MgFe2O4@SiO2-PrNH2/Pd/bimenthonoxime core-shell magnetic nanoparticles as a recyclable green catalyst for heterogeneous Suzuki cross-coupling in aqueous ethanol

Magnetically recoverable MgFe₂O₄@SiO₂-PrNH₂/Pd/bimenthonoxime nanoparticles were prepared and characterized by SEM, EDX, TEM, XRD, XPS, ICP, VSM and FT-IR. The nanocatalyst was used for Suzuki cross-coupling in aqueous ethanol media, and the corresponding biaryl derivatives were synthesized within short reaction time. The catalyst was separated by an external magnet and reused several times.

     

ZnO–Bentonite nanocomposite: an efficient catalyst for discharge of dyes,phenol and Cr(VI) from water

The present work focused on application of ZnO-NPs@bentonite, as a catalyst, for disposal of different pollutants such as dyes, phenol compounds and Cr(VI) ions from water. The prepared ZnO–bentonite nanocomposite was characterized by using FT-IR, X-ray powder diffraction, and Scanning electron microscopy analysis. The results showed that the amount of zinc oxide influenced the catalytic performance of ZnO–bentonite nanocomposite. Small amounts of zinc oxide on bentonite have a positive effect whereas increase in weight ratios has a negative effect.

     

Myristigranol,a new diarylpropane derivative from the wood of Myristica fragrans

Myristigranol, a new diarylpropane derivative, was isolated from the methanol extract of Myristica fragrans wood along with one diarylpropanoid and three stilbenoids. The isolated constituents were exhaustingly identified using the analyses of 1D and 2D NMR spectroscopic techniques and comparison of the literatures reported as well. The antioxidant activity was also determined.

     

Review: Inverse coordination. Inorganic open and cyclic nitrogen heteroatom molecules as coordination centers. A survey of molecular topologies

This review is a follow up to a previous article [I. Haiduc J. Coord. Chem. (2018) doi:10.1080/00958972.2018.1515429.] which illustrated the concept of inverse coordination with structures in which the coordination center is nitrogen alone (mono- and poly-nitrogen moieties). Here the open and cyclic heteroatom molecules with inorganic skeletons and nitrogen donor sites are presented. Organic nitrogen heterocycles will be treated in a further review.

     

Crystallographic and DFT studies on host-guest complexes consisting of zinc bisporphyrinates and 1-phenylethylamine

We have investigated the chirality transfer from 1-phenylethylamine to a 5-amino-1,3-phthalic acid diamide-linked zinc bisporphyrinate through crystallographic and DFT studies. When the hosts were mixed with optically pure 1-phenylethylamine, CD showed moderate signals in the Soret band region. Single crystals of the corresponding 1:1 and 1:2 host-guest complexes were obtained. We present the first crystallographic structure of a 1:2 host-guest complex consisting of a bisporphyrin host and chiral monoamine guests. The structure reveals that the host-guest interactions are different for two guest molecules. The first guest is involved in a hydrogen bond and π-π interactions, while the second one is only involved in π-π interactions, which has not been observed in previous studies. The corresponding chirality transfer mechanism was also rationalized by DFT calculations.

     

Structural characterization and thermal degradation of poly(methylmethacrylate)/zinc oxide nanocomposites

This work is based on the preparation of composites of poly(methylmethacrylate) with zinc oxide nanoparticles synthesized by solution casting method.

Chloroform cast poly(methylmethacrylate) films containing different amounts of ZnO nanoparticles were characterized by XRD, SEM, UV-vis spectroscopy, FTIR spectroscopy and TGA.

The results show that ZnO nanoparticles with a size of 24?nm were fairly dispersed in the polymer matrix. The obtained material had UV shielding capability with optical transparency. Thermal characterization shows that, the nanocomposites were more thermally stable than pure PMMA presenting three degradation steps. Apparent kinetic parameters were determined for each degradation step using peak fitting methodology. According to activation energies, ZnO particles affect simultaneously but oppositely the kinetics of underlying degradation reactions. Thermal stability of the PMMA/ZnO nanocomposites was the result of the overall balance in favor of the inhibiting effect of ZnO.     

