Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.     

Study on the Relationship between Emulsion Properties and Interfacial Rheology of Sugar Beet Pectin Modified by Different Enzymes

The contribution of rheological properties and viscoelasticity of the interfacial adsorbed layer to the emulsification mechanism of enzymatic modified sugar beet pectin (SBP) was studied. The component content of each enzymatic modified pectin was lower than that of untreated SBP. Protein and ferulic acid decreased from 5.52% and 1.08% to 0.54% and 0.13%, respectively, resulting in a decrease in thermal stability, apparent viscosity, and molecular weight (Mw). The dynamic interfacial rheological properties showed that the interfacial pressure and modulus (E) decreased significantly with the decrease of functional groups (especially proteins), which also led to the bimodal distribution of particle size. These results indicated that the superior emulsification property of SBP is mainly determined by proteins, followed by ferulic acid, and the existence of other functional groups also promotes the emulsification property of SBP.     

Response surface methodology toward the optimization of high-energy carotenoid extraction from Aristeus antennatus shrimp

High-energy assisted extraction techniques, like ultrasound assisted extraction (UAE) and microwave assisted extraction (MAE), are widely applied over the last years for the recovery of bioactive compounds such as carotenoids, antioxidants and phenols from foods, animals and herbal natural sources. Especially for the case of xanthophylls, the main carotenoid group of crustaceans, they can be extracted in a rapid and quantitative way with the use of UAE and MAE.     

A Biosilification Fusion Protein for a ‘Self‐immobilising’ Sarcosine Oxidase Amperometric Enzyme Biosensor

Monomeric sarcosine oxidase (mSOx) fusion with the silaffin peptide, R5, designed previously for easy protein production in low resource areas, was used in a biosilification process to form an enzyme layer electrode biosensor. mSOx is a low activity enzyme (10–20 U/mg) requiring high amounts of enzyme to obtain an amperometric biosensor signal, in the clinically useful range <1 mM sarcosine, especially since the K_m is >10 mM. An amperometric biosensor model was fitted to experimental data to investigate dynamic range. mSOx constructs were designed with 6H (6×histidine) and R5 (silaffin) peptide tags and compared with native mSOx. Glutaraldehyde (GA) cross‐linked proteins retained ～5 % activity for mSOx and mSOx‐6H and only 0.5 % for mSOx‐R5. In contrast R5 catalysed biosilification on (3‐mercaptopropyl) trimethoxysilane (MPTMS) and tetramethyl orthosilicate (TMOS) particles created a ‘self‐immobilisation’ matrix retaining 40 % and 76 % activity respectively. The TMOS matrix produced a thick layer (>500 μm) on a glassy carbon electrode with a mediated current due to sarcosine in the clinical range for sarcosinemia (0–1 mM). The mSOx‐R5 fusion protein was also used to catalyse biosilification in the presence of creatinase and creatininase, entrapping all three enzymes. A mediated GC enzyme linked current was obtained with dynamic range available for creatinine determination of 0.1–2 mM for an enzyme layer ～800 nm.     

Doxorubicin Encapsulation in Carbon Nanotubes Having Haeckelite or Stone–Wales Defects as Drug Carriers: A Molecular Dynamics Approach

Doxorubicin (DOX), a recognized anticancer drug, forms stable associations with carbon nanotubes (CNTs). CNTs when properly functionalized have the ability to anchor directly in cancerous tumors where the release of the drug occurs thanks to the tumor slightly acidic pH. Herein, we study the armchair and zigzag CNTs with Stone–Wales (SW) defects to rank their ability to encapsulate DOX by determining the DOX-CNT binding free energies using the MM/PBSA and MM/GBSA methods implemented in AMBER16. We investigate also the chiral CNTs with haeckelite defects. Each haeckelite defect consists of a pair of square and octagonal rings. The armchair and zigzag CNT with SW defects and chiral nanotubes with haeckelite defects predict DOX-CNT interactions that depend on the length of the nanotube, the number of present defects and nitrogen doping. Chiral nanotubes having two haeckelite defects reveal a clear dependence on the nitrogen content with DOX-CNT interaction forces decreasing in the order 0N > 4N > 8N. These results contribute to a further understanding of drug-nanotube interactions and to the design of new drug delivery systems based on CNTs.     

Controlled synthesis of ZnO nanoparticles from a Zn(II) coordination polymer: Structural characterization,optical properties and photocatalytic activity

A zinc coordination polymer derived from pyridine-2,6-dicarboxylate (PDC), {[Zn₂(PDC)₂]}_n, was successfully prepared via conventional, sonication and microwave-irradiation methods. The composition and characteristics of the obtained coordination polymers (CPs) were investigated by elemental analysis, TGA/DTA, X-ray diffraction and spectroscopic techniques. The so obtained CPs were heat-treated in the air at 600 °C for 2 h to produce ZnO of nanosized particles (NPs). It is of interest to note that the synthesis approach of the precursor greatly affects both the nanoparticle size and the structure of the resulting ZnO NPs. Moreover, the smallest particle size was associated with the sample derived from the ultrasonically prepared precursor. TEM analysis revealed that all samples have sphere-like morphologies. Structural analysis of the prepared ZnO samples was conducted and compared using Rietveld analysis of their PXRD patterns. Optical band gap calculations based on analysis of the UV–vis spectra of ZnO samples using Tauc's power law were achieved. The highest band gap of 3.63 eV was observed for ZnO sample obtained from the ultrasonically prepared precursor. Furthermore, the photocatalytic activity of ZnO NPs for the removal of Eosin Y color was monitored. The highest removal efficiency was recorded for ZnO originated from the ultrasonically synthesized precursor. Enhancement of removal efficiency that reached 98% was attained in only a period of 8 min. Its recycling test showed that it can be reused without structural changes over four cycling experiments.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

Congruence criteria for finite subsets of complex projective and complex hyperbolic spaces

We investigate congruence classes and direct congruence classes of m-tuples in the complex projective space ℂP ⁿ . For direct congruence one allows only isometries which are induced by linear (instead of semilinear) mappings. We establish a canonical bijection between the set of direct congruence classes of m-tuples of points in ℂP ⁿ and the set of equivalence classes of positive semidefinite Hermitean m×m-matrices of rank at most n+1 with 1's on the diagonal. As a corollary we get that the direct congruence class of an m-tuple is uniquely determined by the direct congruence classes of all of its triangles, provided that no pair of points of the m-tuple has distance π/2. Examples show that the situation changes drastically if one replaces direct congruence classes by congruence classes or if distances π/2 are allowed. Finally we do the same kind of investigation also for the complex hyperbolic space ℂH ⁿ . Most of the results are completely analogous, however, there are also some interesting differences. Received: 15 January 1996