Phase Diagram of the Quaternary System KCl–MgCl<Subscript>2</Subscript>–NH<Subscript>4</Subscript>Cl–H<Subscript>2</Subscript>O at <Emphasis Type="Italic">t</Emphasis> = 60.00 °C and Their Application

Based on the requirement for the comprehensive exploitation and utilization of the salt lake resources magnesium chloride and potassium chloride, a new technology to produce KCl and ammonium carnallite (NH₄Cl·MgCl₂·6H₂O) by using NH₄Cl as salting-out agent to separate carnallite is proposed. The solubilities of quaternary system KCl–MgCl₂–NH₄Cl–H₂O were measured by the isothermal method at t = 60.00 °C and the corresponding phase diagram was plotted and analyzed. The analysis of this phase diagram shows that there are seven saturation points and eight regions of crystallization. These eight regions of crystallization represent salts corresponding to KCl, NH₄Cl, MgCl₂·6H₂O, (K_1?n (NH₄) _n )Cl, ((NH₄) _n K_1?n )Cl, (K_1?n (NH₄) _n )Cl·MgCl₂·6H₂O, KCl·MgCl₂·6H₂O and NH₄Cl·MgCl₂·6H₂O. According to the phase diagram analysis and calculations, ammonium carnallite (NH₄Cl·MgCl₂·6H₂O) and KCl can be obtained using carnallite as raw materials and ammonium chloride as salting-out agent at t = 60.00 °C. The new technology shows the advantages of being easy to operate and having low energy consumption. The research on this quaternary phase diagram is the foundation for reasonable development of carnallite resources and comprehensive utilization of the salt lake brines.     

Structural requirement of C11b chirality of tetrabenazine analogs as VMAT2 imaging ligands: synthesis and in vivo evaluation

We studied on the structural requirement of C11b chirality of tetrabenazine (TBZ) analogs as vesicular monoamine transporter 2 (VMAT2) ligands. TBZ analogs (2, 6a, 6b) and ¹⁸F-radiolabeled [¹⁸F]6a and [¹⁸F]6b with eliminated C11b chirality were synthesized and characterized. Competition studies demonstrated that 2, 6a and 6b displayed much lower in vivo VMAT2 bindings than TBZ. MicroPET imaging studies of [¹⁸F]6a and [¹⁸F]6b showed negligible accumulation in VMAT2-enriched regions as compared with the known VMAT2 ligand ¹⁸F-FP-(+)-DTBZ. These results suggest that C11b chirality of TBZ analogs is essential for in vivo VMAT2 binding bioactivity.     

Radiolysis products and degradation mechanism studies on di-1-methyl heptyl methyl phosphonate

Di-1-methyl heptyl methyl phosphonate (DMHMP) is a promising alternative extractant for Th-U fuel reprocessing, in which the irradiation stability of extractant should be systematically studied. In this paper, the radiolysis products of DMHMP were analyzed qualitatively and quantitatively with gas and ion chromatograph, the possible radiolysis mechanism of DMHMP was also concluded. Moreover, the effect of structure on the radiolysis products and irradiation stability of neutral organophosphorus compound extractant was also discussed.

     

Progress in fluorene-based wide-bandgap steric semiconductors

Molecular bulks are favorable for the thermal and morphological stability in organic wide-bandgap semiconducting polymers with potential applications in both information and energy electronics. In this review, we present our progress in the design of fluorene-based bulky semiconductors with a fractal four-element pattern. Firstly, we established one-pot methods to spirofluorenes, especially spiro[fluorene-9,9′-xanthene](SFX) serving as the next-generation spiro-based semiconductors. Secondly, we observed the supramolecular forces at the bulky groups and discovered the supramolecular steric hindrance(SSH) effect on polymorphisms, nanocrystals as well as device performance. Thus, a synergistically molecular attractor-repulsor theory(SMART) was proposed for the control of nanocrystal morphology, thin film phase and morphology. Thirdly, the third possible type of defects has been identified to generate green band(g-band) emission in widebandgap semiconductors by the introduction of molecular strain design of cyclofluorene. Finally, the first bulky polydiarylfluorene with highly crystalline and β conformation was achieved by an attractor-repulsor design of tadpole-shape monomer, which offered an effective platform to fabricate stable wide-bandgap semiconducting devices. All the discoveries offer the solid basis to break through bottlenecks of organic/polymer wide-bandgap semiconductors by the improvements of overall performances.     

