Postsynthesis of hierarchical core/shell ZSM-5 as an efficient catalyst in ketalation and acetalization reactions

Hierarchical core/shell Zeolite Socony Mobil-five (ZSM-5) zeolite was hydrothermally postsythesized in the solution of NaOH and diammonium surfactant via a dissolution-reassembly strategy. The silica and alumina species were firstly dissolved partially from the bulky ZSM-5 crystals and then were in situ reassembled into the MFI-type nanosheets with the structure-directing effect of diammonium surfactant, attaching to the out-surface of ZSM-5 core crystals. The mesopores thus were generated in both the core and shell part, giving rise to a micropore/mesopore composite material. The micropore volume and the acidity of the resultant hybrid were well-preserved during this in situ recrystallization process. Possessing the multiple mesopores and enlarged external surface area, the core/shell ZSM-5 zeolite exhibited higher activity in the ketalation and acetalization reactions involving bulky molecules in comparison to the pristine ZSM-5.     

Plasmon enhanced upconversion luminescence of NaYF(4):Yb,Er@SiO(2)@Ag core-shell nanocomposites for cell imaging

NaYF(4):Yb,Er@SiO(2)@Ag core-shell nanocomposites were prepared to investigate metal-enhanced upconversion luminescence. Two sizes (15 and 30 nm) of Ag nanoparticles were used. The emission intensity of the upconversion nanocrystals was found to be strongly modulated by the presence of Ag nanoparticles (NPs) on the outer shell layer of the nanocomposites. The extent of modulation depended on the separation distance between Ag NPs and upconversion nanocrystals. The optimum upconversion luminescence enhancement was observed at a separation distance of 10 nm for Ag NPs with two different sizes (15 and 30 nm). A maximum upconversion luminescence enhancement of 14.4-fold was observed when 15 nm Ag nanoparticles were used and 10.8-fold was observed when 30 nm Ag NPs were used. The separation distance dependent emission intensity is ascribed to the competition between energy transfer and enhanced radiative decay rates. The biocompatibility of the nanocomposites was significantly improved by surface modification with DNA. The biological imaging capabilities of these nanocomposites were demonstrated using B16F0 cells.     

Synchrotron radiolysis and mass spectrometry: a new approach to research on the actin cytoskeleton

Hydroxyl radicals generated from millisecond exposure of aqueous solutions to synchrotron X-rays react with proteins to yield stable oxidative modifications of solvent-accessible amino acid side chains. Following proteolysis, HPLC/MS analysis is performed to quantitate the side chain reactivities, and MS/MS analysis is used to identify the modification site(s). Side chain reactivity is shown to be correlated with solvent accessibility; thus the method provides detailed site-specific information about protein structure. The application of these techniques to the study of the actin cytoskeleton is described in detail, including defining the binding sites of monomeric actin with gelsolin segment-1, the actin monomer binding surface on cofilin, the divalent cation-dependent structure changes of monomeric actin, and the conformational changes associated with actin filamentous assembly.     

Pole-placement self-tuning control of nonlinear Hammerstein system and its application to pH process control

By taking advantage of the separation characteristics of nonlinear gain and dynamic sector inside a Hammerstein model, a novel pole placement self tuning control scheme for nonlinear Hammerstein system was put forward based on the linear system pole placement self tuning control algorithm. And the nonlinear Hammerstein system pole placement self tuning control (NL-PP-STC) algorithm was presented in detail. The identification ability of its parameter estimation algorithm of NL-PP-STC was analyzed, which was always identifiable in closed loop. Two particular problems including the selection of poles and the on-line estimation of model parameters, which may be met in applications of NL-PP-STC to real process control, were discussed. The control simulation of a strong nonlinear pH neutralization process was carried out and good control performance was achieved.     

Vacuum residue coking process simulation using molecular-level kinetic model coupled with vapor-liquid phase separation

In this work,a molecular-level kinetic model was built to simulate the vacuum residue (VR) coking pro-cess in a semi-batch laboratory-scale reaction kettle.A series of reaction rules for heavy oil coking were summarized and formulated based on the free radical reaction mechanism.Then,a large-scale molecular-level reaction network was automatically generated by applying the reaction rules on the vacuum residue molecules.In order to accurately describe the physical change of each molecule in the reactor,we cou-pled the molecular-level kinetic model with a vapor-liquid phase separation model.The vapor-liquid phase separation model adopted the Peng-Robinson equation of state to calculate vapor-liquid equilib-rium.A separation efficiency coefficient was introduced to represent the mass transfer during the phase separation.We used six sets of experimental data under various reaction conditions to regress the model parameters.The tuned model showed that there was an excellent agreement between the calculated val-ues and experimental data.Moreover,we investigated the effect of reaction temperature and reaction time on the product yields.After a comprehensive evaluation of the reaction temperature and reaction time,the optimal reaction condition for the vacuum residue coking was also obtained.     

