Fabrication of magnetic β-CD/chitosan nanocomposite as an efficient and recyclable dye adsorbent

ABSTRACT

In this work, novel magnetic nanocomposite adsorbents were prepared by crosslinking β-cyclodextrin (β-CD) onto chitosan backbones by using epichlorohydrin as a crosslinker and in the presence of Fe₃O₄ nanoparticles. The composition of β-CD-chitosan nanocomposites was characterized via FTIR, XRD, TEM, SEM, and VSM. Then, the as-prepared nanocomposites were treated for elimination of methyl orange (MO). The results indicated that the adsorption of MO exhibited a maximum adsorption capacity of 314 mg g^?1 at 25°C. Moreover, the rates and isotherm data of adsorption matched excellent at different MO concentrations (10, 60, and 120 mg/L) using second-order and Langmuir models with the regression coefficient (R²) of 0.9993 and 9990, respectively. Besides, the thermodynamic data confirmed MO adsorption as an endothermic process. The adsorbent was also confirmed as good materials for re-use and maintained 88% of its initial adsorption capacity for MO after the fifth regeneration cycles. In conclusion, the synthesized magnetic nanocomposites can be applied as cost-effective dye adsorbents with high regeneration efficiency.     

Silver nanoparticles as an efficient,heterogeneous and recyclable catalyst for synthesis of β-enaminones

A simple and efficient protocol has been developed for synthesis of β-enaminones and β-enamino esters catalyzed by silver nanoparticles as a novel, heterogeneous, moisture stable and recyclable catalyst under mild reaction conditions. The reaction was optimized with respect to various parameters such as catalyst screening, catalyst loading, different solvents and temperature. The silver nanoparticle exhibited excellent activity and the methodology is applicable to diverse substrates providing good to excellent yields of desired products. The catalyst was recycled for three consecutive cycles without any significant loss in activity.     

Study of corrosion and friction reduction of electroless Ni–P coating with molybdenum disulfide nanoparticles

One composite coating of Ni–P alloys containing MoS₂ nanoparticles was prepared by electroless technique based on the better friction reduction ability of MoS₂ and better anticorrosion property of electroless Ni–P alloys on carbon steel surfaces. Electrochemical method—that is, using Tafel polarization curves—was carried out in order to study the corrosion performance of the coating. The results indicate that the anticorrosion ability of the composite coating was decreased because of the addition of nano-MoS₂ particles. The corrosional surfaces were studied and analyzed through scanning electron microscopy (SEM). The corrosion mechanism of the composite coatings was mainly ascribed to the formation of microcells around the nanosized MoS₂ particles, and the active ion-like Cl⁻ destroyed the surface film and induced the corrosion on the inside part of the coating. The friction coefficient of electroless composite coatings was measured by end-facing tribometer. It was found that the friction coefficient of the Ni–P–(nano-MoS₂) composite coating decreased greatly compared with those of Ni–P electroless coatings.     

Preparation and characterization of thermo-sensitive microspheres with β-cyclodextrin groups

采用沉淀聚合机理,由一步法和两步法制备聚（N-异丙基丙烯酰胺-甲基丙烯酸缩水甘油酯） [P(NIPAM-co-GMA)]温敏性微球。其中一步法是同时加入所有反应物反应成微球,而两步法是先加NIPAM成微球,再加入GMA,最终均生成P(NIPAM-co-GMA)微球;再将改性的乙二胺代环糊精（EDA-β-CD）通过化学反应引入到P(NIPAM-co-GMA)微球结构中,制备得到聚（N-异丙基丙烯酰胺-甲基丙烯酸-2-羟丙基乙二胺基环糊精） [P(NIPAM-co-GMA/β-CD)]共聚高分子微球。分别用扫描电镜、红外光谱、控温激光粒度仪及光学显微镜对产物的形貌、结构和温敏特性进行了表征。结果表明,两种方法制备的微球均具有良好的单分散性和球形度,均能成功地固载β-环糊精（β-CD）基团,并且都有温度响应特性;但是,同一步法制备的微球相比,两步法制得的微球粒径明显较大,且微球固载有更多的β-CD。     

Chemisorption of halogen on carbons—I Stepwise chlorination and exchange of C-CI with C-H bonds

Stepwise chlorination at 773 K of carbons and the resulting amounts of HC1 released can be interpreted by assuming that saturation of olefinic bonds by Cl₂ occurs first. This is followed by exchange with the chemibound hydrogen and lastly by slight dehydrogenation of the adsorbent, yielding HCl and olefinic bonds. High-temperature chlorination-hydrogenation cycles may be performed many times to a depth of 3.4 meq/g without appreciable weight loss or change in pore structure of an activated carbon.     