蒸汽辅助结晶法合成多级孔整体型ZSM-5分子筛

多级孔分子筛由于其高的比表面积、良好的传质性能和可调控的孔径等特性,引起了广大科研工作者的研究兴趣.近年来,通过选择性脱除骨架硅或铝,成功合成了多级孔沸石分子筛材料.但是由于骨架原子的脱除使分子筛的结晶度降低,进而使其催化效率降低.通过硬模板法(如炭黑、介孔硅球、气凝胶等),也用于合成多级孔沸石分子筛.然而,这种方法制备过程较为复杂,且成本较高.因此,亟需发展新的多级孔分子筛的制备方法.此外,在工业应用中,沸石分子筛催化剂通常需要做成整体柱状或片形以消除固定床反应器的床层压降.合成整体型沸石分子筛的传统方法是在沸石分子筛成型过程中添加SiO2和Al2O3等无机粘结剂.虽然该方法简单易行,但沸石分子筛的孔道结构容易被破坏,而且无机粘结剂的存在使分子筛活性中心的密度减少.为了解决这些问题,合成整体型多级孔沸石分子筛,不仅具有较强的机械稳定性,适应于工业,而且其多级孔道有利于分子的扩散,从而具有较高的催化活性.针对上述问题,我们以海绵作为模板,通过蒸汽辅助结晶(steam-assisted crystallization,SAC)方法,制备具有多级孔道的整体型ZSM-5分子筛.通过X射线衍射(XRD)、氮吸附脱附、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、固态核磁共振和氨气的程序升温脱附(NH3-TPD)等手段对分子筛进行了结构与性质表征.XRD和固态核磁共振的结果表明,成功合成了不同Si/Al的ZSM-5分子筛.SEM和TEM结果进一步确定了合成的整体型多级孔ZSM-5分子筛(记作M-ZSM-n,n代表Si/Al的摩尔比),由于分子筛颗粒的堆积形成的介孔,海绵模板提供的固体骨架形成的大孔,分子筛本身的微孔,共同构成了微孔-介孔-大孔的整体型ZSM-5分子筛.透射电子显微镜上配备的X射线能谱仪(EDS)结果表明,分子筛中的Si和Al元素能够均匀的分布.氮吸附脱附证明所得整体型分子筛具有明显的介孔结构.NH3-TPD结果表明,不同Si/Al的整体型多级孔ZSM-5分子筛具有不同强度的酸性,其酸性强度:ZSM-5(60)相似文献   

A Method for Microalgae Proteomics Analysis Based on Modified Filter-Aided Sample Preparation

With the fast development of microalgal biofuel researches, the proteomics studies of microalgae increased quickly. A filter-aided sample preparation (FASP) method is widely used proteomics sample preparation method since 2009. Here, a method of microalgae proteomics analysis based on modified filter-aided sample preparation (mFASP) was described to meet the characteristics of microalgae cells and eliminate the error caused by over-alkylation. Using Chlamydomonas reinhardtii as the model, the prepared sample was tested by standard LC-MS/MS and compared with the previous reports. The results showed mFASP is suitable for most of occasions of microalgae proteomics studies.     