The role of 8-quinolinyl moieties in tuning the reactivity of palladium(II) complexes: a kinetic and mechanistic study

The rate and mechanism of chloride substitution from Pd(II) complexes, chlorobis-(2-pyridylmethyl)aminepalladium(II), 1, chloro-8-[(2-pyridylmethyl)amino]quinolinepalladium(II), 2, chloro-N-(2-pyridinylmethylene)-8-quinolinaminepalladium(II), 3, and chlorobis(8-quinolinyl)aminepalladium(II), 4, are reported. The labile chloride was substituted from the complexes by thiourea nucleophiles viz, thiourea (Tu), N,N′-dimethylthiourea (Dmtu) and N,N,N′,N′-tetramethylthiourea (Tmtu). The reactions were monitored under pseudo-first-order conditions in methanol using stopped-flow spectrophotometry as a function of concentration and temperature. All the reactions obeyed the rate law k_obs = k₂[Nu] following the order 1 > 3 > 2 > 4 with 4 exhibiting the slowest rate of substitution due to the stronger σ-donor effect of 8-quinolyl moiety of the coordinated ligand, which makes the Pd center more electron-rich. This slows the nucleophilic attack by the nucleophiles. The values of the thermodynamic parameters (ΔH^# and ΔS^#) support an associative substitution mechanism. The trends in the DFT calculated data support the experimentally observed order of the reactivity of the complexes.

     

GC-MS and LC-MS Identification of the Phenolic Compounds Present in the ethyl Acetate Fraction Obtained from Senna tora,L. Roxb. seeds

The aim of this work is to characterize the active constituents present in the ethyl acetate fraction of Senna tora, L. Roxb. seeds. Due to the fact that the main biological activity of S. tora, L seeds is attributed to its phenolic compounds which are mainly isolated from Ethyl acetate fraction, to avoid repetition of work and to save time, it was deemed necessary to confirm the identity of these phenolic compounds. This was done by GC-MS and LC-MS analysis of the ethyl acetate fraction where the structures of the isolated compounds were established on the basis of molecular ion peak and their fragmentation pattern. They were identified as Chrysophanol, Chrysarobin, 10-hydroxy-5-methoxy-2-methyl-1, 4-anthracenedione, Rubrofusarin, Parietin, Griseoxanthone-B, Isotorachrysone, and Cumbiasin B.

     

Microbial transformation of isocoronarin D by Cunninghamella echinulata NRRL 1386

The diterpene isocoronarin D (1) is a bioactive major constituent of labdane diterpene from the aerial parts of Curcuma comosa Roxb. (Zingiberaceae), the Thai medicinal plant. Microbial transformation of 1 was performed by the fungus Cunninghamella echinulata NRRL 1386 to yield three new metabolites, 3β-hydroxyisocoronarin D (2), 6α-hydroxyisocoronarin D (3) and 3β,7α-dihydroxyisocoronarin D (4). The structures of the new compounds were elucidated by spectroscopic techniques.

     

Immobilization of glucose oxidase based on the sodium alginate-modified products of a functionalized metal organic framework and the application for one-pot analysis of glucose

A self-assembled functionalized metal-organic framework, Zn₄O(NH₂BDC)₃ microcrystalline (IRMOF3) could be prepared by washing complex with DMF and CH₂Cl₂. Via modification with sodium alginate (AA), IRMOF3-AA samples could be obtained. IR and TEM were used for structural confirmation of IRMOF3-AA samples. PEG-GOD could be obtained via PEGylation of glucose oxidase (GOD), which could be confirmed by X-ray photoelectron spectroscopy (XPS) and used for further application. IRMOF3-AA@PEG-GOD samples could be obtained by the immobilization of PEG-GOD to IRMOF3-AA, and the best immobilization condition was achieved by adjusting the amount of GOD. From the view point of enzyme mimics, combined with peroxidase-like properties of the IRMOFS-AA samples, the determination of glucose was demonstrated with a linear range from 5?×?10^?5 mol/L to 1.6?×?10^?3 mol L^?1 using tetramethylbenzidine (TMB) as chromogenic substrate. The prepared IRMOF3-AA@PEG-GOD samples exhibited dual functional enzyme-like (peroxidase and GOD-like) activities, with simple experimental steps.

     

Green and Reusable Synthetic Procedure for Pyridine N-Oxides Catalyzed by a Lacunary Polyoxometalate

A lacunary Keggin polyoxometalate of K₈[BW₁₁O₃₉H] · 13H₂O was used as an effective and reusable catalyst for pyridine oxidation. Good yields of pyridine N-oxides were obtained in this catalytic system with hydrogen peroxide in water under mild conditions.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

A novel self-assembly based on double-layer zinc porphyrin sensitizers in supramolecular solar cell

Two new self-assemblies based on zinc porphyrin dyes ZnPx-ZnPA (x?=?1, 2) were synthesized and used for dye-sensitized solar cells. Capping layer dyes consist of zinc porphyrin (ZnP) as core unit and carbazole (P1), phenothiazine (P2) as electron-donating group. The dye ZnPA contains carboxylic group as an anchor porphyrin with upper dyes (denoted as ZnP1 and ZnP2) formed dyads by coordination bonds of Zn-to-ligand self-assembled devices. The assembly modes were also verified by transmission electron microscopy (TEM). The influence of the upper porphyrins on molecular structure as well as photovoltaic performance was investigated via photophysical and electrochemical studies and calculations. With addition of the phenothiazine unit, the ZnP2-ZnPA possesses better light-harvesting capability with a significantly red-shifted Q-band. The photoelectrochemical efficiencies for ZnP2-ZnPA are better than those of ZnP1-ZnPA ascribed to larger J_sc and V_oc.

