acidity and alkalinity condition. Significantly, BUC‐69 performed well in fluorescent sensing of p‐ASA at a low concentration (10^?6 M) in the simulated wastewater prepared with real lake water, and the results were comparable to the values detected by Inductively Coupled Plasma Optical Emission Spectrometer (ICP‐OES). The corresponding mechanism of fluorescent sensing toward p‐ASA with BUC‐69 was proposed and affirmed.