Tailoring particle shape for enhancing the homogeneity of powder mixtures:Experimental study and DEM modelling

The effect of particle shape modification on the segregation reduction of enzyme granules in laundry detergent powder mixtures was investigated,both experimentally and computationally using Deseret Element Method(DEM).The shape of modified enzyme particles was in such a way that the large and dense enzyme particles were layered by other fine particles in the detergent powder,by means of a process known in the literature as“seeded granulation”.It is found that the homogeneity of modified enzyme particles could be improved significantly comparing to the original spherical enzyme particles in powder mixtures.Overall,the results of this research demonstrated that the segregation-induced properties of the dense/spherical enzyme particles could be lowered by altering their shape,which could enable the enzyme particles to behave almost similar to other ingredients during the pile formation process.     

Connectivity of Pore Space as a Control on Two-Phase Flow Properties of Tight-Gas Sandstones

We predict capillary-pressure (drainage) curves in tight-gas sandstones which have little matrix or microporosity using a quantitative grain-scale model. The model accounts for the geometric results of some depositional and diagenetic processes important for porosity and permeability reduction in tight-gas sandstones, such as deformation of ductile grains during burial and quartz cementation. The model represents the original sediment as a dense, disordered packing of spheres. We simulated the evolution of this model sediment into a low-porosity sandstone by applying different amounts of ductile grains and quartz precipitation. A substantial fraction of original pore throats in the sediment is closed by the simulated diagenetic alteration. Because the percolation threshold corresponds to closure of half of the pore throats, the pore space in this type of tight-gas sandstone is poorly connected and is often close to being completely disconnected. The drainage curve for different model rocks was computed using invasion percolation in a network taken directly from the grain-scale geometry and topology of the model. Some general trends follow classical expectations and were confirmed by experimental measurements: increasing the amount of cement shifts the drainage curve to larger pressures. This is related to reduction of the connectivity of pore space resulting from closure of throats. Existence of ductile grains in the ductile grain model also reduces the connectivity of pore space but it treats the throats distribution differently causing the drainage curves to be shifted to larger irreducible water saturation when cement is added to the model. The range of porosities in which these connectivity effects are important corresponds to the range of porosities common for tight gas sandstones. Consequently these rocks can exhibit small effective permeability to gas even at large gas saturations. This problem occurs at larger porosities in rocks with significant content of ductile grains because ductile deformation blocks a significant fraction of pore throats even before cementation begins. Predicted drainage curves agree with measurements on two samples with little microporosity, one dominated by rigid grains, the other containing a significant fraction of ductile grains. We conclude that connectivity of the matrix pore space is an important factor for an understanding of flow properties of tight-gas sandstones.     

Naphthoflavone propargyl ether inhibitors of cytochrome P450

Cytochrome P450 enzymes protect the body from foreign substances through a mechanism that involves oxidation of those substances into more readily excretable polar compounds. It has been shown that some naphthoflavones function as substrates of certain P450 enzymes (CYP1A1 and CYP1B1) and with appropriate structural changes may become inhibitors. Moreover, propargyl ether derivatives of adamantane have been shown to function as selective inactivators of some P450 enzymes (CYP2B1 and CYP2B5). In an attempt to improve the potency and selectivity of inhibition, we have designed and synthesized a series of naphthoflavone propargyl ethers. We report here the synthesis, X-ray crystal structures, and inhibition data (IC₅₀ of EROD inhibition in CYP1A1 and CYP1B1 enzymes) of α-naphthoflavone 2′-propargyl ether, β-naphthoflavone 2′-propargyl ether, α-naphthoflavone 4′-propargyl ether, and β-naphthoflavone 4′-propargyl ether. Crystallographic data: α-naphthoflavone 2′-propargyl ether, , a=7.775(1) ?, b=8.062(1) ?, c=13.110(1) ?, α=84.32(1)°, β=75.42(1)°, γ=86.56(1)°, V=790.8(2) ?³; β-naphthoflavone 2′-propargyl ether, , a=7.605(2) ?, b=7.793(1) ?, c=14.167(2) ?, α=77.06(1)°, β=75.41(1)°, γ=89.54(1)°, V=790.9(2) ?³; α-naphthoflavone 4′-propargyl ether, P21/n, a=14.595(2) ?, b=4.708(1) ?, c=24.745(6) ?, β=106.31(2)°, V=1631.8(7) ?³; β-naphthoflavone 4′-propargyl ether, P1, a=4.8871(5) ?, b= 7.9597(7) ?, c=21.788(3) ?, α=81.771(9)°, β=89.918(10)°, γ=72.223(8)°, V= 797.9(2) ?³.     