Ionic liquid supported on magnetic nanoparticles as highly efficient and recyclable catalyst for the synthesis of β-keto enol ethers

A magnetically ionic liquid supported on γ-Fe₂O₃ nanocatalyst (Al_xCl_y-IL-SiO₂@γ-Fe₂O₃) was synthesized and evaluated as a recoverable catalyst for the synthesis of β-keto enol ethers. The immobilized catalyst proved to be effective and provided the products in high to excellent yield at room temperature. Moreover, the catalyst could be easily recovered by magnetic separation and recycled for six times without significant loss of its catalytic activity.     

Synthesis and structure of a gallate of strontium with Sr–C–Ga three-center two-electron bonds

The addition reaction of strontium bis[bis(trimethylsilyl)amide] with triethylgallane yields quantitatively strontium bis[triethyl-bis(trimethylsilyl)aminogallate] (1). The strontium cation shows the unusual low coordination number of four to two nitrogen and two carbon atoms. Sr–C bond lengths with a mean value of 282 pm are observed with the Sr–C–Ga three-center two-electron bonds. Due to the mainly ionic character of this compound a fast exchange of the bridging and terminal ethyl groups is observed on the NMR time scale.     

Cooperative effect of molecular orientation and β-form on toughening injection-molded isotactic polypropylene with β-nucleating agent

The toughness of conventional injection-molded isotactic polypropylene bars has been investigated with respect to the notch location and β-nucleating agent. Superior toughness is achieved in the β-nucleated bars with notches near the gate, but is absent in the near-gate bars without β-nucleating agent or in the β-nucleated ones far from the gate. With detailed structural analysis across the sample thickness, it is indicated that in these tough bars, extensive flow close to the surface suppresses the formation of β-form to a large extent but favors the generation of oriented α-form, whereas toward inner region, an opposite tendency is presented with the decay of flow strength and the activation of β-nucleating agent. Allowing that this peculiar hierarchical structure is absent in other two kinds of bars, it is deduced that the cooperative effect of molecular orientation of α-form in the skin layer and rich β-form in the inner region is responsible for the significant toughness enhancement in the β-nucleated bars near the gate. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Crosslinking of β-cyclodextrin and combining with ammonium polyphosphate for flame-retardant polypropylene

This work presents the synthesis of crosslinked hexamethylene diisocyanate β-cyclodextrins (HDI-CDs) by reacting β-cyclodextrin (β-CD) with HDI as a crosslinking agent at different feed ratios. As a novel char-forming agent, the HDI-CDs are combined with ammonium polyphosphate (APP) and applied in polypropylene (PP) to form intumescent flame-retardant composites. The structure of HDI-CDs is characterized by Fourier transform infrared spectra (FTIR), ¹³C nuclear magnetic resonance spectroscopy, and nitrogen adsorption–desorption test. The thermogravimetric analysis (TGA) results indicate that HDI-CDs have better char-forming performance than β-CD. FTIR spectra, X-ray diffraction, and Raman spectra characterization demonstrate that the reaction between HDI-CDs and APP contributes to the formation of a more stable char layer than β-CD and APP. According to the results of TGA, scanning electron microscopy, limiting oxygen index (LOI), UL-94, and X-ray photoelectron spectroscopy test, when the crosslinking degree of HDI-CDs is high enough (not less than β-CD:HDI = 1:3.6), the PP/APP/HDI-CDs composites can form a compact and dense char layer during combustion. Among all composites, PP/APP/HDI-CD(4) shows the best flame-retardant performance, which can pass the UL 94 V-0 rating with an LOI value of 32.8% when the loading of flame retardants is 28 wt %. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48320.     

