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71.
A new germanosilicate zeolite named SCM-15 (Sinopec Composite Material No. 15), the first zeolite containing a 3-dimensional (3D) channel system with interconnected 12-, 12-, and 10-ring channels (pore sizes: 6.1×7.2, 6.1×7.4, and 5.2×5.9 Å), has been synthesized using neutral 4-pyrrolidinopyridine as organic structure-directing agents (OSDAs). Its structure has been determined by combining single-crystal electron diffraction (SCED) and synchrotron powder X-ray diffraction (SPXD) data. The unique open framework structure of SCM-15 is related to that of FOS-5 ( BEC ), ITQ-7 ( ISV ), PKU-16 ( POS ), ITQ-26 ( IWS ), ITQ-21, Beta polymorph B, and SU-78B, since all these framework structures can be constructed from similar chains which are connected through shared 4-ring or double 4-ring (d4r) units. Based on this relation, six topologically reasonable 3D large or extra-large pore hypothetical zeolites are predicted.  相似文献   
72.
The complex of diethylenetriaminepentaacetate (DTPA) with the paramagnetic gadolinium ion [Gd(III)] is a well-known blood pool contrast agent for magnetic resonance imaging (MRI). To obtain MRI pictures from other anatomical structures, for instance from tissues containing cells with phagocytic activity, larger colloidal complexes have to be constructed. Therefore, in view of modifying the physiological behaviour, the DTPA chelate was first hydrophobized by covalently linking it to phosphatidylethanolamine (PE), and the resulting conjugate was then incorporated into nanometre-sized, sonicated phospholipid vesicles. Qualitative information on the affinity of the PE–DTPA derivative for Gd(III) ions was derived from competition experiments using the dye Arsenazo. Furthermore, it was found that only the membranotropic adducts residing in the outer shell of the vesicle bilayer are accessible to the lanthanide ion. The vesicular particulate was also used as a vehicle to transport PE–DTPA into the coating of so-called magnetoliposomes which consist of nanometre-sized iron oxide cores onto which a phospholipid bilayer is strongly chemisorbed. After loading the resulting structures with Gd(III), this new type of magnetoliposome may offer unique potentialities as a novel bi-label MRI contrast medium.  相似文献   
73.
A series of Mn(II) aminophosphonate complexes were successfully synthesized and intercalated into the hydroxy double salt [Zn5(OH)8]Cl2·yH2O. Complex incorporation led to an increase in the interlayer spacing from 7.8 to 10–12 Å. Infrared spectroscopy showed the presence of the characteristic vibration peaks of the Mn(II) complexes in the intercalates' spectra, indicating successful incorporation. The complex-loaded composites had somewhat lower proton relaxivities than the pure complexes. Nevertheless, these intercalates may have use as MRI contrast agents for patients with poor kidney function, where traditional Gd(III)-based contrast agents cause severe renal failure.  相似文献   
74.
In this article, we report the radical polymerization in the presence of peroxide and commercially available or designed reducing agent monomer (RAM) for the preparation of branched poly(methyl methacrylate)s (PMMAs). The reaction behavior of the RAM was studied by NMR. Triple‐detection SEC (TD‐SEC) analysis was used to confirm the branching structure of the prepared PMMAs and to investigate the influence of peroxide concentration and RAM concentration on molecular weight and branched structure. The obtained branched PMMAs exhibited high molecular weights and relatively narrow polydispersities at high conversion of MMA. Interestingly, a significant increase in molecular weight and degree of branching of the obtained polymers are observed in higher BPO concentration, these results are quite different from that reported in the literature. The unique radical polymerization mechanism in the RAM/BPO redox‐initiated radical polymerization system resulted in branched PMMAs with high molecular weights at relatively high RAM and BPO concentrations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 833–840  相似文献   
75.
A simple method for nanocrystalline cellulose (NCC)/fluorinated polyacrylate was developed by RAFT‐mediated surfactant‐free emulsion polymerization, in which the nanocomposites formed a core‐shell spherical morphology. The influence of the content of NCC‐g‐(PAA‐b‐PHFBA) (AA was acrylic acid, HFBA was hexafluorobutyl acrylate) on the properties of latex and film were systematically studied. The monomer conversion, the tensile strength, and water–oil repellency of film increased first and then decreased, the latex particle size decreased first and then decreased, when the content of NCC‐g‐(PAA‐b‐PHFBA) increased from 1 to 6 wt %. Elongation at break and thermal stability distinctly decreased when the content of NCC‐g‐(PAA‐b‐PHFBA) gradually increased. XPS showed that the fluorine‐containing groups well concentrated at the film–air interfaces during the annealing process. SEM analysis revealed that the treated fiber had a rugged surface, and the treated fabric had an excellent water repellency. In addition, this green grafting method in water offered a new perspective for the fabrication of exceptional NCC‐based nanocomposites with NCC as the core and also helped to promote the potential applicability of NCC in a range of multipurpose applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1305–1314  相似文献   
76.