     

New aurone epoxide and auronolignan from the heartwood of Cotinus coggygria Scop

New aurone epoxide, 2,10-oxy-10-methoxysulfuretin (14), and new auronolignan (15), named cotinignan A, were isolated by silica gel column and semipreparative HPLC chromatography from the methylene chloride/methanol extract of Cotinus coggygria Scop. heartwood. In addition, thirteen known secondary metabolites namely sulfuretin, 2,3-trans-fustin, fisetin, butin, butein, taxifolin, eriodictyol, 3',5,5',7–tetrahydroxyflavanone, 3',4',7-trihydroxyflavone, 3-O-methyl-2,3-trans-fustin, 3-O-galloyl-2,3-trans-fustin, β-resorcylic acid and 3-O-β-sitosterol glucoside were isolated as well. Their structures were elucidated by 1D and 2D NMR, HR-ESI-MS, IR and UV. Ten out of eleven isolated flavonoids possess 7, 3' and 4' hydroxy groups. These structural features could be considered as chemotaxonomic characteristic of flavonoids from C. coggygria. Cotinignan A (15) represents new subclass of secondary metabolites - auronolignans.

     

Biochemical relevance of Cr(III) complexes of isoniazid: synthesis,characterization, DFT,antibacterial screening,antioxidant activity and glucose-lowering effect in STZ-induced diabetic rats

Molecular mechanism suggests that the incorporation of an antioxidant organic moiety to chromium will be a sound strategy for the synthesis of safer and more effective hypoglycemic compounds. Two Schiff base ligands were derived by condensation of isonicotinyl hydrazide with salicylaldehyde/o-hydroxyacetophenone which further yield four novel chromium(III) complexes of types [Cr(L)Cl₂(H₂O)] and [Cr(L)₂]Cl. The ligands and complexes were characterized by analytical and spectroscopic techniques. DFT study at the basic set B3LYP and TD-SCF/6-311-G level was employed to confirm the geometry of the investigated compounds. Ligands were tested for their antioxidant activity and exhibited good antioxidant activity. Assessment of insulin-like activity of the complexes was initially performed in vitro by measuring the inhibition of α-amylase. The complex with highest in vitro activity was investigated for in vivo antidiabetic activity on the model of STZ-induced diabetic rats, which demonstrated that complex 4 significantly lowers the blood glucose level in rats. Toxicity level and antioxidant activity of the complex were also tested, which exhibit good tolerance level and antioxidant activity. Histological analysis of the pancreas of animals under investigation reveals the good condition of the pancreas treated with the complex. Ligands and complexes were also tested for antibacterial activity against Escherichia coli.

     

Assembly of polyoxometalate-templated metal-organic framework with effective peroxidase-like catalytic activity

A new polyoxometalate (POM)-templated 3-D copper(II)-triazole framework [Cu₁₀(trz)₁₀(OH)₆(Cl)₄][H₃PW₁₂O₄₀]·2H₂O (trz = 1,2,3-triazole) has been synthesized and characterized by single crystal X-ray diffraction and other routine methods. The 3-D POM/copper(II)-triazole hybrid framework with a 1-D channel possesses a pcu topology under the template of bulk Keggin-type phosphotungstate. As a new kind of peroxidase mimetic, the new compound effectively catalyzed oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H₂O₂. The electrostatic interactions and hydrogen bonds/π-π stacking interactions among TMB, trz, and phosphotungstate are responsible for the enhancement of peroxidase-like activity. In addition, application for colorimetric sensing of H₂O₂ is also explored; the new compound exhibits a wide linear range (1–80?μM), low detection limit (0.21?μM), and fast response (2?min).

     

Gas chromatography tandem mass spectrometry for the screening of adulterants in seized captagon™ tablets

Background: Amphetamine type stimulants (ATS) are the second most popular illegal drugs used worldwide, after cannabis. The production of ATS has increased across the world, including the Middle East. Fenethylline (Captagon?), amphetamine derivative, sold as a street drug usually contains several adulterants and diluents. In Saudi Arabia, like other countries, samples of illicit ATS are submitted to laboratories to test for the adulterated compounds.

