Broadband and band-selective IMPRESS-gHMBC: compensation of refocusing inefficiency with synchronized inversion sweep

Compensation of refocusing inefficiency in a gHMBC experiment by replacing the rectangular pi pulse with a pair of adiabatic pulses with synchronized inversion sweep (CRISIS) significantly improves the performance of the gHMBC experiment. The CRISIS-gHMBC experiment retains the pure absorptive shapes in F1 and hence results in better lineshape and higher resolution than the current versions of magnitude mode gHMBC spectra. When used as a broadband experiment, CRISIS-gHMBC, owing to better refocusing efficiency of the adiabatic pulse pairs, gives improved performance across the 13C spectral width. Moreover, it is shown that CRISIS-gHMBC is a robust and improved alternative and when used along with the IMPRESS (Improved Resolution using Symmetrically Shifted pulses) technique further increases the sensitivity and resolution without additional experimental time. The IMPRESS-CRISIS combination is demonstrated for broadband gHMBC and band-selective gHMBC experiments. The ICbs-gHMBC [IMPRESS-CRISIS-band-selective gHMBC] experiment is an attractive and better alternative to individual band-selective gHMBC.     

LLDPE/纳米SiO_2复合材料的力学性能和光学性能研究

采用熔融共混方法制备了LLDPE 纳米SiO2 复合材料 ,并对该体系的力学性能和光学性能进行了系统研究 .结果表明 ,随着纳米SiO2 的加入 ,复合材料的弹性模量显著提高 ,冲击强度与拉伸强度呈峰形变化 ,且均在SiO2 含量为 3phr左右达到最大值 .加入少量的纳米SiO2 后 ,复合材料薄膜对长波红外线 (7～ 1 1 μm)的吸收能力较LLDPE膜有了显著提高 ,透光率略有下降但雾度提高 ,透光质量得到改善 .同时表明 ,纳米SiO2 的表面处理方法对膜的光学性能有显著影响     

Pt/Al2O3蜂窝状催化剂上NO选择性催化还原反应动力学研究

采用多次涂层和浸渍法制备了蜂窝状Pt/Al2O3催化剂，并在高空速和大气体流量条件下对无梯度循环式反应器和积分反应器上催化剂的活性进行了比较。同时采用循环式反应器对动力学数据进行了测定。根据Langmuir-Hinshelwood模型和实验结果，推测了NO-C3H6-O2体系的SCR反应机理，并导出了NO和C3H6反应速率的数学表达式。据此所计算的理论模拟值能够与实验值很好地吻合。实验结果表明，氧气浓度对NO和C3H6的反应速率有明显的影响，二者均随着氧浓度c (O2)的增加达到峰值，再增加氧气浓度时，C3H6的反应速率r(C3H6)保持不变，而NO反应速率r (NO)却下降，而且下降的程度随着温度的升高而加剧。同时，随着氧气浓度增加，r (NO)达到最大值时的温度亦随之下降。     

Li_3PO_4包覆LiMn_2O_4正极材料的结构表征和电化学性能

采用共沉淀法在尖晶石LiMn2O4颗粒表面包覆Li3PO4.XRD、SEM研究结果表明,包覆后的材料仍为尖晶石结构,粒径均匀.电化学性能测试表明,Li3PO4包覆层的存在,减少了正极材料与电解液的直接接触,抑制了高温下电解液对LiMn2O4材料的侵蚀,从而有效改善了高温下材料的循环性能.在40℃时,包覆样品的比容量衰减率都低于未包覆样品,其中包覆1%Li3PO4的样品的初始比容量为110.4mAh/g,50次循环后比容量为84.1mAh/g.     

A NEW KIND OF FIBER-SPUN FROM POLYSULFONAMIDE/ZINC SOLUTION

In this paper, we succeed in fabricating high-temperature fiber of polysulfonamide/ZnO. Polysulfonamide/ZnO nanocomposite was prepared by in-situ polymerization. Some studies and characterization of Polysulfonamide/ Zinc oxide nanocomposite with ZnO 0.5% have been done. It includes ηr,, Crystal degree and thermal property. Experiment＇s results showed that, ZnO as filler can improve crystal degree of polysulfonamide fiber. The crystal degree has been bnproved, from lower than 20% up to 27%. ηr of polysulfonamide/ Zinc oxide nanocomposite solution with ZnO 0.5% is 2.03. The maxinum weight loss of the nanocomposite occurred at 453.5 ℃.     

