Schiff Base型大环化合物的合成研究进展

研究发现Schiff base型大环化合物具有优异的抗菌和过渡金属离子的萃取性能,已经成为有机化学的研究热点之一。综述了Schiff base型大环化合物的合成方法研究进展,并对合成中的一些诸如模板离子的大小与缩合比,脱模板作用等问题作了简要探讨。     

Luminescent Organic–Inorganic Hybrids of Functionalized Mesoporous Silica SBA-15 by Thio-Salicylidene Schiff Base

Novel organic–inorganic mesoporous luminescent hybrid material N,N′-bis(salicylidene)-thiocarbohydrazide (BSTC-SBA-15) has been obtained by co-condensation of tetraethyl orthosilicate and the organosilane in the presence of Pluronic P123 surfactant as a template. N,N′-bis(salicylidene)-thiocarbohydrazide (BSTC) grafted to the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TESPIC) was used as the precursor for the preparation of mesoporous materials. In addition, for comparison, SBA-15 doped with organic ligand BSTC was also synthesized, denoted as BSTC/SBA-15. This organic–inorganic hybrid material was well-characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy (HRTEM), and photoluminescence spectra, which reveals that they all have high surface area, uniformity in the mesostructure. The resulting materials (BSTC-SBA-15 and BSTC/SBA-15) exhibit regular uniform microstructures, and no phase separation happened for the organic and the inorganic compounds was covalently linked through Si–O bonds via a self-assemble process. Furthermore, the two materials have different luminescence range: BSTC/SBA-15 presents the strong dominant green luminescence, while BSTC-functionalized material BSTC-SBA-15 shows the dominant blue emission.     

Crosslinked polyurethane–epoxy hybrid emulsion with core–shell structure

An epoxy resin was used to prepare crosslinked polyurethane hybrid emulsion through the blocked NCO prepolymer mixing process. Due to their hydrophobicity, the amine chain extender, blocked –NCO, and epoxy are located inside the emulsion particles. Thus, the crosslinking reaction occurs mostly in the interior of the particles. In this way, the crosslinking density of the resin is increased without the use of solidifying agents or heating during film formation, and the stability of the emulsions remains uninfluenced. The effects of the type of amine chain extender and the type, dosage, and addition mode of the epoxy resin were studied in terms of mechanical properties and swelling properties in water and toluene of the cast films. Additionally, the stability of the single-pack hybrid emulsion was studied. The results showed that the sample prepared with diethylene triamine had good stability, chemical resistance, and high mechanical strength. The modulus and water resistance of the films increased with the epoxy resin content, which could reach 20 wt%. The type of amine chain extender affected the stability of the emulsions significantly. The molar ratio of NH/NCO at 1:1 led to the best film performance. The optimal temperature of the chain-extension reaction was approximately 80°C. The hybrid emulsions could be stored for at least 6 months without apparent performance changes.     

Swelling Behavior of Calcium–Ions Crosslinked Bipolymeric Sodium Alginate–Lignosulphonic Acid Blends

A series of blends based on lignosulfonic acid (LSA) and sodium alginate (NaAlg) were prepared with varying proportions of NaAlg and LSA using a solution-casting method. The swelling /degradation behavior of blends was studied so that they can be used for gastrointestinal drug delivery. Effect of crosslinking, pH, alginate content, and treatment with strong acid on swelling properties of the blends was investigated. It was found that blends show pH-sensitive swelling and show less water uptake due to crosslinking, while crosslinking is reduced in the presence of strong acid. Thus these blends offer their strong candidature for possible use in drug delivery.     

Synthesis of Schiff base–containing benzoxazine derivatives

The excellent chemical and physical properties of benzoxazine resins and the functionality of Schiff bases were combined in one compound's structure, creating newly designed benzoxazine derivatives that can form complexes with metals. The new type of benzoxazine monomer was synthesized via the ring-closure reaction of formaldehyde, aniline, and three newly designed Schiff bases. The presence of the Schiff base in the molecular structure of these novel benzoxazine monomers enables them to trap metals as the functional compounds, like Cu, from a solution. Thermally initiated polymerization occurs at a lower temperature by the formation of intermolecular and intramolecular hydrogen bonds between imine, oxazine, Schiff base hydroxyl groups, and the newly generated hydroxyl groups. The thermal behavior of the bisbenzoxazine monomers was investigated with Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry, and then they were cured at 120, 180, and 230°C. According to the magnetic susceptibility, FTIR, scanning electron microscopy with energy dispersive X-ray spectroscopy, TGA, and microwave plasma atomic emission spectroscopy results, it is shown that Cu(II) complexes of the compounds were also succesfully synthesized, and they proved to be successful in catching metal. This is due to the functionality of Schiff bases forming the metal complexation in the compounds. The poly(bisbenzoxazine)s also showed high limiting oxygen index (31–37), low ring-opening temperature (150–190°C), high char yield (35%–49%), and excellent thermal stability, due to the highly crosslinked nature of the polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47908.     

Highly active silica–alumina–titania catalyst for photoinduced non-oxidative methane coupling

Novel SiO₂–Al₂O₃–TiO₂ systems showed the high photocatalytic activity for photoinduced non-oxidative methane coupling at room temperature, which was recognized as the synergistic effect of Ti and Al in silica matrix.     