Objective: The objective of the proposed study was to apply gas chromatography/mass spectrometry (GC/MS) for fenethylline profiling of seized samples collected from the Saudi market (n?=?55).

Methodology: The GC/MS analysis was performed on a general purpose column (30?m?×?0.25?mm i.d) coated with 0.25?µm cross bond, 5% diphenyl dimethyl polysiloxane (Rtx-5MS). The mass was operated in the electron impact mode.

Results and discussion: Analyzed samples gave positive results for amphetamine in the concentration range between 1.35% and 37.32% of the powder, caffeine in the range between 22.74 and 44.92%, in addition to different concentrations of levoglucosenone, theophylline, D-allose, lidocaine, methamphetamine, dextromethorphan, and other adulterants. Finally, the presence of other substances in fenethylline street samples could result in intoxication. This significantly contributes to the potential risk of drug addiction among public.     

A hydroxyquinoline-appended ruthenium(II)-polypyridyl complex that induces and stabilizes G-quadruplex DNA

A polypyridyl ruthenium(II) complex with hydroxyquinoline-derived ligand has been synthesized and characterized. The ability to act as telomeric quadruplex inducer and stabilizer, and quadruplex-binding properties of the complex have been evaluated by absorption and emission analyses, fluorescent intercalator displacement (FID) titrations, circular dichroism (CD) spectroscopy, polymerase chain reaction (PCR) stop assay, color reaction studies, fluorescence resonance energy transfer (FRET) melting assay, Job plot, and molecular modeling. Observations revealed that the complex could well induce and stabilize the formation of antiparallel G-quadruplex of telomeric DNA in the presence or absence of metal cations, and showed superior G-quadruplex selectivity over duplex DNA with remarkable ΔT_m value of 18.0?°C even at 50-fold excessive supplies of calf thymus (ct) DNA. The complex exhibited high interaction affinity of 2.56?×?10⁶ M^?1 with G-quadruplex DNA and evident luminescence enhancements of 3.1 and 4.2 times for quadruplex binding in Na⁺ and K⁺ buffer, respectively. In addition, the 1:1 [quadruplex]/[complex] binding mode ratio was determined. The results suggest that the complex can be developed as potential anticancer reagent through binding and stabilization of G-quadruplex DNA.

     

Surface Property Characterization of Plasma-Polymerized Tetraf luoroethylene Deposits

Plasma-polymerized tetrafluoroethylene (PPTFE) deposits were characterized by contact angle measurements and critical surface tension γ_Cmeasurements.

The measurements showed surface property changes of the deposits as a function of time and treatments: helium and nitrogen in the feed gas, plasma degradation of the films, and of vacuum/temperature posttreatments. The process was a flow rf plasma vapor deposition process, inductively-coupled, using tetrafluoroethylene as the monomer gas.

The study aimed toward effecting variable surface properties of the film deposits via plasma process parameters and gas feed admixtures. In addition, the nature and structure of the fluorocarbon deposits were elucidated using surface property characterization and ESCA techniques.     

Catalysis by Amberlyst A-21: A Greener Approach to 4,5,6,7-Tetrahydro-1H-indazol-3(2H)-ones via Construction of Cyclohexanones

The 4,5,6,7-tetrahydro-1H-indazol-3(2H)-one derivatives have been synthesized in good yields via a two-step method in a single pot. The initial step involved the construction of cyclohexanone ring from aromatic aldehydes and β-ketoester in i-PrOH using an inexpensive and reusable catalyst (i.e., Amberlyst A-21) under mild reaction conditions. The utility of this catalyst has been demonstrated in synthesizing a range of cyclohexanone derivatives. The catalyst can be recovered and recycled, which makes this procedure simple, convenient, economically viable, and environmental friendly.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

The Enantiomeric Discrimination of 5-Hexyl-2-methyl-3,4-dihydro-2H-pyrrole by Sulfobutyl ether-β-cyclodextrin: A Case Study

1-Pyrrolines are important intermediates of active natural products, such as the 2,5-dialkyl-1-pyrroline derivatives found in fire ant venoms. Here, 5-hexyl-2-methyl-3,4-dihydro-2H-pyrrole was synthesized by the enzymatic transamination/cyclization of 2,5-undecadione, and enantiodifferenciation was successfully achieved by capillary electrophoresis with sulfobutyl ether-β-cyclodextrin as the chiral selector. The rationale of the enantiomeric discrimination was based on the results of a docking simulation that revealed the higher affinity of (S)-5-hexyl-2-methyl-3,4-dihydro-2H-pyrrole for the sulfobutyl ether-β-cyclodextrin.