Synthesis of Hexahydrospiro[pyrazolo[3,4‐b]quinoline‐4,1′‐pyrrolo[3,2,1‐ij]quinoline‐2′,5(1H,4′H)‐diones] from 5,6‐dihydro‐4H‐pyrrolo[3,2,1‐ij]quinoline‐1,2‐dione Using Fe3O4@Cu(OH)x as a Nanocatalyst

The tricyclic isatin, 5,6‐dihydro‐4H‐pyrrolo[3,2,1‐ij]quinoline‐1,2‐dione, undergoes three‐component, one‐pot reactions with 1‐aryl‐3‐methylpyrazole‐5‐amines and cyclohexane‐1,3‐diones producing hexacyclic spiro products, hexahydrospiro[pyrazolo[3,4‐b]quinoline‐4,1‐pyrrolo[3,2,1‐ij]quinoline‐2′,5(1H,4′H)‐diones]. Comparable spiro condensation products are also obtained using 4‐hydroxy‐2H‐1‐benzopyran‐2‐one in place of cyclohexane‐1,3‐diones.     

Thermal degradation of polymers: Part XXV—Synthesis, polymerisation and thermal characterisation of m-acetamidostyrene and m-acetoxystyrene homopolymers

m-Acetoxystyrene and m-acetamidostyrene have been synthesised and homopolymerised using 2,2′-azoisobutyronitrile as free radical initiator. The resulting polymers have been characterised by a variety of methods including thermogravimetry (TG) and differential scanning calorimetry (DSC). Glass transition temperatures have been measured for samples of different molecular weight.

TG and DSC have been used to compare the degradation behaviour of poly(m-acetoxystyrene) and poly(m-acetamidostyrene) with polystyrene in air and nitrogen atmospheres.     

Influence of silanization on voltammetry at electrodes modified with silica films of controlled porosity formed by electrochemically initiated sol-gel processing

Silica sol-gel (SG) films with templated pores were deposited on glassy carbon (GC) electrodes by an electrochemically initiated process. Generation-4 poly(amidoamine), PAMAM, dendrimer was included in the tetraethoxysilane precursor to facilitate pore formation. The PAMAM adsorbs to the GC, which blocks SG formation at those sites on the electrode. The pore size was 10?±?5?nm. After removal of the PAMAM, cyclic voltammetry of Fe(CN)₆ ^3? and Ru(NH₃)₆ ³⁺ at pH?6.2 showed that the residual negative charge on the silica attenuated the current for the former and increased the current for the latter, presumably by electrostatic repulsion and ion-exchange preconcentration, respectively. This premise was supported by repeating the measurements at the isoelectric point. Methylation of the silanol sites was used to eliminate the charge of the SG. At the end-capped SG, the voltammetry of Fe(CN)₆ ^3? and Ru(NH₃)₆ ³⁺ yielded currents that were independent of pH over the range 2.1 to 7.2. Circumventing the need for the silanization by using (3-glycidyloxypropyl)trimethoxysilane as the sol-gel precursor failed because the oxygen plasma treatment to remove the PAMAM attacked the organically modified sol-gel backbone. The resulting modified electrode mitigated the influence of proteins on the voltammetry of test species and stabilized functionalize nanoparticle catalysts under hydrodynamic conditions.     

Organoplatinum(IV) tris-chelate complexes, each having a cyclic metallacarbonate ring: synthesis, characterization and kinetic studies of the formation

The complexes [Pt[(CH2)4](NN)], 1a (NN = 2,2'-bipyridine) and 1b (NN = 1,10-phenanthroline) react with 2,3-epoxypropylphenyl ether in the presence of CO2 to give tris-chelate platina(IV)cyclopentane complexes characterized by 1H and 13C NMR spectroscopy as [Pt[(CH2)4](CH2CHCH2OPhOCO2)(NN)], 2. The reactions proceed by the SN2 mechanism and the rates were independent of concentration of CO2. It is demonstrated that for 1a, the reaction proceeds 2.32 times faster than the similar reaction in which the dimethyl analog, [PtMe2(2,2'-bipyridine)], is used. The analog tris-chelate complex [Pt[(CH2)4](CH2CHPhOCO2)(phen)], 3a, was similarly synthesized.     

CompassR Yields Highly Organic-Solvent-Tolerant Enzymes through Recombination of Compatible Substitutions

The CompassR (computer-assisted recombination) rule enables, among beneficial substitutions, the identification of those that can be recombined in directed evolution. Herein, a recombination strategy is systematically investigated to minimize experimental efforts and maximize possible improvements. In total, 15 beneficial substitutions from Bacillus subtilis lipase A (BSLA), which improves resistance to the organic cosolvent 1,4-dioxane (DOX), were studied to compare two recombination strategies, the two-gene recombination process (2GenReP) and the in silico guided recombination process (InSiReP), employing CompassR. Remarkably, both strategies yielded a highly DOX-resistant variant, M4 (I12R/Y49R/E65H/N98R/K122E/L124K), with up to 14.6-fold improvement after screening of about 270 clones. M4 has a remarkably enhanced resistance in 60 % (v/v) acetone (6.0-fold), 30 % (v/v) ethanol (2.1-fold), and 60 % (v/v) methanol (2.4-fold) compared with wild-type BSLA. Molecular dynamics simulations revealed that attracting water molecules by charged surface substitutions is the main driver for increasing the DOX resistance of BSLA M4. Both strategies and obtained molecular knowledge can likely be used to improve the properties of other enzymes with a similar α/β-hydrolase fold.     