Extraction of Zinc with Long-Chain β-Diketones and 4-Acyl-5-pyrazolones

Abstract

The extraction of zinc with long-chain 4-acyl-5-pyrazolones and β-diketones was studied. For comparison with the commercial extractant LIX 54, the extraction parameters were studied for their dependence on pH and on the influence of ammonia and tartrate. Among the examined compounds, 1-phenyl-3-methyl-4-(2-ethylhexanoyl)-5-pyrazolone shows the best extraction results. Zinc as well as nickel and cadmium can be extracted from tartrate solution. The separation of zinc and cadmium is possible. The extraction is disturbed by the presence of complexing agents such as ammonia or cyanide.     

Fabrication and characterization of porous β-tricalcium phosphate scaffolds coated with alginate

All porous materials have a common limitation which is lack of strength due to the porosity. In this study, two different methods have been used to produce porous β-tricalcium phosphate (β-TCP) scaffolds: liquid-nitrogen freeze casting and a combination of the direct-foaming and sacrificial-template methods. Among these two methods, porous β-TCP scaffolds with acceptable pore size and compressive strength and defined pore-channel interconnectivity were successfully fabricated by the combined direct-foaming and sacrificial-template method. The average pore size of the scaffolds was in the range of 100–150 µm and the porosity was around 70%. Coating with 4 wt% alginate on porous β-TCP scaffolds led to higher compressive strength and low porosity. In order to make a chemical link between the β-TCP scaffolds and the alginate coating, silane coupling agent was used. Treated β-TCP scaffold showed improvements in compressive strength of up to 38% compared to the pure β-TCP scaffold and 11% compared to coated β-TCP scaffold.     

Modified ethylene/α-octene co-polymer elastomer composites with sacrificial bonds crosslinking networks and their reinforced mechanical performance

The low tensile strength of ethylene/α-octene co-polymer (POE) limits its application as high-strength materials. In this study, 3-amino-1,2,4-triazole (ATA) was grafted onto maleic anhydride functionalized POE (PM) by melt reaction to obtain side chains capable of forming hydrogen bonding and metal coordination bonding, and then ferric chloride hexahydrate and POE are blended with them to obtain composite materials with high strength and fracture energy. The introduction of iron-based coordination bonding and hydrogen bonding double dynamic crosslinking network endow thermoplastic elastomers with excellent mechanical strength and high toughness. Fourier transform infrared spectroscopy, rheological tests, and X-ray photoelectron spectroscopy reveal the existence of non-covalent crosslinking networks. Based on the strengthening and toughening of non-covalent dynamic crosslinking network, the tensile strength of the modified POE elastomer composites achieves 12.5 MPa along with the elongation at break of 3540%. In addition, the modified POE elastomer composites exhibit improved melt elasticity and thermal stability.     

N-Ethylation of aniline with ethanol or diethyl carbonate over alkali and alkaline zeolites Y and β

Vapour phase ethylation of aniline was carried out over alkali and alkaline earth exchanged zeolites Y and β. Reaction conditions were optimised for N-alkylation by varying reaction parameters like temperature, WHSV, mole ratio and time on stream. Over all zeolites, N-alkylation is much higher than C-alkylation. Diethyl carbonate is a better N-alkylating agent than ethanol. Among the catalysts studied, Kβ is a good N-monoalkylating catalyst with 41% aniline conversion and 100% selectivity at 473 K, WHSV 19.8 h⁻¹ and diethyl carbonate/aniline ratio 2.     

Study on β-cyclodextrin grafting with chitosan and slow release of its inclusion complex with radioactive iodine

