Highly efficient selective hydrogenation of adiponitrile to hexamethylene diamine over barium and melamine formaldehyde resin-modified nickel-cobalt-based zeolitic imidazolate framework-derived catalyst.

In the present study, the catalyst modified with alkaline oxide can enhance the selectivity to primary amines. However, the addition of alkaline oxide inevitably reduces catalytic activity. In this study, NiCo-NC@BaO-MFC catalyst derived from zeolitic imidazolate framework-67, Ba(CH3COO)2, and melamine formaldehyde (MF) resin was prepared and used for the hydrogenation of adiponitrile (ADN) to hexamethylene diamine (HDMA). The carbon layer obtained from the MF resin effectively prevents the interaction between barium (Ba) and the active center, thus improving target product selectivity without decreasing catalytic activity. The results of the density functional theory (DFT) calculation and characterization indicated that the effect of synergy between nickel (Ni) and cobalt (Co) bimetals induces an electron density growth on the Ni surface, bringing the d-band center toward the Fermi surface. Meanwhile, the high electron density of the active center compensates for the electron-deficient state of the carbon atom in -CN, thus improving the catalytic activity. Furthermore, it was found that the introduction of Ba promotes the formation of nucleophilic hydrogen anions, which facilitates the hydrogenation of 6-aminohexylimine (AHIM) to HDMA and inhibits the intramolecular condensation of AHIM, hence improving the selectivity to HDMA. The NiCo-NC@BaO-MFC catalyst gives 98.6 % ADN conversion and 97.2 % selectivity to HDMA in an alkali-free system.

Low-grade sepiolite with low loading of Na/La salts for simultaneous removal of ammonia and phosphate from wastewater.

Efficient treatment of wastewater is of paramount importance for protecting the ecosystem. In this work, we prepared a low-grade sepiolite with low Na/La salt loadings (Na/La-Sep) and employed it for the simultaneous removal of ammonia (N) and phosphate (P) species in the wastewater. The key factors influencing the nutrient removal efficiency of Na/La-Sep, such as the concentration of the La/Na salt solution, the co-existing ion type, and surface zero charges, were investigated. Na/La-Sep exhibits excellent N and P adsorption capability and reduced the N and P concentrations in the spiked and real-world wastewaters to below the allowable N and P discharge limits. Due to the extraordinarily low cost of low-grade sepiolite and the low loading of Na/La salts, Na/La-Sep has a substantially lower cost when compared to other reported clay mineral adsorbents. Furthermore, the N and P removal mechanisms by Na/La-Sep were unraveled by combining the kinetic studies, the molecular dynamics (MD) simulation, and the electron density difference. The present findings might shed light on a new way to develop cost-efficient and high-efficiency adsorbents for alleviating eutrophication and deepen the understanding of N and P removal at a molecular level.

Preparation and application of silver/chitosan-sepiolite materials with antimicrobial activities and low cytotoxicity.

Antimicrobial materials can prevent microbial infection and affect the beauty and structure of interior walls. Herein, a hybrid material silver/chitosan-sepiolite (Ag/5CTs-Sep) with antimicrobial activities was prepared via impregnation. Its antimicrobial properties were investigated via the disk diffusion method. Results showed that the width of inhibition zone of Ag/5CTs-Sep against Staphylococcus aureus (S. aureus), Escherichia coli (E. coli) and Aspergillus niger reached 58.15, 32.95 and 35.18 mm, respectively. The Sep was a suitable carrier for increasing thermal stability and antimicrobial durability, and chitosan improved the dispersion of silver to enhance antimicrobial activities. In addition, characterization indicated that the modification of Sep by CTs can promote the formation of lattice oxygen in Ag/5CTs-Sep, which can induce a high reactive oxygen species (ROS) content, causing the death of microbials. The antifungal mechanism revealed that the death of Aspergillus niger was due to Ag/5CTs-Sep that induced the production of high ROS level and damaged cell membrane. Moreover, Ag/5CTs-Sep possessed low cytotoxicity, and an applied test of the water-based coatings showed that the addition of Ag/5CTs-Sep could both effectively inhibit microorganisms and meet the performance standards for water-based coatings. This work may provide new guidance for the design and application of antibacterial materials.

Preparation of organic-inorganic chitosan@silver/sepiolite composites with high synergistic antibacterial activity and stability.

Organic-inorganic antibacterial materials chitosan@silver/sepiolite (CTs@Ag/Sep) was prepared by grafting organometallic chelate of chitosan and silver on sepiolite. The prepared samples were characterized, and their antibacterial properties were detected. The carrier sepiolite was beneficial for the thermal stability of the composite material. The utilization of silver was enhanced and its amount of usage could be obviously reduced by introduction of nontoxic chitosan which was benefical for the formation of highly dispersed silver nanoparticles on the CTs@Ag/Sep by the interaction between the silver ion and the plentiful amino and hydroxyl groups on the chitosan, thus improved the antibacterial activities and stability. The average width of the inhibition zone of CTs@Ag/Sep against Staphylococcus aureus (S. aureus), Escherichia coli (E. coli) and Aspergillus niger were 51.8, 31.8, and 44.7 mm, respectively. The cytotoxicity of CTs@Ag/Sep was further evaluated with A549 cells, and the results indicated that it exhibited low cytotoxicity to eukaryotic cells.