Highly porous corundum–mullite ceramics – Structure and properties

The aim of this study was to improve the mechanical properties of porous corundum ceramics by adding various types of SiO₂ source (SiO₂, SiC and Si₃N₄), but at the same time retaining high porosity (at least 55%). Ceramics were fabricated by slip casting. Pores were formed using aluminium's reaction with water. It was found that the bending strength of the material can be improved and relatively high porosity retained by producing corundum–mullite composites. Addition of 3.7 equivalent wt% of SiO₂ source increased the bending strength by up to 250% in comparison with unmodified corundum ceramics. The apparent porosity decreased by up to ca. 8%. If the amount of SiO₂ source was increased from 3.7 equivalent wt% to 7.3 equivalent wt%, the bending strength decreased. The best mechanical properties were achieved with samples that were modified with SiC and Si₃N₄ nanopowders. This is due to better dispersion in Al₂O₃ matrix.     

Highly effective molybdena–manganese catalyst for propane oxidative dehydrogenation

A manganese oxide catalyst impregnated with molybdenum exhibits high yield, productivity and stability in the oxidative dehydrogenation of propane to propene. This catalyst exhibits catalytic activity and yield to propene at temperatures as low as 623 K. This revised version was published online in August 2006 with corrections to the Cover Date.     

5-CM-Salophen Schiff Base as an Effective Inhibitor for Corrosion of Mild Steel in 0.5 M HCl

5-CM-Salophen Schiff base was examined as an inhibitor for corrosion of mild steel in 0.5 M hydrochloric acid (HCl). The gravimetric data revealed corrosion inhibition effectiveness of the Schiff base even at low concentrations. Polarization measurements showed that the Schiff base is a mixed-type corrosion inhibitor. The polarization resistance (R_p) increased with increasing the Schiff base concentration. Also, the values of the double-layer capacitance decreased after addition of the inhibitor due to adsorption of the Schiff base on the surface. The inhibition mechanism was investigated by plotting the Langmuir adsorption isotherm and calculating the potential of zero charge (E_PZC) for mild steel samples. Scanning electron microscopy (SEM) analysis confirmed the results of the corrosion tests.     

Efficient and Mild Synthesis of Novel Diazo Dyes through Coupling Reaction of Schiff Base Diazonium Salts with β-naphthol

In this study, efficient and mild method for synthesis of some novel diazo dyes containing Schiff bases has been reported. All of the intermediates and final products were obtained in good to high yields and appropriate reaction times. The structures of desired products were determined using physical and spectroscopy data such as; IR, ¹H NMR, ¹³C NMR, mass spectra, and C.H.N. analyses. The worldwide availability, larger scale synthesis, high yields, and short reaction times are the advantages of the present method.     

Structure–Function Studies on IMD-0354 Identifies Highly Active Colistin Adjuvants

Infections caused by multidrug-resistant (MDR) bacteria, particularly Gram-negative bacteria, are an escalating global health threat. Often clinicians are forced to administer the last-resort antibiotic colistin; however, colistin resistance is becoming increasingly prevalent, giving rise to the potential for a situation in which there are no treatment options for MDR Gram-negative infections. The development of adjuvants that circumvent bacterial resistance mechanisms is a promising orthogonal approach to the development of new antibiotics. We recently disclosed that the known IKK-β inhibitor IMD-0354 potently suppresses colistin resistance in several Gram-negative strains. In this study, we explore the structure–activity relationship (SAR) between the IMD-0354 scaffold and colistin resistance suppression, and identify several compounds with more potent activity than the parent against highly colistin-resistant strains of Acinetobacter baumannii and Klebsiella pneumoniae.     

Highly functional biobased polyols and their use in melamine–formaldehyde coatings

Highly functional sucrose soyate polyol (SSP) resins were synthesized by ring-opening epoxidized sucrose soyate with methanol or ethanol and were subsequently crosslinked with a melamine–formaldehyde (MF) resin in the presence of an acid catalyst or blocked acid catalyst. The biobased polyols were characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, proton nuclear magnetic resonance spectroscopy, Brookfield viscosity, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The thermal properties of the biobased MF coatings were studied using differential scanning calorimetry and dynamic mechanical analysis. As controls, a soybean oil polyol (SBOP) with lower functionality and a commercial polyester polyol were studied for comparison. Overall, MF coatings formulated with SSPs showed superior properties to coatings formulated with SBOP and comparable properties to the commercial polyester which was attributed to the high hydroxyl functionality.     

Highly Selective and Active Niobia-Supported Cobalt Catalysts for Fischer–Tropsch Synthesis

The performance of Co/Nb₂O₅ was compared to that of Co/γ-Al₂O₃ for the Fischer–Tropsch synthesis at 20 bar and over the temperature range of 220–260 °C. The C₅₊ selectivity of Nb₂O₅-supported cobalt catalysts was found to be very high, i.e. up to 90 wt% C₅₊ at 220 °C. The activity per unit weight cobalt was found to be similar for Nb₂O₅ and γ-Al₂O₃-supported catalysts at identical reaction temperature. However, due to the low porosity of crystalline Nb₂O₅, the cobalt loading was limited to 5 wt% and consequently the activity per unit weight of catalyst was lower than of Co/γ-Al₂O₃ catalysts with higher cobalt loadings. This low activity was largely compensated by increasing the reaction temperature, although the C₅₊ selectivity decreased upon increasing reaction temperature. Due to the high intrinsic C₅₊ selectivity, Nb₂O₅-supported catalysts could be operated up to ~250 °C at a target C₅₊ selectivity of 80 wt%, whereas γ-Al₂O₃-supported catalysts called for an operation temperature of ~210 °C. At this target C₅₊ selectivity, the activity per unit weight of catalyst was found to be identical for 5 wt% Co/Nb₂O₅ and 25 wt% Co/Al₂O₃, while the activity per unit weight of cobalt was a factor of four higher for the niobia-supported catalyst.