Combining click-multicomponent reaction: one-pot synthesis of triazolyl methoxy-phenyl indazolo[2,1-b]phthalazine-trione derivatives

[(1,2,3-Triazol-4-yl)methoxy-phenyl]-2H-indazolo[2,1-b]phthalazine-trione derivatives were synthesized in a simple and efficient method from the one-pot four-component condensation reaction of phthalhydrazide, aromatic propargyloxy aldehydes, active methylene compounds (dimedone and 1,3-cyclohexanedione), and azides in the presence of Cu(OAc)(2)/sodium ascorbate and p-toluenesulfonic acid as catalysts in good to excellent yields.     

Diamagnetic repulsion—A versatile tool for label-free particle handling in microfluidic devices

We report the exploration of diamagnetic repulsion forces for the selective manipulation of microparticles inside microfluidic devices. Diamagnetic materials such as polymers are repelled from magnetic fields, an effect greatly enhanced by suspending a diamagnetic object in a paramagnetic Mn²⁺ solution. The versatility of diamagnetic repulsion is demonstrated for the trapping, focussing and deflection of polystyrene particles for three example applications. Firstly, magnet pairs with unlike poles facing each other were arranged along a microcapillary to trap plugs of differently functionalised particles for a simultaneous surface-based assay in which biotin was selectively bound to a plug of streptavidin coated particles utilising only 22 nL of reagent. Secondly, by slightly modifying the magnetic field design, the rapid focussing of particles into a narrow central stream at a flow rate of 650 μm s⁻¹ was accomplished for particle pre-concentration. In a third application, 5 and 10 μm polystyrene particles were separated from each other in continuous flow by passing the particle mixture through a microfluidic chamber with a perpendicular magnetic field, a method termed diamagnetophoresis. The separation was investigated between flow rates of 20–100 μL h⁻¹, with full resolution of the particle populations being achieved at 20 μL h⁻¹. These experiments show the potential of diamagnetic repulsion for simple, label-free manipulation of particles and other diamagnetic objects such as cells for a range of bioanalytical techniques.     

The development of a comprehensive toolbox based on multi-level,high-throughput screening of MOFs for CO/N2 separations

The separation of CO/N₂ mixtures is a challenging problem in the petrochemical sector due to the very similar physical properties of these two molecules, such as size, molecular weight and boiling point. To solve this and other challenging gas separations, one requires a holistic approach. The complexity of a screening exercise for adsorption-based separations arises from the multitude of existing porous materials, including metal–organic frameworks. Besides, the multivariate nature of the performance criteria that needs to be considered when designing an optimal adsorbent and a separation process – i.e. an optimal material requires fulfillment of several criteria simultaneously – makes the screening challenging. To address this, we have developed a multi-scale approach combining high-throughput molecular simulation screening, data mining and advanced visualization, as well as process system modelling, backed up by experimental validation. We have applied our recent advances in the engineering of porous materials'' morphology to develop advanced monolithic structures. These conformed, shaped monoliths can be used readily in industrial applications, bringing a valuable strategy for the development of advanced materials. This toolbox is flexible enough to be applied to multiple adsorption-based gas separation applications.

The separation of challenging mixtures through adsorption is a multidimensional problem that requires a holistic approach. Our toolbox combines experiments, molecular and process simulations with data visualization to find optimal, porous materials.     

Influence of graphene nanoscrolls on the crystallization behavior and nano‐mechanical properties of polylactic acid

Graphene nanoscrolls (GNS), one‐dimensional carbon‐based nanomaterials, have been predicted to possess extraordinary characteristics due to their unique open topology with scrolled graphene monolayers. In this study, the conversion of planar 2‐D graphene nanoplatelets (GNPs) to tubular and scrolled 1‐D GNSs is described. The effects of GNS as a nucleating agent to modulate the morphology, crystallization, and nano‐mechanical properties of polylactic acid (PLA) were studied. The nucleating effect of GNS and its unique topological characteristics proves to influence the crystallization of PLA. Fourier transform infrared (FTIR) spectroscopy indicated nonpreferential interactions of PLA chains around GNS due to the bulky and helical PLA macromolecular chains. Superior interfacial interactions and strain in GNS provide better load transfer between GNS and PLA matrices, resulting in higher modulus and hardness. This study is the first detailed analysis to elucidate the role of unique GNS to favorably modulate the properties of a polymer.     

