A new acylated flavonoid tetraglycoside with anti-inflammatory activity from Tipuana tipu leaves

A new acylated kaempferol glycoside, kaempferol 3-O-α-l-rhamnopyranosyl-(1 → 6)-O-[β-d-glucopyranosyl-(1 → 2)-4-O-acetyl-α-l-rhamnopyranosyl-(1 → 2)]-β-d-galactopyranoside, has been isolated from the leaves of Tipuana tipu (Benth.) Lillo growing in Egypt, along with three known flavonol glycosides, kaempferol 3-O-rutinoside, quercetin 3-O-rutinoside (rutin) and kaempferol 3-O-[α-l-rhamnopyranosyl-(1 → 6)]-[α-l-rhamnopyranosyl-(1 → 2]-β-d-glucopyranoside. Structure elucidation was achieved through different spectroscopic methods. Structure relationship with anti-inflammatory activity using carrageenin-induced rat paw oedema model is discussed.     

Flow control using bifrequency motion

We used a second-order approximation for the periodic lift coefficient of a circular cylinder under monofrequency and bifrequency cross-flow motions. Two lock-in modes exist under monofrequency fundamental (i.e., near the Strouhal number) motion. In the first mode, the work is done by the flow on the cylinder, whereas in the second mode the work is done by the cylinder on the flow. Under monofrequency superharmonic (i.e., near three times the Strouhal number) motion, the work is always done on the flow. We then replaced the monofrequency motions by a bifrequency one, consisting of a fundamental term combined with a small-magnitude superharmonic term. We examined the effect of the magnitude and phase of the superharmonic motion term on the two modes of lock-in which we obtained when only the fundamental motion term is applied, considering two different frequencies that belonged to the two lock-in modes. Under the bifrequency motion, the work can be done on the flow or on the cylinder. This can be controlled using the superharmonic motion term, even when its magnitude is 5% of magnitude of the fundamental motion term. Other flow variables, such as the magnification of the lift, can be remarkably altered through the added superharmonic motion term. The phase of the third superharmonic lift-coefficient component relative to the fundamental one is the most responsive variable to the phase of the superharmonic motion component relative to the fundamental one.     

Synthesis,DFT Calculations,Antiproliferative, Bactericidal Activity and Molecular Docking of Novel Mixed-Ligand Salen/8-Hydroxyquinoline Metal Complexes

Despite the common use of salens and hydroxyquinolines as therapeutic and bioactive agents, their metal complexes are still under development. Here, we report the synthesis of novel mixed-ligand metal complexes (MSQ) comprising salen (S), derived from (2,2′-{1,2-ethanediylbis[nitrilo(E) methylylidene]}diphenol, and 8-hydroxyquinoline (Q) with Co(II), Ni(II), Cd(II), Al(III), and La(III). The structures and properties of these MSQ metal complexes were investigated using molar conductivity, melting point, FTIR, ¹H NMR, ¹³C NMR, UV–VIS, mass spectra, and thermal analysis. Quantum calculation, analytical, and experimental measurements seem to suggest the proposed structure of the compounds and its uncommon monobasic tridentate binding mode of salen via phenolic oxygen, azomethine group, and the NH group. The general molecular formula of MSQ metal complexes is [M(S)(Q)(H₂O)] for M (II) = Co, Ni, and Cd or [M(S)(Q)(Cl)] and [M(S)(Q)(H₂O)]Cl for M(III) = La and Al, respectively. Importantly, all prepared metal complexes were evaluated for their antimicrobial and anticancer activities. The metal complexes exhibited high cytotoxic potency against human breast cancer (MDA-MB231) and liver cancer (Hep-G2) cell lines. Among all MSQ metal complexes, CoSQ and LaSQ produced IC₅₀ values (1.49 and 1.95 µM, respectively) that were comparable to that of cisplatin (1.55 µM) against Hep-G2 cells, whereas CdSQ and LaSQ had best potency against MDA-MB231 with IC₅₀ values of 1.95 and 1.43 µM, respectively. Furthermore, the metal complexes exhibited significant antimicrobial activities against a wide spectrum of both Gram-positive and -negative bacterial and fungal strains. The antibacterial and antifungal efficacies for the MSQ metal complexes, the free S and Q ligands, and the standard drugs gentamycin and ketoconazole decreased in the order AlSQ > LaSQ > CdSQ > gentamycin > NiSQ > CoSQ > Q > S for antibacterial activity, and for antifungal activity followed the trend of LaSQ > AlSQ > CdSQ > ketoconazole > NiSQ > CoSQ > Q > S. Molecular docking studies were performed to investigate the binding of the synthesized compounds with breast cancer oxidoreductase (PDB ID: 3HB5). According to the data obtained, the most probable coordination geometry is octahedral for all the metal complexes. The molecular and electronic structures of the metal complexes were optimized theoretically, and their quantum chemical parameters were calculated. PXRD results for the Cd(II) and La(III) metal complexes indicated that they were crystalline in nature.     

