Crystal and molecular structure of 1R,3S,5S,7R,10R-3,6,6,10,14-Pentamethyltricyclo[10.3.0.05,7]pentadeca-11,14-diene-1, 10-dihydroxy-2,13-dione (Japodagrol), C20H28O4

A new cytotoxic macrocyclic diterpenoid named Japodagrol, C₂₀H₂₈O₄, has been isolated from the ornamental plantJatropha podagrica, family Euphorbiaceae, grown in Nigeria. The structure of the title compound, C₂₀H₂₈O₄, was solved by X-ray analysis.M _r =332.44, monoclinic space groupC2,a=23.285(4),b=6.5105(12),c=12.505(3) Å,=98.504(17),V=1874.8 ų,Z=4,D _c =1.178 Mg/m³. CuK radiation (graphite crystal monochromator, =1.54184 A), (CuK)=6.13 cm^–1,F(000)=720,T=290 K. Final conventionalR factor=0.035,R _w =0.038 for 3349 observed reflections. The structure was solved with the programDirdif. The 5-membered ring is closed to a half-chair form. The compound contains inter- and intramolecular hydrogen bonds.     

Chemical composition and anti-inflammatory activities of the essential oils from Acacia mearnsii de Wild

The volatile oils of the leaves and the stem bark of Acacia mearnsii de Wild obtained by hydro-distillation were analysed by gas chromatography–mass spectrometry. A total of 20, 38, 29 and 38 components accounted for 93.8%, 92.1%, 78.5% and 90.9% of the total oils of the fresh, dry leaves and fresh, dry stem bark, respectively. The major components of the oil were octadecyl alcohol (25.5%) and phytol (10.5%); cis-verbenol (29.5%); phytol (10.1%) and phytol (23.4%) for the fresh leaves, dried leaves, fresh stem, dry stem bark, respectively. Oral administration of essential oils at a dose of 2% showed significant (p < 0.05) anti-inflammatory properties in the albumin-induced test model in rats. Oils from the fresh leaves and dry stems inhibited inflammation beyond 4 h post treatment. The potent anti-inflammatory activity of essential oils of A. mearnsii hereby confirmed its traditional use in treating various inflammatory diseases.     

Equilibrium and fractal-like kinetic studies of the sorption of acid and basic dyes onto watermelon shell (<Emphasis Type="Italic">Citrullus vulgaris</Emphasis>)

In the present study, batch experiments were used to determine adsorption characteristics of Watermelon Shell Biosorbent (WSB) for the uptake of anionic and cationic dyes from aqueous solution. Various factors such as initial dye concentration, adsorbent dosage, pH, contact time and temperature were systematically investigated and discussed. WSB was characterized by Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy and Fourier Transform Infrared Spectroscopy. The adsorption kinetics was best described by Elovich and Diffusion-Chemosorption models for Basic red 2 (BR2) (cationic dye) and Orange G (OG) (anionic dye) respectively. However, the fractional time index “α” and non-integer “n” order by Fractal-like pseudo-first order kinetic affirmed that the mechanism of interaction of both dyes with WSB was by chemical reaction. The applicability of four adsorption isotherm models for the present system was tested. The equilibrium data were found to be well represented by the Extended Langmuir isotherm equation. The monolayer adsorption capacity of WSB for BR2 and OG adsorption was found to be 125 and 27 mg/g, respectively. The effect of temperature on the adsorption process was also investigated and the values of thermodynamic parameters ΔG°, ΔH° and ΔS° revealed that the adsorption system was spontaneous.     

Synthesis of chloro,fluoro, and nitro derivatives of 7‐amino‐5‐aryl‐6‐cyano‐5H‐pyrano pyrimidin‐2,4‐diones using organic catalysts and their antimicrobial and anticancer activities

Chloro, fluoro, and nitro derivatives of 7‐amino‐5‐aryl‐6‐cyano‐5H‐pyrano pyrimidin‐2,4‐diones were produced by reacting malononitrile, barbituric acid, and aromatic aldehydes together with a DABCO catalyst in an aqueous one‐pot reaction. This is the first report of these compounds being synthesized with DABCO as a catalyst, which produced the compounds in yields in excess of 90%. The 2,4‐difluoro derivative ( 11 ) was novel. The structures of the synthesized compounds were elucidated by means of ¹H, ¹³C, and 2D NMR spectroscopy. Compound 2 (2‐Cl derivative) had MBC values of <200μM against both Staphylococcus aureus and MRSA, and the 2‐nitro derivative 5 had an MBC of 191μM against the Gram–ve Escherichia coli. The synthesized compounds were also tested for their anticancer activity against a HeLa cell line, where all the compounds showed better activity (IC₅₀ values between 129μM and 340μM) than 5‐fluorouracil, a commonly known anticancer drug.     