Selective Cl-Decoration on Nanocrystal Facets of Hematite for High-Efficiency Catalytic Oxidation of Cyclohexane: Identification of the Newly Formed Cl-O as Active Sites.

Understanding the structure-reactivity relationship at the atomic scale is of great theoretical importance for rational design of highly active catalysts, which has long been a central concern in catalysis communities and interface science. Herein, we developed a high-efficiency catalyst for catalytic oxidation of C6H12 by poststructural decoration on well-defined single-crystal facets of hematite. Especially for Cl-decorated {012} facets, the conversion and KA oil selectivity are improved about 3.4 times and 2 times, respectively. A better catalytic performance of the newly formed active site is derived from the charge difference between Cl and the neighboring outmost O atoms, which is affected by the geometric and electronic structures of the original catalyst surface. Based on the experimental results and the theoretical analysis, we concluded that the contribution of various O terminations to Cl-decoration follows the order O(I) > O(III) > O(II). Cl-decorated {001} facets show the highest intrinsic activity, whereas Cl-decorated {012} facets show the best catalytic performance because of their more active sites for Cl-decoration.

Different Crystal Form Titania Supported Ruthenium Nanoparticles for Liquid Phase Hydrodeoxygenation of Guaiacol.

Titania supported Ruthenium-based catalysts were prepared for liquid phase hydrodeoxygenation of guaiacol to cyclohexanol. The catalytic performance is affected by the different crystal forms of titania supports. Anatase and rutile titania supported catalyst 5%Ru/a-r-TiO2 presents higher BET surface area, better dispersion of Ru particles with smaller particle size of 3-4 nm, more acidic centers, and more Ruδ+ located at the boundary between anatase titania and rutile titania. Hence, 5%Ru/a-r-TiO2 gives the best catalytic performance of 95.33% conversion of guaiacol and 79.23% selectivity to cyclohexanol, other products mainly include cyclohexane, benzene, cyclohexanone and 1,2-cyclohexanediol. Based on the results of this work, the possible reaction path for guaiacol hydrodeoxygenation was proposed.

Boosting one-step conversion of cyclohexane to adipic acid by NO2 and VPO composite catalysts.

We demonstrate VPO composites as efficient catalysts for highly selective oxidation of cyclohexane to adipic acid with NO2. In particular, the Ni-Al-VPO composite catalyst exhibits the striking conversion of cyclohexane (60.6%) and exceptionally high selectivity towards adipic acid (85.0%). Moreover, N2O is an environmentally harmful gas, and its yield in the present process is only 0.03 t/t adipic acid, which is far below that obtained using the industrial method (0.3 t/t adipic acid). This work provides a new strategy for the one-step synthesis of dicarboxylic acids from cycloalkanes.

Pressor mechanism evaluation for phytochemical compounds using in silico compound-protein interaction prediction.

In this study, a method was applied to evaluate pressor mechanisms through compound-protein interactions. Our method assumed that the compounds with different pressor mechanisms should bind to different target proteins, and thereby these mechanisms could be differentiated using compound-protein interactions. Twenty-six phytochemical components and 46 tested target proteins related to blood pressure (BP) elevation were collected. Then, in silico compound-protein interactions prediction probabilities were calculated using a random forest model, which have been implemented in a web server, and the credibility was judged using related literature and other methods. Further, a heat map was constructed, it clearly showed different prediction probabilities accompanied with hierarchical clustering analysis results. Followed by a compound-protein interaction network was depicted according to the results, we can see the connectivity layout of phytochemical components with different target proteins within the BP elevation network, which guided the hypothesis generation of poly-pharmacology. Lastly, principal components analysis (PCA) was carried out upon the prediction probabilities, and pressor targets could be divided into three large classes: neurotransmitter receptors, hormones receptors and monoamine oxidases. In addition, steroid glycosides seem to be close to the region of hormone receptors, and a weak difference existed between them. This work explored the possibility for pharmacological or toxicological mechanism classification using compound-protein interactions. Such approaches could also be used to deduce pharmacological or toxicological mechanisms for uncharacterized compounds.

Hyperplane intercept vector calibration method in grey analytical systems.

A novel vector calibration method, hyperplane intercept, is proposed for grey analytical systems to resolve the concentrations of the chemical components from the multi-component data gained from attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. This method is capable of quantifying a particular component known to be present in the mixture without having to know the identity of the rest of the components. Through the target factor analysis (TFA), a section of the IR spectrum of the interested component is chosen to calculate the concentration by the proposed hyperplane intercept method. Results calculated from on-line ATR-FTIR spectroscopy data of cyclohexanone ammoximation process are used to illustrate the simplicity and efficiency of this proposed method.