A Systematic Study of ZnO/CuO Core/Shell Nanostructures Pegylated by Microwave Assistant Reverse Micelles (RM) Method

In this work we synthesized ZnO/CuO nanostructures pegylated by simple and fast microwave method assistant reverse micelles, Reverse micelles protocol creates many advantages in stability, particle size control, morphology, density, loading level, distribution, uniformity, charge and purification. Based on the statistical results ZnO/CuO nanostructures placed in the hydrophilic substrate. The effect of microwave and concentration of surfactant on the surface area, pore diameter and pore volume of the final product was systematically studied using Taguchi technique. ZnO/CuO core/shell pegylated nanostructures, indicating a ZnO as core and CuO as shell and continuous micelles chains around this structures. Products were characterized by UV–Vis spectra, X-ray diffraction, scanning electron microscopy, Dynamic light scattering, Energy-dispersive X-ray spectroscopy, transmission electron microscopy and nitrogen adsorption (i.e. Brunauer–Emmett–Teller surface area analysis).     

An experimental investigation of creaming phenomenon using a novel optical method: A case study of mineral oil-in-water emulsion

The present study elucidates the creaming phenomenon of mineral oil-in-water macroemulsion using a new noninvasive method based on turbidimetry. Additionally, microscopic observation of the phenomenon is carried out to derive an in-depth understanding of the mechanisms. Accumulation of the particles in the emulsions under the formed cream is monitored during a relatively prolonged period of time. Backflow of continuous and dispersed phases in temporary channels is observed at the proximity of the cream. In addition to the backflow, a high traffic density of the dispersed particles and deflocculation of the cream are the main reasons for the accumulation of the dispersed phase particles and a temporary stability against creaming. The deflocculation hinders cream growth and increases the stratification of the cream. A low concentration zone of the dispersed phase with the width of ～100?µm is observed under the cream.     

Quantitative analysis of fluorimated ethylchloroformate derivatives of non-protein amino acids using positive and negative chemical ionization gas chromatography-mass spectometry

The GC-MS characterization of the ethylchloroformate derivatives of amino acids in an aqueous medium has been applied to non-protein amino acids. Derivatization of non-protein amino acids using ethylchloroformate, trifluoroethanol, and pyridine produced strong [M + 1]⁺ and [M - 1]⁻ ions in positive and negative chemical ionization (CI) modes, respectively. Twenty-one out of the twenty-three non-protein amino acids studied produced detectable ion chromatograms in both ionization modes when methane was used as the CI reagent gas. Mass spectra of these non-protein amino acid derivatives showed characteristic [M - 19]⁺, [M + 1]⁺, [M + 29]⁺, and [M + 41]⁺ peaks in the positive chemical ionization mode, and [M - 1]⁻, and [M + 35]⁻ peaks in the negative chemical ionization mode. The detection limits and the linear dynamic range of trifluorethanol ethylchloroformate derivatives of non-protein amino acids were studied using positive chemical ionization. The detection limits are mostly in the femtomole range.     

Molecular structure and character of bonding of mono and divalent metal cations (Li+, Na+, K+, Mg2+, Ca2+, Zn2+, and Cu+) with guanosine: AIM and NBO analysis

The B3LYP/6-311++G (d,p) density functional approach was used to study the gas-phase metal affinities of Guanosine (ribonucleoside) for the Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, and Cu⁺ cations. In this study we determine coordination geometries, binding strength, absolute metal ion affinities, and free energies for the most stable products. We have also compared the results for Guanosine, with our previously reported results for 2′-Deoxyguanosine. Based on the results, it is obvious that MIA is strongly dependent on the charge-to-size ratio of the cation. Guanosine interacts more strongly with Zn²⁺ than do with Mg²⁺, Ca²⁺, and Cu⁺ and therefore stronger interactions lead to higher MIA. In both free molecules and their complexes, the Syn orientation of the base is stabilized by an intramolecular O5′–H···N3 hydrogen bond and the anti orientation of the base is stabilized by an intramolecular C–H···O hydrogen bond formed between the (C8-H8) and the O5′ atom of the sugar moiety. It is also interesting to mention that linear correlation between calculated MIA values and the atomic numbers (Z) of the metal ions of Li⁺, Na⁺, and K⁺ were found. Furthermore, the influences of metal cationization on the strength of the N-glycosidic bond, torsion angles, angle of pseudorotation (P), and intramolecular C–H···O and O–H···O hydrogen bonds have been studied. Natural bond orbital (NBO) analysis was performed to calculate the charge transfer and natural population analysis of the complexes. Quantum theory of atoms in molecules (QTAIM) was also applied to determine the nature of interactions.