Data-free inference of the joint distribution of uncertain model parameters

A critical problem in accurately estimating uncertainty in model predictions is the lack of details in the literature on the correlation (or full joint distribution) of uncertain model parameters. In this paper we describe a framework and a class of algorithms for analyzing such “missing data” problems in the setting of Bayesian statistics. The analysis focuses on the family of posterior distributions consistent with given statistics (e.g. nominal values, confidence intervals). The combining of consistent distributions is addressed via techniques from the opinion pooling literature. The developed approach allows subsequent propagation of uncertainty in model inputs consistent with reported statistics, in the absence of data.     

On the pseudorandomness of binary and quaternary sequences linked by the gray mapping

Binary and quaternary sequences are the most important sequences in view of many practical applications. Any quaternary sequence can be decomposed into two binary sequences and any two binary sequences can be combined into a quaternary sequence using the Gray mapping. We analyze the relation between the measures of pseudorandomness for the two binary sequences and the measures for the corresponding quaternary sequences, which were both introduced by Mauduit and Sárközy. Our results show that each ‘pseudorandom’ quaternary sequence corresponds to two ‘pseudorandom’ binary sequences which are ‘uncorrelated’.     

UV–visible and infrared absorption spectra of transition metals-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and transition metals (TM 3d)-doped lead phosphate glasses were prepared. Ultraviolet–visible absorption spectra were measured in the range 200–1100 nm before and after successive gamma irradiation. Experimental results indicate that the undoped lead phosphate glass reveals before irradiation strong and broad ultraviolet absorption which is related to the co-sharing of absorption due to both trace iron impurities and lead ions (Pb²⁺). In the TM-doped glasses, characteristic absorption bands are obtained in both the UV and/or visible regions due to each respective TM ion in addition to that observed by the base undoped UV absorption. Gamma irradiation produces with the undoped glass a prominent induced ultraviolet broad band centered at about 300 nm originating mostly from the contribution of trace iron impurities and the visible spectra reveal markedly high shielding behavior towards successive gamma irradiation, due to the presence of both high content of heavy Pb²⁺ ions and the sharing of phosphate as a partner. With TM-doped samples, the observed induced bands are virtually varying and related to the type of the sharing TM ions. Infrared absorption spectra reveal in the undoped and TM-doped glasses characteristic structural phosphate groups mainly consisting of metaphosphate and pyrophosphate units. Transition metals are assumed to cause depolymerization of the phosphate glass network with different ratios but the changes in IR spectral data are limited due to the low doping level. Gamma irradiation of the samples is assumed to cause changes in the bond angles or bond lengths of the structural phosphate units within network as evident in the variation of the intensities of the IR bands.     

Synthesis of novel 2-phenoxybenzo[<Emphasis Type="Italic">g</Emphasis>][1,2,4]triazolo[1,5-<Emphasis Type="Italic">a</Emphasis>]quinazoline and its derivatives starting with diphenyl-<Emphasis Type="Italic">N</Emphasis>-cyanoimidocarbonate

Cyclocondensation reaction of 3-hydrazinyl-2-naphthoic acid with diphenyl-N-cyanoimidocarbonate furnished the target 2-phenoxy-benzo[g][1,2,4]triazolo[1,5-a]quinazolin-5(4H)-one (1) in high yield. Alkylation, thionation and chlorination of the lactam group in the compound 1 produced a variety of derivatives 2–17. Their structures were characterized by NMR and HREI-MS analyses.     