Electrodeposited iodide ions imprinted polypyrrole@bismuth oxyiodide film for an electrochemically switched renewable extractor towards iodide ions

Effective extraction and regeneration of radioactive iodide is one of urgent concerns for the safe utilization of nuclear energy. As a novel environmentally benign ion separation technique, electrochemically switched ion extraction(ESIE) process can be applied for effective capture and recovery of iodide ions(I^-). Herein, a novel kelp seaweed-like core/shell I^-imprinted polypyrrole@bismuth oxyiodide(PPy/I^-@BiOI) composite film is successfully prepared for the sel...     

Facile synthesis of metal-organic frameworks embedded in interconnected macroporous polymer as a dual acid-base bifunctional catalyst for efficient conversion of cellulose to 5-hydroxymethylfurfural

5-Hydroxymethylfurfural (5-HMF), as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels, has been attracted extensive attention. In this research, using Pickering high internal phase emulsions (Pickering HIPEs) as template and functional metal-organic frameworks (MOFs, UiO-66-SO₃H and UiO-66-NH₂)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process, which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF. The effects of the emulsion parameters including the amount of surfactant (ranging from 0.5% to 2.0% (mass)), the internal phase volume fraction (ranging from 75% to 90%) and the acid/base Pickering particles mass ratio (ranging from 0:6 to 6:0) on the morphology and catalytic performance of solid catalyst were systematically researched. The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion, and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield. The highest 5-HMF yield, about 40.5%, can be obtained by using polymer/MOFs composite as catalyst (Poly-P12, the pore size of (53.3 ±11.3) μm, the acid density of 1.99 mmol·g^-1 and the base density of 1.13 mol·g^-1) under the optimal reaction conditions (130 ℃, 3 h). Herein, the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method, which provided a favorable experimental basis and theoretical reference for achieving efficient production of high added-value product from abundant biomass.     

Research on nodular iron joint welded with nickel-iron electrode by the moire fringe method

Nickel-iron type cast iron electrodes are widely used for weldingQT600-3 nodular iron.Nevertheless,the research work has demonstrated thatthe strength of these heterogeneous welded joints is low.In this paper,the uni-axial tension of the joints is studied by the Moire fringe method,and the dis-placement,strain and stress in the total fields are obtaind.Based on the unevendistribution of strain and stress,the reason of crack initiation and propagation isdiscussed.Through examining the appearance of the fracture by scanning elec-tron microscope,a lot of spherical substances distributed on the fracture surfaceare found,which may be another reason leading to cracking of the welded jointunder the lower tensile stress.These new findings will help to improve theproperties of nickel-iron type cast iron electrodes and the strength of the weldedjoint.     

Resolution and chemical formula identification of aromatic hydrocarbons and aromatic compounds containing sulfur, nitrogen, or oxygen in petroleum distillates and refinery streams

An all-glass heated inlet system has been interfaced to a dual-trap Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The inlet vaporizes a mixture of species of widely different boiling points, and the interface maintains a large (factor of 10(10)) pressure gradient between the inlet and the mass spectrometer, making possible the analysis of petroleum distillates and refinery streams at very high mass resolution. Ions generated by low-energy electron ionization in the source trap of the spectrometer are transferred to the analyzer trap, where the pressure is at least 2 orders of magnitude lower. Singly-charged ions from a mass window of ～20 u are isolated by stored-waveform radial ejection, to reduce space charge and increase digital resolution: routine mass resolving power >200?000 (based on magnitude-mode peak full width at half-height) is thereby achieved throughout the full mass window. The mass window may be incremented stepwise to cover the full mass range of several hundred units. The FT-ICR mass spectrum of a gas oil aromatic neutral fraction contained peaks resulting from the resolution of ions having 358 distinct formulas over a mass range of ～42 u. C(3)/SH(4), (13)C/CH, (13)CH/N, CH(2)/N, and other mass doublets were baseline-resolved, yielding typical mass measurement inaccuracies of ～1 ppm. For example, (13)C(12)C(17)H(20)S(+) and C(21)H(17)(+), which differ by only 0.0011 u at ～269 u, were clearly resolved. A 40?000 resolving power low-voltage spectrum of the aromatic neutrals, acquired by use of a Kratos MS-50 double-focusing instrument, was processed with a computer-based deisotoping/formula assignment procedure. The algorithm of the program is outlined and illustrated. Remarkably good agreement exists between the FT-ICR and MS-50 results. However, instrumental rather than indirect resolution of ions clearly enhances analytical accuracy and significantly reduces data-processing time. Thus, we have demonstrated that FT-ICR is the mass analysis of choice for differentiating hydrocarbons from heteroatom-containing compounds in petroleum distillates and refinery streams.