Dielectric barrier discharge plasma pre-treatment to facilitate the acetylation process of corn starch under heating/cooling cycles.

The objective of the current work was to evaluate the impacts of dielectric barrier discharge plasma and repeated dry-heat treatments on the acetylation process of corn starch. The combined modification resulted in a higher substitution degree of acetate groups on starch chains compared to the acetylation treatment alone. This outcome was linked to the increase in surface area and structural organization level of granules achieved through the application of plasma and heating/cooling cycles, respectively. The successful esterification of starch structure was verified through FTIR (1710 cm-1) and 1H NMR (2 ppm). With the increase in plasma treatment duration up to 20 min, gelatinization enthalpy increased (10.81 J/g) due to the cross-linking reaction. Starch acetate produced through the combined treatment could find the application in the development of low-calorie food formulations due to its high resistant starch (70.5 g/100 g) and low viscosity (43 mPa s).

Synthesis of chiral Cu(II) complexes from pro-chiral Schiff base ligand and investigation of their catalytic activity in the asymmetric synthesis of 1,2,3-triazoles.

A pro-chiral Schiff base ligand (HL) was synthesized by the reaction of 2-amino-2-ethyl-1,3-propanediol and pyridine-2-carbaldehyde in methanol. The reaction of HL with CuCl2·2H2O and CuBr2 in methanol gave neutral mononuclear Cu(II) complexes with general formula of [Cu(HL)Cl2] (1) and [Cu(HL)Br2] (2), respectively. By slow evaporation of the methanolic solutions of 1 and 2, their enantiomers were isolated in crystalline format. The formation of pure chiral crystals in the racemic mixture was amply authenticated by single crystal X-ray analysis, which indicated that S-[Cu(HL)Cl2], R-[Cu(HL)Cl2], and S-[Cu(HL)Br2] are crystallized in chiral P212121 space group of orthorhombic system. Preferential crystallization was used to isolate the R and S enantiomers as single crystals and the isolated compounds were also studied by CD analysis. Structural studies indicated that the origin of the chirality in these compounds is related to the coordination mode of the employed pro-chiral ligand (HL) because one of its carbon atoms has been converted to a chiral center in the synthesized complexes. Subsequently, these complexes were used in click synthesis of a ß-hydroxy-1,2,3-triazole and the results of catalytic studies indicated that 1 and 2 can act as enantioselective catalysts for the asymmetric synthesis of ß-hydroxy-1,2,3-triazole product under mild condition. This study illustrates the significant capacity of the use of pro-chiral ligands in preparing chiral catalysts based on complexes which can also be considered as an effective approach to cheap chiral catalysts from achiral reagents.

Solid state cationization reaction of microporous starch with betaine hydrochloride under repeated heating/cooling cycles: Design of a green approach for corn starch modification.

In this research, the cationization process of microporous starch with betaine hydrochloride (BHC) in the presence of H3PO4 (as a catalyst) under heating/cooling cycles was reported for the first time. Granular microporous starch was initially prepared from normal corn starch (NS) through amyloglucosidase treatment. Then, solid state cationization reaction of microporous starch (MS) with betaine hydrochloride (BHC) was performed under repeated dry-heat modification. The cationic microporous starch showed higher substitution degree (0.031) and reaction efficiency (89.1 %) in comparison with cationic starch based on NS (0.021, 60.3 %), which this can be attributed to the increased probability of effective collision between BHC molecules and starch granules after enzymatic treatment. The analysis of cationic starches by FTIR and 13C NMR confirmed the presence of cationic functional groups on starch chains. Further examinations on the modified starches by single and dual treatments were accomplished with respect to morphology, particle size distribution, X-ray powder diffraction (XRD), colour parameters, zeta potential, amylose content, viscosity, solubility, and swelling power. The greenness of the suggested dual treatment (score: 82) in this work was evaluated and compared to a conventional method reported in literature (score: 67) on the preparation of cationic starches.

Solid state malic acid esterification on fungal α-amylase treated corn starch: Design of a green dual treatment.

For the first time, the current work applied fungal α-amylase treated corn starch in granular form to produce solid state malate-esterified starch (MES). The pores and channels created on the granules after the enzymatic modification could provide more possibilities for malic acid to esterify the starch, resulting in the increase of substitution degree (0.084) and reaction efficiency (86.6%) compared to NS. Based on the obtained results, the dual treatment significantly increased solubility, amylose content, and syneresis, but reduced transparency, viscosity, digestibility rate, and swelling power compared to those of NS. The occurrence of esterification onto starch chains was confirmed by FT-IR at 1720 cm-1. Other techniques including SEM, XRD, and DSC were employed to examine changes in the structure of starch granules after applying each treatment. Also, the greenness of the combined modification (score: 77) was proved by using a new methodology named Eco-Scale.

Cu(II)-Hydrazide Coordination Compound Supported on Silica Gel as an Efficient and Recyclable Heterogeneous Catalyst for Green Click Synthesis of ß-Hydroxy-1,2,3-triazoles in Water.