Impact of calibrator concentrations and their distribution on accuracy of quadratic regression for liquid chromatography–mass spectrometry bioanalysis

Despite the common use of quadratic regression in LC–MS bioanalysis, how calibrator concentrations should be determined is still vague. Both the number and concentrations of calibrators are usually selected arbitrarily to each one's preference. The purposes of this research were to evaluate the impact of calibrator concentrations and to find new approaches with improved accuracy and reduced cost for LC–MS bioanalysis. It was found for the first time that the lower and upper limits of quantitation plus their geometric mean are the three critical concentrations for quadratic regression. When different concentration ranges, different response precisions, and various degrees of downward quadratic responses were simulated, the best accuracy was obtained by including these critical concentrations and using fewer calibrator concentrations with more replicates per concentration, instead of using more calibrator concentrations in duplicate. In many cases, when the aforementioned three concentrations are used, as few as two replicates per concentration are enough for routine use and up to 20% of time and cost can be saved. Furthermore, downward quadratic response should be eliminated or reduced as much as possible and upper limit quality control must be included in each batch to monitor the accuracy at the high concentration end. The retrospective data analysis of published experimental results corroborates the aforementioned findings. Finally, the typical “concerns” and potential applications of the new quadratic regression approaches are discussed.     

Degradative capability ofPseudomonas putida on acetonitrile

Pseudomonas putida, capable of utilizing acetonitrile as a sole source of carbon and nitrogen, was isolated from contaminated soil and water samples collected from industrial sites. TheP. putida cells were immobilized in calcium alginate beads. The degradation of acetonitrile by the immobilized cells ofP. putida was investigated. The immobilized cells degraded different concentrations of acetonitrile into ammonia and carbon dioxide. The effect of aeration on the degradation rate was also studied. Oxygen limitation was suggested in the alginate-immobilized system. The rate of degradation of acetonitrile increased with increase in the rate of aeration.     

Addition of an azido group to epoxidised fatty acid methyl esters of Jatropha curcas by epoxy cleavage

Azidohydrin was synthesized from the seed oil of Jatropha curcas by use of simple chemical reactions. This entailed first, transesterification of the seed oil of J. curcas to produce the fatty acid methyl esters, epoxidation of the fatty acid methyl esters to form the epoxides, then azidation of the epoxidised fatty acid methyl esters. The yield of the azidation reaction was 93.60 %, and the distribution of azide and alcohol functionality on the fatty acid was approximately random. The reactants and products were monitored and confirmed by FTIR and NMR spectroscopy.     

Mono- and dinuclear nickel(II) complexes of resolved Schiff-base ligands with extended quinoline substituents

The coordination chemistry of four enantiopure tetradentate bis(iminoquinoline) ligands with nickel(II) salts is reported. The previously reported ligands CBQ, CPQ, BBQ, and BPQ result from the condensation of (1R,2R)-cyclohexyldiamine or (R)-BINAM with two equivalents of 2-formylbenzo[h]quinoline or 8-isopropyl-2-quinolinecarboxaldehyde {CBQ = (1R,2R)-cyclohexanediamine-N,N'-bis(benzo[h]quinoline-2-ylmethylene), CPQ = (1R,2R)-cyclohexanediamine-N,N'-bis[[(8-isopropyl)-2-quinolinyl]methylene], BBQ = [(R)-1,1'-binaphthalene]-2,2'-diamine-N,N'-bis(benzo[h]quinoline-2-ylmethylene), BPQ = [(R)-1,1'-binaphthalene]-2,2'-diamine-N,N'-bis[[(8-isopropyl)-2-quinolinyl]methylene]}. Reaction of NiI(2) with the (1R,2R)-cyclohexyl ligands gives the mononuclear distorted trigonal-bipyramidal (TBP) complexes [Ni(N(3)-CBQ)I(2)] and [Ni(N(3)-CPQ)I(2)]. Incomplete iodide abstraction from [Ni(N(3)-CPQ)I(2)] with AgOTf leads to partial replacement of the iodide with hydroxide from adventitious water to give [Ni(N(3)-CPQ)I(1.6)(OH)(0.4)] (distorted TBP). The corresponding reaction with [Ni(N(3)-CBQ)I(2)] again fails to remove all of the iodide, resulting instead in conversion to the syn dinuclear [Ni(2)(CBQ)(μ-X)(2)I(2)] (X = Cl(0.925)I(0.075)) complex, where chloride abstraction from the solvent (CH(2)Cl(2)) has resulted in a mixed halide system and the metal centers are square-pyramidal. Reaction of Ni(OTf)(2) with CBQ leads to the isolation of the octahedral cation [Ni(CMBQ)(2)](2+), with CMBQ [(1R,2R)-cyclohexanediamine-mono-N-(benzo[h]quinoline-2-ylmethylene)] being the partial hydrolysis product of CBQ. [Ni(CMBQ)(2)][OTf](2) crystallizes as a 1:1 mixture of P and M helical diastereomers. The coordination of NiI(2) with the (R)-BINAM derived ligands yields the anti dinuclear P-helical complexes [Ni(2)(BBQ)(μ-I)(2)I(2)] and [Ni(2)(BPQ)(μ-I)(2)I(2)]: one nickel ion is coordinated in each bidentate iminoquinoline pocket and the geometry at the metal centers is distorted square-pyramidal. Characterisation by (1)H NMR, UV-Vis, electronic circular dichroism (ECD) spectroscopy, combustion analysis, and HRMS is reported in addition to structural and halide abstraction studies.     