A convenient route toward one‐pot multicomponent synthesis of spirochromenes and pyranopyrazoles accelerated via quinolinic acid

In the present work, the catalytic activity of quinolinic acid (QUIN) was studied for the synthesis of spirochromene and pyranopyrazole derivatives from readily available materials. The salient features of these one‐pot multicomponent protocols are the clean reaction profile, easy isolation of products, no chromatographic separation techniques, high efficiency, short reaction time, and high yield of products plus using QUIN as a new, inexpensive, commercially available, and efficient organocatalyst.     

Construction of molecularly imprinted nanoparticles by employing ultrasound waves for selective determination of doxepin from human plasma samples: Modeling and optimization

In this work, molecularly imprinted nanoparticles (MINPs) were applied as selective adsorbent for ultrasound‐assisted micro‐solid‐phase extraction (UAMSPE) of doxepin (DP) from human plasma samples, which was then cleaned up, pre‐concentrated and subjected to HPLC. The MINPs were synthesized based on a non‐covalent approach by precipitation polymerization utilizing methacrylic acid and styrene as functional monomers, DP as template, ethylene glycol dimethacrylate as cross‐linker and 2,2‐azobisisobutyronitrile (AIBN) as initiator. The obtained MINPs were characterized by Fourier transform‐infrared and field emission scanning electron microscopy. Factors influencing the efficiency of UAMSPE such as sonication time, volume of eluent solvent and amount of sorbent were investigated using a central composite design and the optimal points were identified as 4 min of sonication time, 380 μL of eluent solvent and 30 mg of sorbent. Under optimized conditions, the proposed method has linear responses in the range of 0.2–2000 ng mL^–1, with a satisfactory limit of detection of 0.04 ng mL^–1 and limit of quantification of 0.11 ng mL^–1.     

Synthesis of four series of quinoline‐based heterocycles by reacting 2‐chloroquinoline‐3‐carbonitriles with various types of isocyanides

Four distinct sets of functionalized quinolines were synthesized by reacting 2‐chloroquinoline‐3‐carbonitriles with various types of isocyanides under appropriate conditions. The palladium‐catalysed reaction of less hindered aliphatic and aromatic isocyanides with 2‐chloroquinoline‐3‐carbonitriles yielded 2‐alkyl(aryl)‐1‐imino‐1H‐pyrrolo[3,4‐b]quinolin‐3(2H)‐one derivatives; however, the catalysed reaction of more hindered isocyanides such as tert‐butyl isocyanide produced the corresponding 3‐cyanoquinoline‐2‐carboxamides. Interestingly, chloroquinoline‐3‐carbonitriles reacted with ethyl isocyanoacetate in the presence of Cs₂CO₃ to generate imidazo[1,5‐a]quinoline derivatives; notably, tosylmethyl isocyanide under the same conditions formed unprecedented 2‐tosyl‐3‐cyanoquinolines.     

Bis‐aroylhydrazone based on 2,2′‐bis substituted diphenylamine for synthesis of new binuclear organotin (IV) complexes: Spectroscopic characterization,crystal structures,in vitro DNA‐binding,plasmid DNA cleavage,PCR and cytotoxicity against MCF7 cell line

New dinuclear organotin (IV) complexes, Me₄Sn₂L, Ph₄Sn₂L and Bu₄Sn₂L, have been synthesized from reaction of R₂SnCl₂ (R = Me, Ph and Bu) with a 2,2′‐bis‐substituted diphenylamine arοylidene hydrazone, H₄L. The synthesized compounds were investigated by elemental analysis and infrared, ¹H‐NMR and ¹¹⁹Sn‐NMR spectroscopy. The structures of H₄L, Me₄Sn₂L and Bu₄Sn₂L were also confirmed by X‐ray crystallography. H₄L molecules adopt (E)‐configuration and keto‐tautomeric form in the solid state. In all complexes, the bis‐hydrazone acts as a tetra‐anionic ligand with two contiguous ONO tridentate domains that coordinate the two R₂Sn moieties in the enolate form. The coordination environments of both tin centers are five‐coordinate. DNA‐binding studies were performed by UV–Vis spectroscopy, and the results indicate that the synthesized compounds significantly interact with calf thymus‐DNA in the intercalative mode. The results of polymerase chain reaction assay show that all the compounds affect on amplification of DNA, and complexes are more effective than ligands. The in vitro cytotoxicity against the human breast cancer line (MCF7) was determined using the MTT assay, and H₄L and the dibutytin complex showed higher activity.     

Hydrogen-abstraction reactions of fully hydrogenated silicon fullerene cages with the amino radical: a density functional study

Structural Chemistry - We applied density functional theory calculations to study reactions NH2 ?+ SinHn fullerenes (n?=?4, 6, 8, 10, 20, 24, 30, 36, and 50). The reactions...