β-CD-2-CTS was synthesized by β-cyclodextrin reacting with p-toluenesulfonyl chloride, then grafting with chitosan. The infrared spectra analysis and ¹³C NMR confirmed that β-cyclodextrin reacted with p-toluenesulfonyl chloride at the 2-position carbon atom in the substituted glucose unit of β-cyclodextrin and formed β-CD-2-OTs. In the ¹³C NMR of β-CD-2-OTs, the characteristic peak of the 2-postion carbon atom in the substituted glucose unit of β-cyclodextrin appeared at 78.43 ppm. β-CD-2-CTS was characterized with infrared spectra analysis and X-ray diffraction. In the infrared spectra of β-CD-2-CTS, the characteristic peak of α-pyanyl vibration of β-CD was at 848.6 cm⁻¹. The characteristic peak of β-pyanyl vibration of CTS was at 894.9 cm⁻¹. The X-ray diffraction analysis showed that the peak at 2θ = 20° decreased greatly in β-CD-2-CTS. The polymer inclusion complex of β-CD-2-CTS with iodine was prepared and its inclusion ability was studied. The experimental results showed that a nice bit of iodine was included with β-CD-2-CTS and formed a stable inclusion complex. After the subcutaneous implantation of the polymer inclusion complex of β-CD-2-CTS with ¹³¹I₂ in rats, ¹³¹I₂ exhibited the property of slow release. ¹³¹I₂ in the blood of rats decreased slowly. ¹³¹I₂ in the blood of rats maintained approximately half of maximum for 70 days later, and maintained much higher radioactivity in the organs of rats compared to the inclusion complex of β-CD with ¹³¹ I₂, too. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2414–2421, 2001     

Functional Characteristics of Oleogel Prepared from Sunflower Oil with β-Sitosterol and Stearic Acid

β‐Sitosterol (Sit) and stearic acid (SA) were combined at varying ratios (w/w) and added to sunflower oil (SFO) at the concentration of 20 g/100 g oil for preparing edible fat‐like oleogel. The oleogel was characterized using an optical microscope, Fourier transform infrared spectroscopy (FTIR), X‐ray diffractometer (XRD), differential scanning calorimeter, and texture analyzer. The oil‐binding capacity, melting temperature, and firmness of the oleogel increased with the increase in the amount of SA in the gelator combination (Sit:SA, w/w). The microscopic analysis showed that the gel network formed based on the crystallization and self‐organization of gelator molecules, and both gelators showed an independent crystalline behavior in the oleogel. In addition, the FTIR spectra showed that the gel network formed via physical entanglements and was stabilized by non‐covalent interactions such as hydrogen bonding. Furthermore, XRD diffraction patterns indicated high lateral packing of molecular layers in oleogel prepared with the Sit and SA combination compared with oleogel prepared with a single gelator. On the other hand, for studying the effect of varying concentrations of gelator combinations, the Sit3:SA2 (w/w) combination was added to SFO at concentrations of 10, 15, 20, 25, and 30 g/100 g oil. Specific characteristics such as the oil‐binding capacity and firmness of the oleogel improved as the concentration of the gelator combination (Sit3:SA2) increased from 10 up to 30 g/100 g oil. Therefore, it can be concluded that the saturated fat alternative oleogel can be prepared from SFO with a specific Sit and SA combination ratio and concentration.     

Ternary Cu₂SnS₃ cabbage-like nanostructures: large-scale synthesis and their application in Li-ion batteries with superior reversible capacity

In this paper, novel ternary Cu(2)SnS(3) cabbage-like nanostructures are synthesized on a large scale via a facile solvothermal route. The individual Cu(2)SnS(3) cabbage-like hierarchitecture is constructed from 2D nanosheets with thickness of about 15.6 nm. The Cu(2)SnS(3) electrodes exhibit an initial reversible capacity of 842 mAh g(-1) and still reach 621 mAh g(-1) after 50 cycles. Such an admirable performance could be related to their 3D porous structural features as well as the high electrical conductivity induced by Cu. The electrochemical properties of the 3D hierarchical nanostructures imply its potential application in high energy density Li-ion batteries.     

