Chemical characterisation of bioactive compounds in Medicago sativa growing in the desert of Oman

Medicago sativa Linn growing in Omani desert were chemically characterised using flame photometry, inductively coupled plasma, gas chromatography–mass spectrometry and high performance liquid chromatographic (HPLC) analysis. HPLC analyses were performed to determine the phenolics and flavonoids present in M. sativa. The major compounds detected in M. sativa leaves were protchaechenic acid (3.22%), hydroxyl benzoic acid (1.05%), β-Phenyl caffate (0.97%) and kaempherol (0.89%). Pterostilbene, a cholesterol-lowering compound, was detected in M. sativa.     

Atrane complexes chemistry as a tool for obtaining trimodal UVM-7-like porous silica

Abstract

The use of atrane complexes as hydrolytic precursors enables the homogeneous incorporation of manganese (25 ≤ Si/Mn ≤ 48) throughout the porous walls of the nanoparticles of a surfactant-templated bimodal mesoporous silica (UVM-7). The subsequent leaching of the manganese nanodomains allows adding controlled microporosity to the host silica framework. The resulting final silica material presents three pore systems structured at different length scales: interparticle textural-type macroporosity (ca. 43.2 nm), ordered intraparticle mesoporosity (ca. 2.63 nm; after template removal), and well-dispersed microporosity (< 2 nm; as consequence of the lixiviation of the Mn-rich domains). The good dispersion of the guest element (Mn) in the silica intermediate provided by the atrane route is responsible for the disordered but regular microporosity achieved.     

NH4I-catalyzed chalcogen(S/Se)-functionalization of 5-membered N-heteroaryls under metal-free conditions

Herein, we described the NH₄I-catalyzed CH bond chalcogenation of N-heteroaryls in the presence of a minimum amount of DMSO/H₂O/acetic acid as additives (2.5/2.5/1?M equiv., respectively), under metal-free conditions. Under optimized conditions, a wide variety of sulfenyl/selenyl imidazo[1,2-α]pyridines were prepared in very good yields. Moreover, the present approach was also highly efficient for the chalcogenation of different 5-membered N-heteroaryls, e.g., indole, imidazothiazole, indazole and imidazopyrimidine derivatives.     

Supramolecular assemblies based on organometallic quinonoid linkers: a new class of coordination networks

Self-assembly of coordination frameworks exhibiting original architectures is an active area of research. Generally, such assemblies are constructed from organic spacers and transition metals of different geometrical structures. Herein, we report a novel class of supramolecular coordination assemblies with organometallic linkers based on metalated quinonoid and thioquinonoid complexes that serve as spacers. The organometallic ligands are stable and have the general formula [Cp*M(eta(4)-benzoquinone)] (o- and p-benzoquinone, Cp*=C(5)Me(5), M=Rh, Ir) and [Cp*Ir(eta(4)-thiobenzoquinone)] (o- and p-thiobenzoquinone). These units bind through both oxygen or sulfur atoms to metal ions of different coordination geometry, such as Cu(I), Ag(I), and Pt(II), to generate supramolecular coordination networks, with the metalated quinonoid or thioquinonoid linkers acting as backbones and the metal centers as nodes. This novel family of supramolecular assemblies exhibits short pi-pi and MM interactions. These results illustrate successfully the role of the organometallic linkers to produce an impressive range of novel supramolecular architectures that hold promise for the development of functional materials.     

Chemical Validation of Mycobacterium tuberculosis Phosphopantetheine Adenylyltransferase Using Fragment Linking and CRISPR Interference**

The coenzyme A (CoA) biosynthesis pathway has attracted attention as a potential target for much-needed novel antimicrobial drugs, including for the treatment of tuberculosis (TB), the lethal disease caused by Mycobacterium tuberculosis (Mtb). Seeking to identify inhibitors of Mtb phosphopantetheine adenylyltransferase (MtbPPAT), the enzyme that catalyses the penultimate step in CoA biosynthesis, we performed a fragment screen. In doing so, we discovered three series of fragments that occupy distinct regions of the MtbPPAT active site, presenting a unique opportunity for fragment linking. Here we show how, guided by X-ray crystal structures, we could link weakly-binding fragments to produce an active site binder with a K_D <20 μM and on-target anti-Mtb activity, as demonstrated using CRISPR interference. This study represents a big step toward validating MtbPPAT as a potential drug target and designing a MtbPPAT-targeting anti-TB drug.     

