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.     

Phytochemical analysis, cytotoxic activity and constituents-activity relationships of the leaves of Cinnamomum iners (Reinw. ex Blume-Lauraceae)

The leaves of Cinnamomum iners (Reinw. ex Blume-Lauraceae) have been refluxed successively with chloroform and alcohol to get chloroform extract and alcoholic extract. Both the extracts have been assayed for cytotoxicity against human colorectal tumour cells. The chloroform extract exhibited significant cytotoxicity with IC(50) 31?μg mL(-1) (p??200?μg mL(-1). The chloroform extract has been further proceeded for chemical analysis by GC-TOFMS and 178 components were identified including acids, amines, amides, aldehydes, alcohols, esters, benzene derivatives, bicyclic compounds, terpenes, hydrocarbons, naphthalene derivatives, furan derivatives, azulenes, etc. Nine components representing 51.73% of the total chloroform extract were detected as major components. Caryophyllene (14.41%) and Eicosanoic acid ethyl ester (12.17%) are the most prominent components of the chloroform extract. β-Caryophyllene (14.41%) as most abundant compound supports potent cytotoxicity as shown by chloroform extract.     

Detonation performance of nitroaromatic decorated carbon nanotubes

Structural Chemistry - In this study, density functional theory (DFT) was employed to predict thermochemical and energetic properties for single-walled carbon nanotubes (SWCNTs) decorated with one...     

New 5-bromo-2-hydroxybenzaldehyde S-ethylisothiosemicarbazone and its mixed-ligand Cu(II) complex with imidazole: synthesis, characterization and DFT calculation

A new Schiff base ligand of 5-bromo-2-hydroxybenzaldehyde S-ethyl-isothiosemicarbazone (H₂L) was synthesized and its mixed-ligand Cu(II) complex was also prepared by reaction of Cu(NO₃)₂·3H₂O with H₂L and imidazole. Their structures were fully characterized by elemental analysis, FT-IR, molar conductivity and UV-Vis methods. The analytical data suggest that the metal, H₂L and imidazole ratios in the Schiff base complex are 1:1:1. Single crystal diffraction was also used to better understand the molecular structure of the Cu(II) complex. The results of physico-chemical analyses of the Schiff base complex reveal the coordination geometry around the central atom is square planar. The H₂L ligand (NNO donor) is coordinated to the metal center as a tridentate bionegatively agent. Another position of the square planar geometry is occupied by the imidazole ligand. Furthermore, computational studies of the new complex were performed by carrying out DFT calculations. Geometry optimization and natural band analysis of the complex is discussed in further detail.      

Preparation and Characterization of Cu2S Nanoparticles Via Ultrasonic Method

This study reports on the synthesis of Cu₂S nanoparticles via an ultrasonic method by employing Na₂SO₃ as a reducing agent. Morphology, structure, and composition of the obtained products were characterized by X-ray diffraction, energy dispersive X-ray analysis, scanning electron microscope and photoluminescence spectroscopy. The effects of time and power of irradiation were studied.