Grid Resolution Effects on VSFMDF/LES

The grid dependence of LES/VSFMDF is studied on a series of grids with progressively increased resolution reaching over 10 million grids for simulation of a turbulent piloted nonpremixed methane jet flame (Sandia D). In VSFMDF, the effects of the subgrid scale chemical reaction and convection appear in closed forms. The modeled transport equation for the VSFMDF is solved by a hybrid finite-difference/Monte Carlo scheme. A flamelet model is employed to relate the instantaneous composition to the mixture fraction. The simulated results are assessed via comparison with laboratory data. In addition, the dependence of predicted statistics on the grid size of the simulation is studied. The first order moments converge for the finest grid, but the higher order statistics including the PDFs are more sensitive to the grid resolution.     

Hubbard model on the triangular lattice: spiral order and spin liquid

We investigate the half-filled Hubbard model on an isotropic triangular lattice with the variational cluster approximation. By decreasing the on-site repulsion U (or equivalently increasing pressure) we go from a phase with long-range, three-sublattice, spiral magnetic order, to a nonmagnetic Mott insulating phase--a spin liquid--and then, for U less or similar to 6.7t, to a metallic phase. Clusters of sizes 3, 6, and 15 with open boundary conditions are used in these calculations, and an extrapolation to infinite size is argued to lead to a disordered phase at U = 8t, but to a spiral order at U greater or similar to 12.     

Stereoselective Synthesis and Structure of New Types of Calix[4]resorcinarenes. Complexation of Tetrakis(O,O‐Phosphorus)Bridged‐Calix[4]resorcinarenes with Heavy Metal Atoms

The acid‐catalyzed (with HCl) condensation reactions of resorcinol ( 1 ) with 1‐naphthaldehyde ( 2 ) and isobutyraldehyde ( 3 ) furnished the tetrameric macrocyclic compounds 4 and 6 . Detailed NMR‐investigations of the acetylated tetrameric species 5 surprisingly support a structure not in agreement with the expected all‐cis conformation. The chair conformation (C_2h symmetry) of the acetylated derivative 5 was established through a crystal X‐ray diffraction study. The naphthyl substituents are arranged in trans position above and below the plane made up by the resorcinol units. The reaction of resorcinol 1 with isobutyraldehyde, in accord with expectation, led to the calix[4]resorcinaren ( 6 ). The ¹H NMR spectra of compound 6 and 7 appeared at room temperature as broad signals, indicating a conformation of C_2v symmetry. The reaction of the C‐methyl‐tetrakis‐P‐(chlorodioxaphosphocin)‐calix[4]resorcinarenes ( 8 ) and ( 10 ) with suitable N‐trimethylsilyl organic amines were conducted in tetrahydrofuran suspension, furnishing the P–N‐substituted calix[4]resorcinarenes ( 9 ) and ( 11 ). While in the complexation of C‐methyl‐tetrabromotetrakis‐P‐(dimethylaminodioxaphosphocin)‐calix[4]resorcinarene ( 13 ) with (tht)AuCl (tht = tetrahydrothiophene) the expected, neutral tetra‐substituted complex 15 was formed, the reaction of 13 with moist acetonitrile led to the anionic atomic framework 14 . X‐ray structure determinations of the complexes 14 and 15 show that both possess the cone conformation. In the gold complex 15 , the Au–Cl groups form a loose aggregate, with three Au…Cl contacts of 316–340 pm; one of the groups points towards the centre of the cone. The copper(I) complex 14 displays crystallographic mirror symmetry, with a central Cu₄Cl₅ unit involving tetrahedrally coordinated copper.     