Metal-Chelate Affinity Precipitation with Thermo-Responsive Polymer for Purification of <Emphasis Type="Italic">ε</Emphasis>-Poly-<Emphasis Type="SmallCaps">l</Emphasis>-Lysine

ε-Poly-l-lysine (ε-PL) is a natural preservative for food processing industry. A thermo-responsive polymer, attached with Cu²⁺ or Ni²⁺, was prepared for metal-chelate affinity precipitation for purification of ε-PL. The low critical solution temperatures (LCSTs) of these polymers were close to the room temperature (31.0–35.0 °C). The optimal adsorption conditions were as follows: pH 4.0, 0 mol/L NaCl, ligand density 75.00 μmol/g, and 120 min. The ligand Cu²⁺ showed a stronger affinity interaction with ε-PL and the highest adsorption amount reached 251.93 mg/g polymer. The elution recovery of ε-PL could be 98.42% with 0.50 mol/L imidazole (pH = 8.0) as the eluent. The method could purify ε-PL from fermentation broth and the final product was proved as electrophoretic pure by SDS-PAGE. Moreover, these affinity polymers could be recycled after the purification of ε-PL and the recoveries were above 95.00%.

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Graphical Abstract Scheme for affinity precipitation of ε-PL

     

Comparison of Gasoline-Ranged <Emphasis Type="Italic">n</Emphasis>-Alkanes Conversions Using Dielectric Barrier Discharge: A Kinetic Study

Here, we compared the conversion of gasoline-ranged n-alkanes (C₆–C₉) using dielectric barrier discharge. For an energy density of ~68 J/L and an initial n-alkane concentration of ~230 ppm, when carbon number increased from 6 to 9, the energy efficiency of n-alkane conversion increased from 117 to 240 mmol/kWh, CO _x selectivity decreased from 46 to 20%, and ozone concentration increased from 216 to 240 ppm. The effect of energy density and initial n-alkane concentration were also investigated. The understanding of initial step of conversion was greatly aided by a proposed kinetic model. The pathways of consecutive reactions from the initiation to products were also discussed.     

Research on the Solid State Fermentation of Jerusalem Artichoke Pomace for Producing <Emphasis Type="Italic">R</Emphasis>,<Emphasis Type="Italic">R</Emphasis>-2,3-Butanediol by <Emphasis Type="Italic">Paenibacillus polymyxa</Emphasis> ZJ-9

R,R-2,3-butanediol (R,R-2,3-BD) was produced by Paenibacillus polymyxa ZJ-9, which was capable of utilizing inulin without previous hydrolysis. The Jerusalem artichoke pomace (JAP) derived from the conversion of Jerusalem artichoke powder into inulin extract, which was usually used for biorefinery by submerged fermentation (SMF), was utilized in solid state fermentation (SSF) to produce R,R-2,3-BD. In this study, the fermentation parameters of SSF were optimized and determined in flasks. A novel bioreactor was designed and assembled for the laboratory scale-up of SSF, with a maximum yield of R,R-2,3-BD (67.90 g/kg (JAP)). This result is a 36.3% improvement compared with the flasks. Based on the same bath of Jerusalem artichoke powder, the total output of R,R-2,3-BD increased by 38.8% for the SSF of JAP combined with the SMF of inulin extraction. Overall, the utilization of JAP for R,R-2,3-BD production was beneficial to the comprehensive utilization of Jerusalem artichoke tuber.     

NEW METHOD FOR LOW ORDER SPECTRAL MODEL AND ITS APPLICATION

In order to overcome the deficiency in classical method of low order spectral model, a new method for low order spectral model was advanced. Through calculating the multiple correlation coefficients between combinations of different functions and the recorded data under the least square criterion, the truncated functions which can mostly reflect the studied physical phenomenon were objectively distilled from these data. The new method overcomes the deficiency of artificially selecting the truncated functions in the classical low order spectral model. The new method being applied to study the inter-annual variation of summer atmospheric circulation over Northern Hemisphere, the truncated functions were obtained with the atmospheric circulation data of June 1994 and June 1998. The mechanisms for the two-summer atmospheric circulation variations over Northern Hemisphere were obtained with two-layer quasi-geostrophic baroclinic equation.