气相分子吸收光谱法测定地下水中亚硝酸盐氮、氨氮、硝酸盐氮

采用气相分子吸收光谱法测定地下水中的亚硝酸盐氮(NO2^-)、氨氮(NH4^+)、硝酸盐氮(NO3^-)。考察NO2^-,NH4^+和NO3^-测定时的相互干扰,并给出了相应的消除方法。研究结果表明,测定NO2^-时,NH4^+和NO3^-无干扰;NO2^-对测定NH4^+和NO3^-产生干扰,可分别采用分段法和加入2滴10%氨基磺酸溶液的方法消除干扰;对于不含NO2^-或NO2-含量不高的地下水样品,可简化操作步骤直接测定NO3^-。该方法测定结果的相对标准偏差为0.73%~2.74%(n=12),样品加标回收率为97.67%~100.28%。所用检测仪器具有流动注射、自动进样及在线绘制标准曲线的功能,简化了标准方法中的样品前处理过程,减少了样品的损失,实现了自动化分析,大幅提高了检测结果的准确度和工作效率。     

Synthesis and Kinetic Study on the Chromium(III) Complex [Cr(ASA)(en)2]Cl·2H2O

In order to explore the transfer mechanism of chromium(III) in mammals, a novel complex [Cr(ASA)(en)₂]Cl· 2H₂O, bis(ethylenediamine‐ κ ² N,N′)(4‐aminosalicylic acid‐ κ ² O,O′) chromium(III) monochloride dihydrate was synthesized (4‐aminosalicylic acid=H₂ASA, ethylenediamine=en). The crystal structure belongs to orthorhombic system with the space group P2₁2₁2₁ by means of X‐ray diffraction. The characteristic for transfer of Cr³⁺ from the compound to the low‐molecular‐mass chelator EDTA and the iron‐binding protein apoovotransferrin (apoOTf) was followed by UV‐visible (UV‐Vis) and fluorescence spectra in 0.01 mol·L^?1 Hepes at pH 7.4. The second order rate constants were calculated. Those spectra in conjunction were used to obtain more accurate information about the interaction of chromium complex with apoOTf. The experimental results indicate that Cr³⁺ can be transferred from the complex to apoOTf with the retention of the 4‐aminosalicylic acid acting as a synergistic anion.     

Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P_2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P₃ via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

SO_4~(2-)/TiO_2催化合成乙酸戊酯

以Ti(OBu)4为原料,采用溶胶-凝胶法制备了固体超强酸SO24-/TiO2,其结构经XRD,DRS及IR表征。以SO24-/TiO2为催化剂,通过乙酸与戊醇反应合成了乙酸戊酯。讨论了影响酯化率的主要因素。实验结果表明,当催化剂用量为0.6 g,乙酸87.3 mmol,醇酸摩尔比为1.4∶1.0,于115℃反应6 h时,平行实验的平均酯化率可达94.2%。     

Micellar effects of surfactants in cleavage of 4-nitro-phenyl diethyl phosphonate by hydroperoxide anion

We have studied the nucleophilicity of the hydroperoxide anion relative to 4-nitrophenyl diethyl phosphonate (NPDEPS) in the presence of cetyltrimethylammonium bromide (water, 25 °C) while varying the acidity of the medium and the hydroperoxide anion concentration over a broad range. The increase in the reaction rate when the reaction is transferred to a micellar pseudophase is as high as ∼10-fold, which is explained by concentration effects. In CTAB micelles, as in water, the hydroperoxide ion is one of the most effective α-nucleophiles, and the size of the α-effect, characterized by the ratio of the second-order rate constants for reactions of HOO⁻ and OH⁻ anions with NPDEPS, remains practically constant and reaches a value of ∼50-fold. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 357–363, November–December, 2006.