As the spacer length in 1,2-dimethylimidazolium-based dications increases beyond a specific point (six methylene units), they fail in structure-directing towards STW zeolites in any synthetic conditions. These dications can instead produce, under fluoride concentrated conditions, either *BEA [in the case of the eight-methylene-unit structure-directing agent (SDA)] or MWW (ten methylene units) zeolites. For any length of the dication, the default zeolite (MTW) is a relatively dense zeolite containing a unidimensional channel, whereas the zeolite demanding most specificity (STW, *BEA or MWW) is more porous, affording a larger concentration of the dication to be occluded. This work provides the first reported fluoride synthesis of pure silica MWW zeolites. Charge balance of the organic dications in this zeolite was achieved by combining “structural” silanolates, regular “connectivity defects” and occluded fluoride. Molecular mechanics calculations showed a perfect fit of the decamethylenebis(dimethylimidazolium) dication in the sinusoidal intralayer pore system of MWW. The calculations showed also that the dication is able to stabilize the interlayer space without disturbing the hydrogen-bonding system that holds the layers together in the as-made material. The 19F magic-angle spinning (MAS) NMR presented two distinct resonances at −71 and −83 ppm, which, on the basis of DFT calculations, we tentatively assigned to fluoride occluded in [4662] and [415262] cages of the MWW structure, respectively. The same DFT study determines a different chemical shift of one methyl 13C nuclear magnetic resonance according to the imidazolium ring residing in the sinusoidal channels or in the large cup cavities, thus explaining an experimentally observed splitting of that resonance.  相似文献   
77.
In this work, a series of novel shape memory liquid crystalline (LC) epoxides with lateral substituent were prepared and characterized. Dynamic mechanical analysis (DMA) and shape memory testing were used to investigate on the thermo-mechanical properties and shape memory effects of prepared samples. The results showed that the modulus in the rubbery region (ER ) decreased as the length of lateral alkyl group increases. And more than 95% of the deformation can be fixed as the sample was cooled down below the glass transition temperature (Tg), which was determined by differential scanning calorimetry (DSC) measurement, and can be recovered completely as heating. Effects of the curing agent and substituent on the shape memory behavior were also studied. We found that LC epoxides cured by aromatic diamine have a higher recovery speed. The recovering speeds of the shape memory decreased as the length of lateral alkyl group inscreased. The local ordered structures and the lateral substituent played an important role in shape memory effects.  相似文献   
78.
A series of new sterically modulated chlorocoumarin‐substituted (benz)imidazolium salts and their bis‐N‐heterocyclic carbene silver(I) complexes were prepared and characterized. The complexes were prepared in good yields following the in situ deprotonation method by treating azolium salts with silver(I) oxide in the dark. All the compounds were characterized using various spectroscopic and analytical methods. Additionally, one of the benzimidazolium salts was characterized using single‐crystal X‐ray diffraction technique. In this salt, intermolecular π–π stacking interactions operate between benzimidazole as well as coumarin heterocyclic systems with adjacent molecules. In the preliminary antibacterial studies, the silver complexes were found more active than the corresponding salts against a panel of bacterial strains. Interestingly, the complexes displayed improved antibacterial efficacy against Escherichia coli strain, comparable with that of the standard drug ampicillin.  相似文献   
79.
Abstract

A method of Fourier transform near-infrared (FT-NIR) spectroscopy combined with partial least squares (PLS) model was successfully applied to investigate the hydrolysis kinetics of four kinds of silane coupling agents (phenyltriethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltriethoxysilane) in an acid-catalyzed EtOH system. The fast scanning speed and high sensitivity of the FT-NIR spectroscopy, and the powerful data processing ability of the PLS, enabled the method to quantitatively and accurately catch the fast changing H2O concentration during the hydrolysis processes without delay, realizing the study of the fast-paced hydrolysis reactions of the silane coupling agents. The results showed that electrophilic substitution occurred in the hydrolysis reactions, which followed second-order reactions and greatly depend on the catalyst concentration and reaction temperature. The hydrolysis rate constants, activation energy, and Arrhenius Frequency factors were gained. In conclusion, the FT-NIR PLS model is a powerful tool for hydrolysis kinetics researching of the silane coupling agents.  相似文献   
80.
In this work, a novel nucleating agent (NA) based on substituted‐aryl phosphate salts was introduced into poly(L‐Lactide) (PLLA). The nonisothermal and isothermal crystallization behaviors of nucleated PLLA samples were investigated through differential scanning calorimetry (DSC), wide angle X‐ray diffraction, and polarized optical microscope (POM). Furthermore, the effect of annealing treatment on the cold crystallization behaviors of nucleated samples was also investigated. The results show that the crystallization of PLLA, whether for the melt crystallization (including nonisothermal and isothermal crystallization process) or for the cold crystallization (including the cold crystallization occurring during the DSC heating process and during the annealing process), is greatly dependent upon the content of NA. At relatively lower NA content (≤0.1 wt%), the nucleation effect of NA is inconspicuous, however, at higher NA content (≥0.2 wt%), it exhibits great nucleation effect for the crystallization of PLLA. Further results show that the double endothermic peak of PLLA depends on the temperature applied for the crystallization. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   
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