Trifluoromethyl Dihydrothiazine-Based β-Secretase (BACE1) Inhibitors with Robust Central β-Amyloid Reduction and Minimal Covalent Binding Burden

The β-site amyloid precursor protein cleaving enzyme 1 (BACE1, also known as β-secretase) is a promising target for the treatment of Alzheimer's disease. A pK_a lowering approach over the initial leads was adopted to mitigate hERG inhibition and P-gp efflux, leading to the design of 6-CF₃ dihydrothiazine 8 (N-(3-((4S,6S)-2-amino-4-methyl-6-(trifluoromethyl)-5,6-dihydro-4H-1,3-thiazin-4-yl)-4-fluorophenyl)-5-cyanopicolinamide). Optimization of 8 led to the discovery of 15 (N-(3-((4S,6S)-2-amino-4-methyl-6-(trifluoromethyl)-5,6-dihydro-4H-1,3-thiazin-4-yl)-4-fluorophenyl)-5-(fluoromethoxy)pyrazine-2-carboxamide) with an excellent balance of potency, hERG inhibition, P-gp efflux, and metabolic stability. Oral administration of 8 elicited robust Aβ reduction in dog even at 0.16 mg/kg. Reflecting the reduced hERG inhibitory activity, no QTc prolongation was observed at high doses. The potential for reactive metabolite formation of 15 was realized in a nucleophile trapping assay using [¹⁴C]-KCN in human liver microsomes. Utilizing covalent binding (CVB) in human hepatocytes and the maximum projected human dosage, the daily CVB burden of 15 was calculated to be at an acceptable value of below 1 mg/day. However, hepatotoxicity was observed when 15 was subjected to a two-week tolerance study in dog, which prevented further evaluation of this compound.     

Enhancement of immobilized enzyme activity by pretreatment of β-glucosidase with cellobiose and glucose

In this study, β-glucosidase from Aspergillus niger was pretreated with cellobiose and glucose to prevent loss of enzyme activity, and pretreated β-glucosidase was immobilized on silica gel as a carrier by covalent binding. To enhance the activity of immobilized β-glucosidase, the effects of substrate concentration and reaction conditions, including temperature, time, and agitation speed, were investigated. The optimal concentrations of cellobiose and glucose, temperature, time, and agitation speed were determined to be 0.02 M, 40 °C, 20 min, and 130 rpm, respectively. The activity of immobilized β-glucosidase after pretreatment was increased to about 176% of that of non-pretreated β-glucosidase. In addition, the optimal pH and temperature of the non-pretreated and pretreated immobilized β-glucosidases were both pH 5.5 and 65 °C, respectively. Moreover, the immobilized β-glucosidases were used repeatedly 20 times, and the enzyme activities were maintained at levels higher than 80% of their initial activities.     

An efficient and recyclable thermoregulated phosphine–palladium catalyst for the carbonylative Suzuki coupling of aryl halides with arylboronic acids in water

An efficient protocol has been developed for the carbonylative Suzuki coupling of aryl halides using the thermoregulated phosphine–palladium as a reusable catalyst in pure water. This protocol was applied to a wide variety of hindered and functionalized aryl iodides and bromides with arylboronic acids, to afford the desired biaryl ketones in good to high yields. The palladium catalyst was easily recovered in the aqueous phase and reused up to eight cycles without a significant decrease in its activity.     

Preparation and electrochemical behavior of water-soluble inclusion complex of ferrocene with β-cyclodextrin polymer

A new water-soluble inclusion complex of ferrocene (Fc) with β-cyclodextrin polymer (β-CDP) was prepared by a facile strategy and characterized by ¹H NMR spectroscopy, elemental analysis, powder X-ray diffractometry, thermogravimetry, UV–vis spectroscopy and cyclic voltammetry. Compared with Fc and the inclusion complex of Fc with β-cyclodextrin (Fc-β-CD), the solubility of ferrocene-β-cyclodextrin polymer (Fc-β-CDP) was greatly enhanced due to the water-soluble β-CDP host. The ratio of β-cyclodextrin (β-CD) unit in β-CDP to Fc was determined as 1:1. At 25 °C, the dissociated constant of Fc-β-CDP was measured as 3.65 mM by UV–vis spectroscopy and cyclic voltammetry. The electrochemical properties of Fc-β-CDP in water were studied. The diffusion coefficients of oxidation state and reduction state were calculated as 3.52 × 10⁻⁷ cm² s⁻¹ and 3.93 × 10⁻⁷ cm² s⁻¹. The resulting value of standard rate constant was measured as 1.95 × 10⁻³ cm s⁻¹. The diffusion activation energy was calculated as 21.8 kJ mol⁻¹.