The rheology of suspensions of porous zeolite particles in polymer solutions

We present data and predictive models for the shear rheology of suspended zeolite particles in polymer solutions. It was found experimentally that suspensions of zeolite particles in polymer solutions have relative viscosities that dramatically exceed the Krieger–Dougherty predictions for hard sphere suspensions. Our investigations show that the major origin of this discrepancy is due to the selective absorption of solvent molecules from the suspending polymer solution into zeolite pores. The effect raises both the polymer concentration in the suspending medium and the particle volume fraction in the suspension. Consequently, both the viscosity of the polymer solution and the particle contribution to the suspension viscosity are increased. We propose a predictive model for the viscosity of porous zeolite suspensions by incorporating a solvent absorption parameter, α, into the Krieger–Dougherty model. We experimentally determined the solvent absorption parameter by comparing viscosity data for suspensions of porous and nonporous MFI zeolite particles. Our results are in good agreement with the theoretical pore volume of MFI particles.     

Efficient strategies for boosting the performance of 2D graphitic carbon nitride nanomaterials during photoreduction of carbon dioxide to energy-rich chemicals

Nowadays, the alarming growing interest in providing a solution to increasing concentration of atmospheric carbon dioxide (CO₂) and the associated pollution has attracted global attention. The consequential effects of CO₂ are detrimental to the environment owing to the continuous depletion of carbon-emitting fossil fuels. Photocatalytic CO₂ reduction (CO₂R) to valuable chemicals and fuels is one the promising alternative option to mitigate the global menace instigated by CO₂ emissions. If the strategies for enhancing the CO₂R are unavailable, inefficient, or inappropriate, then efficiency conversion CO₂ to valuable products can become problematic. In that case, the emission of CO₂ results in synchronizing upsurge in the global-mean air surface temperature on the earth and sea levels from 1980 to 2100. This study presents different strategies for boosting the photocatalytic performance of 2D graphitic carbon nitride (g-C₃N₄) for CO₂R reaction. The first part consists of the fundamental principles of photocatalysis. The second part presents some answers to the question: what governs the mechanism of photocatalytic CO₂R? The existing literature lack comprehensive information about the strategical influence of available reactor designs on the photoactivity of 2D g-C₃N₄ for CO₂ conversion to energy-rich chemicals and ways to improve them as discussed in this study. This was then followed by strategies about the synthetic methods for enhancing photocatalytic CO₂R over 2D g-C₃N₄ materials before the discussion of the strategies for enhancing the CO₂ photoreduction on the 2D g-C₃N₄ nanomaterials. Some groups of g-C₃N₄ nanomaterials for photoreduction of CO₂R were also discussed. Unlike the previous reviews in the field, the present study presents some innovation to bridge the knowledge gaps of the previous reviews and corresponding insight thereof. For future breakthroughs, this study also explains some problems with the interpretation in the field. We also highlight insights into innovation on exclusion and inclusion criteria about the performance metrics and present some queries, concerns, and problems with the previous studies. The concluding part consists of research outlooks, including commonly overlooked challenges and future perspectives for ensuring highly efficient strategies, applications of 2D g-C₃N₄ photocatalysts, and CO₂ conversion to meet industrial scale expectations. The present study hypothesized that considering the current technological age, the experiment should go beyond presenting only illustration and analysis about the band energy, but the detailed explanation/information about the pathways of the various products formed using molecular dynamics system and artificial intelligence aspects should be combined in the future studies.