Selective potentiometric determination of nitrite ion using a novel (4-sulphophenylazo-)1-naphthylamine membrane sensor

A novel polymeric membrane sensor sensitive to (4-sulphophenylazo-)1-naphthylamine (SPAN) based on the use of tris(bathophenanthroline) Ni(II)–SPAN ion pair as an ion exchanger in plasticised PVC membrane is described. The sensor exhibits a linear calibration plot with near-Nernstian anionic slope of −55.0±0.3 mV log[SPAN]⁻¹ over the concentration range 10⁻⁶–10⁻² mol l⁻¹ at pH 7. The sensor shows working range over the pH 6–8, response time of 20 s for 10⁻⁵ mol l⁻¹ and operational lifetime of 8 weeks. The sensor is used for quantification of micro quantities of nitrite ion by a prior conversion into the more lipophilic SPAN ion, which is measured with adequate sensitivity, and high selectivity using SPAN sensor. Validation of the method according to the quality assurance standards shows good performance characteristics. The sensor is satisfactory utilised for potentiometric determination of nitrite ion in wastewater samples and meat products. The results are favourably compared with data obtained using the standard spectrophotometric procedure involving the same reaction.     

Vibrational spectrum and structure of CoO6: a model compound for molecular oxygen reversible binding on cobalt oxides and salts; a combined IR matrix isolation and theoretical study

The formation and structure of a novel species, a disuperoxo-cobalt dioxide complex (CoO(6)), has been investigated using matrix isolation in solid neon and argon, coupled to infrared spectroscopy and by quantum chemical methods. It is found that CoO(6) can be formed by successive complexation of cobalt dioxide by molecular oxygen without activation energy by diffusion of ground state O(2) molecules at 9K in the dark. The IR data on one combination and seven fundamentals, isotopic effects, and quantum chemical calculations are both consistent with an asymmetrical structure with two slightly nonequivalent oxygen ligands complexing a cobalt dioxide subunit. Evidence for other, metastable states is also presented, but the data are not complete. The electronic structure and formation pathway of this unique, formally +VI oxidation state, complex has been investigated using several functionals of current DFT within the broken-symmetry unrestricted formalism. It has been shown that the M06L pure local functional well reproduce the experimental observations. The ground electronic state is predicted to be an open shell (2)A' doublet with the quartet states above by more than 9 kcal/mol and the sextet lying even higher in energy. The ground state has a strong and complex multireference character that hinders the use of more precise multireference approaches and requires caution in the methodology to be used. The geometrical, energetic, and vibrational properties have been computed.     

One‐pot Synthesis of 1,2,3,4‐Tetrahydropyrimidin‐2(1H)‐thione Derivatives and their Biological Activity

2‐Thioxo/oxo‐1,2,3,4‐tetrahydropyrimidine‐5‐carboxylate derivatives 2a , 2b , 2c , 2d were prepared by the reaction of ethyl acetoacetate and thiourea or urea with aldehydes using NH₄Cl as a catalyst. Compounds 2a and 2c reacted with mono and bihalogenated compounds such as ethyl iodide, chloroacetonitrile, epichlorohydrin, acetyl chloride, ethyl bromoacetate, chloroacetic acid, chloroacetylchloride, and/or oxalyl chloride to afford compounds 3 , 4a , 4b , 5 , 6a , 6b , 7 , 8 , 9 and 10 , respectively. Compounds 2a , 2c , and 7 were allowed to react with p‐fluorobenzaldehyde to yield the corresponding products 11a , 11b , and 12 , respectively. Oxidation of 2a and 2c gave 2b , 13a , 13b , 14 , 15 , 16 dependent on the oxidizing agent used. Vilsmeiere‐Haack formylation of 2a and 2b with POCl₃/DMF afforded 17a and 17b . Chlorination of 2b and 2d gave the chlorinated derivative 18a and 18b , which reacted with thiourea to give thioureidopyrimidine 19a and 19b . Reactions of 2a with hydrazine monohydrate, semicarbazide hydrochloride, and sodium hydroxide gave compounds 20 , 21 , 22 , respectively. The cytotoxicity and in vitro anticancer evaluation of some prepared compounds have been assessed against two different human tumor cell lines including breast adenocarcinoma MCF‐7 and human hepatocellular carcinoma HepG2. Antimicrobial and antioxidant activities of some compounds were investigated. The newly synthesized compounds were characterized by IR, ¹H‐NMR, ¹³C‐NMR, and mass spectral data.