Stress Degradation Behavior of Desipramine Hydrochloride and Development of Suitable Stability-Indicating LC Method

A simple reverse phase liquid chromatographic method was developed for the quantitative determination of desipramine hydrochloride and its related impurities in bulk drugs which is also stability-indicating. During the forced degradation at hydrolysis, oxidative, photolytic and thermal stressed conditions, the degradation results were only observed in the oxidative stress condition. The blend of the degradation product and potential impurities were used to optimize the method by an YMC Pack Pro C₁₈ stationary phase. The LC method employs a linear gradient elution with the water–acetonitrile–trifluoroacetic acid as mobile phase. The flow rate was 1.0 mL min^?1 and the detection wavelength 215 nm. The stressed samples were quantified against a qualified reference standard and the mass balance was found close to 99.0% (w/w) when the response of the degradant was considered to be equal to the analyte (i.e. desipramine). The developed RP-LC method was validated in agreement with ICH requirements.     

Regioselective,Solvent‐ and Metal‐Free Chalcogenation of Imidazo[1,2‐a]pyridines by Employing I2/DMSO as the Catalytic Oxidation System

Highly efficient molecular‐iodine‐catalyzed chalcogenations (S and Se) of imidazo[1,2‐a]pyridines were achieved by using diorganoyl dichalcogenides under solvent‐free conditions. This approach afforded the desired products that had been chalcogenated regioselectively at the C3 position in up to 96 % yield by using DMSO as an oxidant, in the absence of a metal catalyst, and under an inert atmosphere. This mild, green approach allowed the preparation of different types of chalcogenated imidazo[1,2‐a]pyridines with structural diversity. Furthermore, the current protocol was also extended to other N‐heterocyclic cores.     

Effect of dimensions of multi-walled carbon nanotubes on its enrichment efficiency of metal ions from environmental waters

The effect of dimensions (length and external diameter) of multi-walled carbon nanotubes (MWCNTs) on its preconcentration efficiency towards some metal ions (Pb²⁺, Cd²⁺, Cu²⁺, Zn²⁺ and MnO₄⁻) from environmental waters prior to their analysis by flame atomic absorption spectroscopy (FAAS) was investigated. MWCNTs (as-received from the manufacturer) of various external diameters and lengths were involved. Other variables optimized included effects of pH of water sample, composition and volume of eluent, mass of the MWCNTs, breakthrough volume and coexisting ions. Maximum recovery of metal ions was obtained at pH 9 where it was thought that precipitation of metals as their hydroxides played the major factor in metals uptake by MWCNT. It was suggested that the use of appropriate dimensions of MWCNTs may support the trapping process of the precipitated metal hydroxides by MWCNTs. It was found that long MWCNT of length 5-15 μm and external diameter 10-30 nm gave the highest enrichment efficiency towards almost all the targeted metal ions. It could be used for preconcentration of MnO₄⁻, Cu²⁺, Zn²⁺ and Pb²⁺ with almost full recovery; but not for Cd²⁺ due to its low recovery. The optimized solid phase extraction (SPE) procedure was capable of determining metal ions in the linear range 20-100 ng mL⁻¹ (except for Zn²⁺ from 20 to 150 ng mL⁻¹). Detection limits were 0.709 ng mL⁻¹ for MnO₄⁻, 0.278 ng mL⁻¹ for Pb²⁺, 0.465 ng mL⁻¹ for Cu²⁺, 0.867 ng mL⁻¹ for Zn²⁺. Application of the optimized SPE procedure to environmental waters (tap water, reservoir water and stream water) gave spike recoveries of the metals in the range of 81-100%.