Salicylic Acid Stimulates Defense Systems in Allium hirtifolium Grown under Water Deficit Stress

Nowadays, the use of the growth regulator salicylic acid for improving a plant’s resistance to environmental stresses such as drought is increasing. The present study investigated the effect of salicylic acid on the physiological traits, antioxidant enzymes, yield, and quality of Allium hirtifolium (shallots) under drought conditions for three years (2016–2017, 2017–2018, and 2018–2019). The experiment was conducted as a split-plot based on a randomized complete block design with four repeats. Irrigation as the main factor in four levels of 100% (full irrigation), 75% and 50% of the plant water requirements with non-irrigation (dryland), and salicylic acid as the sub-factor in four levels of 0, 0.75, and 1 mmol, were the studied factors in this research. The combined analysis of three-year data showed that drought reduced leaf relative water content (RWC), membrane stability index (MSI), chlorophyll content, onion yield, and increased activity of antioxidant enzymes, proline content, tang, and allicin of shallots. Shallot spraying with salicylic acid improved leaf RWC, MSI, chlorophyll content, and onion yield. The highest yield of onion (1427 gr m⁻²) belonged to full irrigation and foliar application of 1 mmol salicylic acid. The lowest yield (419.8 gr m⁻²) belonged to plats with non-irrigation and non-application of salicylic acid. By improving the effective physiological traits in resistance to water deficit, salicylic acid adjusted the effects of water deficit on the yield of shallots. Foliar application of 1 mmol salicylic acid in dryland and irrigation of 50% of the plant water requirement increased onion yield by 15.12% and 29.39%, respectively, compared to the control treatment without salicylic acid.     

Aqueous flow in the presence of a perforated iris-fixated intraocular lens

The aim of this study is to investigate the characteristics of the aqueous humour flow in the anterior chamber of the eye in the presence of a perforated, phakic, iris-fixated intraocular lens (pIOL). Such pIOLs are implanted in the anterior chamber in front of the iris and therefore they interfere with aqueous motion. The aim of this work is to investigate whether a perforation in the body of the pIOL can improve its fluid dynamics performance. Numerical simulations are conducted using the free computational fluid dynamics program OpenFOAM. The aqueous humour is modelled as a Newtonian incompressible fluid and, when temperature effects are considered, the Navier–Stokes equations are coupled to the energy equation, using Boussinesq’s approach to account for fluid density changes associated temperature variations. The pressure drop across the anterior chamber is calculated considering perforations in the pIOL of various sizes and also studying the extreme case in which the passage between the iris and the pIOL gets plugged, thus leaving the hole in the pIOL as the only possible pathway for aqueous flow. The study shows that the presence of a hole in the pIOL can only have a significant role on the pressure in the eye if the normal aqueous flow in the region between the pIOL and the iris gets blocked and has a negligible effect on the wall shear stress on the cornea.     

Modification of cellulose by graft polymerization for use in drug delivery systems

Cellulose-based biodegradable polymers—as microspheres or hydrogels—are suitable for drug delivery systems. In this work, cellulose microfibers were converted to cellulose esters for subsequent graft copolymerization either by free radical or atom transfer radical polymerization (ATRP). For the former, carboxymethyl cellulose (CMC) was prepared and then modified through grafting of poly(hydroxyethyl acrylate) or polyacrylamide. ATRP was achieved by chloroacetylation of cellulose followed by graft copolymerization of hydroxyethyl acrylate or acrylamide monomers. The degree of substitution for CMC and chloroacetylated cellulose (CAC) was determined by the method described in US Pharmacopeia NF24 and by titration method, respectively. CMC, CAC, and the grafted copolymers were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal gravimetric analysis, X-ray diffraction, and atomic force microscopy; the latter technique clearly shows the chain growth of the synthetic polymers on the backbone surface. Furthermore, cephalexin antibiotic was loaded on the copolymers, and the resultant in vitro drug release studied in three different media (buffer solutions with pH equal to 3, 6.1, and 8).