A hydrazone ligand, (E)-6-(2-((2-hydroxynaphthalen-1-yl)methylene)hydrazinyl)nicotinohydrazide (H2L), was synthesized and characterized by spectroscopic methods. The reaction of H2L with CuCl2·2H2O in methanol gave Cu(II) coordination compound, [Cu(HL')(Cl)]·CH3OH (1), which was characterized by elemental analysis and spectroscopic methods (Fourier transform infrared (FT-IR) and UV-vis). The structure of 1 was also determined by single-crystal X-ray analysis. Structural studies confirmed the formation of esteric group during the synthesis of 1. Compound 1 was immobilized on 3-aminopropyltriethoxysilane (APTS)-functionalized silica gel through the amidification reaction and the obtained heterogeneous coordination compound was utilized as a catalyst for the three-component azide-epoxide-alkyne cycloaddition reaction in water as a green solvent. The structural properties of the heterogeneous catalyst were characterized by a combination of FT-IR, UV-vis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy-dispersive spectrometry (EDS) analyses. The effect of the amount of catalyst and temperature on the cycloaddition reaction was studied, and the obtained 1,2,3-triazoles were characterized by spectroscopic studies and single-crystal X-ray analysis. The catalytic investigations revealed that this catalytic system has high activity in the synthesis of ß-hydroxy-1,2,3-triazoles. It was also found that the aromatic and aliphatic substituents on the alkyne and epoxide together with the reaction temperature have considerable effects on the activity and regioselectivity of this catalytic system.

A synthetic manganese-calcium cluster similar to the catalyst of Photosystem II: challenges for biomimetic water oxidation.

Herein, we report the synthesis, characterization, crystal structure, density functional theory calculations, and water-oxidizing activity of a pivalate Mn-Ca cluster. All of the manganese atoms in the cluster are Mn(iv) ions and have a distorted MnO6 octahedral geometry. Three Mn(iv) ions together with a Ca(ii) ion and four-oxido groups form a cubic Mn3CaO4 unit which is similar to the Mn3CaO4 cluster in the water-oxidizing complex of Photosystem II. Using scanning electron microscopy, transmission electron microscopy, energy dispersive spectrometry, extended X-ray absorption spectroscopy, chronoamperometry, and electrochemical methods, a conversion into nano-sized Mn-oxide is observed for the cluster in the water-oxidation reaction.

The effect of the orientation of the Jahn-Teller distortion on the magnetic interactions of trinuclear mixed-valence Mn(ii)/Mn(iii) complexes.

Two new trinuclear manganese complexes, [Mn3(L1)(µ-OCH3)2(N3)2]·CH3OH (1) and [Mn3(L2)(µ-OCH3)2(N3)2]·CH3OH (2), have been obtained from the reaction of Mn(OAc)2 4H2O, NaN3 and the preformed N6O4-donor H4L1 or H4L2 compartmental ligands, which are synthesized via Schiff base condensation of pentaethylenehexamine with 2-hydroxybenzaldehyde or 2-hydroxy-3-methoxybenzaldehye, respectively. Complexes 1 and 2 have been characterized by spectroscopic methods and single-crystal X-ray analysis. The structural studies indicate that both 1 and 2 are mixed-valence complexes containing angular Mn(iii)-Mn(ii)-Mn(iii) cores in which the metal centers are connected to each other by phenoxido and methoxido bridging groups. The coordination environment around the manganese ions is analogous in both complexes, but for a change in the direction of the Jahn-Teller distortion around the external Mn(iii) ions when going from 1 to 2, which is mainly attributed to the steric effect of different substituents on the phenyl rings of the ligands. The analysis of the magnetic susceptibility data indicates the presence of antiferromagnetic intramolecular coupling in both complexes, but the interaction in 1 was found to be nearly one order of magnitude weaker than that in 2. This fact is rationalized on the basis of the different orientation of the Jahn-Teller distortion, which modifies the magnetic exchange pathway through the phenoxido bridges from the equatorial-axial connection type observed in 1 to the axial-axial linkages displayed by 2.

Inhibition of quorum sensing related virulence factors of Pseudomonas aeruginosa by pyridoxal lactohydrazone.

Pseudomonas aeruginosa quorum sensing (QS) system is a cell to cell signaling mechanism that regulates virulence factors and pathogenicity. Therefore, the QS system in P. aeruginosa may be an important target for pharmacological intervention. The present study aimed to investigate the effects of sub-MIC concentrations of (S,E)-2-hydroxy-N-(3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl)propane hydrazide (pyridoxal lactohydrazone) against P. aeruginosa QS related virulence factors. We investigated the effect of sub-MIC concentrations of chiral pyridoxal lactohydrazone, which formed by the reaction of chiral lactic acid hydrazide and pyridoxal (one form of Vitamin B6) as bioactive reagents, on virulence factors. Treated PAO1 cultures in the presence of tested compound at 1/4 and 1/16 MIC (32 and 8 µg/mL respectively) showed significant inhibition of virulence factors including motility, alginate and pyocyanin production and susceptibility to H2O2 (P < 0.001). Also, the pyridoxal lactohydrazone showed anti-QS activity in Chromobacterium violaceum CV026 biosensor bioassay. Because of quorum sensing is a promising target for anti-virulence therapy and also important role of LasR regulatory protein in the initiation of P. aeruginosa QS system, we carried out molecular docking for understanding the interactions of pyridoxal lactohydrazone with the LasR receptor. The results of docking study suggested that the pyridoxal lactohydrazone has potential to inhibit the LasR protein. The results indicated that sub-MIC concentrations of this compound exhibited inhibitory effect on P. aeruginosa QS related virulence factors.

N,N'-(Pyridine-2,6-di-yl)dibenzamide.

The mol-ecule of the title compound, C19H15N3O2, is completed by the application of crystallographic twofold symmetry, with the pyridine N atom lying on the rotation axis. The mol-ecular structure is approximately planar, the dihedral angle between the mean planes of the pyridine and benzene rings being 7.53 (11)°. In the crystal, N-H⋯O hydrogen bonds link the mol-ecules into a two-dimensional array perpendicular to the c axis.