Mg改性对Co/γ-Al2O3-TiO2催化燃烧丙烷性能影响

采用分步浸渍法制备了系列Mg改性的Co/γ-Al_2O_3-TiO_2催化剂,通过X射线衍射(XRD)、紫外可见漫反射光谱(DR-UV-vis)、N_2吸附-脱附(BET)、X射线光电子能谱(XPS)和H_2程序升温还原(H_2-TPR)等技术对催化剂进行表征,并考察了其对丙烷燃烧的催化性能。结果表明,Co在原始γ-Al_2O_3-TiO_2载体和Mg改性MgO/γ-Al_2O_3-TiO_2载体上均以Co_3O_4的形式存在;Mg掺入后与Al_2O_3作用形成MgAl_2O_4尖晶石,改善了载体的织构性质,提升了Co_3O_4在催化剂载体表面的暴露数量和分散程度。此外,MgAl_2O_4与Co_3O_4相互作用提升了Co_3O_4颗粒表面Co~(3+)/Co~(2+)和O_(ads)/O_(latt)的比例,并削弱了Co-O键键能,从而提升了其对丙烷的催化燃烧活性。当Mg负载量为15%(质量分数)时,在Co/MgO(15%)/γ-Al_2O_3-TiO_2催化剂上进行丙烷燃烧,丙烷90%转化率的温度比无Mg掺杂的Co/γ-Al_2O_3-TiO_2催化剂的降低了45℃,并且连续反应40 h其活性保持稳定。     

邻苯二胺合钴氧合反应的研究Ⅰ 水溶液中配合物及其氧合配合物稳定常数的测定

自１９３８年Tsumaki报道犤１犦氧载体以来，这方面的研究已有很大进展犤２犦，只是理论研究居多。氧载体的氧合常数是氧载体研究中的一个重要参数，它的测定是氧载体研究中的一项重要内容，用pH电位法测定氧载体的氧合常数已有研究报道犤２～４犦，作者在研究中发现，邻苯二胺合钴（o－Phdn－Co）配合物在固相和水溶液中与O２反应时表现出很大差异，其反应产物的组成比分别为液相配合物Co∶O２＝２∶１，而固相配合物Co∶O２＝１∶２，为究其成因和进行理论探讨，有必要先测定其氧合常数。由于o－Phdn－Co配合物的配位常数也未见文献…     

Systematic investigation of the hydrothermal syntheses of Pr(III)-PDA (PDA = pyridine-2,6-dicarboxylate anion) metal-organic frameworks

A series of novel two-dimensional (2D) and three-dimensional (3D) praseodymium coordination polymers, namely, {[Pr3(PDA)4(HPDA)(H2O)8] x 8H2O}n (2), {[Pr2(PDA)3(H2O)3] x H2O}n (3), {[Pr(PDA)(H2O)4] x ClO4}n (4), and { [Pr2(PDA)2(H2O)5SO4] x 2H2O}n (5) (PDA = pyridine-2,6-dicarboxylic anion), was designed and synthesized under hydrothermal conditions. Complexes 1-3 (chainlike polymer, {[Pr(PDA)(HPDA)(H2O)2] x 4H2O}n (1) was also obtained independently by us, although it has been reported recently by Ghosh et al.) were fabricated successfully by simply tuning the Pr/PDA ratio and exhibited various and intriguing topological structures from a 1D chain to a 3D network. While the synthetic strategy of 5 was triggered and further performed only after 1 was structurally characterized. The complexes were characterized by X-ray single-crystal determination, spectroscopic, and variable-temperature magnetic susceptibility analyses. In complex 2 an unusual nanosized square motif as a building block constructed by eight Pr ions was further assembled into a highly ordered 2D grid compound. In complex 3 the decanuclear Pr metal-based structure as a repeat unit interpenetrated to form a novel 3D polymer. Complex 4 was a 3D network polymer fabricated through a hexanuclear Pr ring as a building block, and ClO4- anions as guests were trapped in the cavity. In complex 5 six Pr atoms, two SO4(2-) anions, and carboxylic oxygen bridges constructed an intriguing rectangle structure as a repeat unit in the grid to form a 2D coordination polymer in which the unique bi-bidentate coordination mode of SO4(2-) anion was observed.     

Effect of humidity on the adsorption kinetics of lung surfactant at air-water interfaces

The in vitro adsorption kinetics of lung surfactant at air-water interfaces is affected by both the composition of the surfactant preparations and the conditions under which the assessment is conducted. Relevant experimental conditions are surfactant concentration, temperature, subphase pH, electrolyte concentration, humidity, and gas composition of the atmosphere exposed to the interface. The effect of humidity on the adsorption kinetics of a therapeutic lung surfactant preparation, bovine lipid extract surfactant (BLES), was studied by measuring the dynamic surface tension (DST). Axisymmetric drop shape analysis (ADSA) was used in conjunction with three different experimental methodologies, i.e., captive bubble (CB), pendant drop (PD), and constrained sessile drop (CSD), to measure the DST. The experimental results obtained from these three methodologies show that for 100% relative humidity (RH) at 37 degrees C the rate of adsorption of BLES at an air-water interface is substantially slower than for low humidity. It is also found that there is a difference in the rate of surface tension decrease measured from the PD and CB/CSD methods. These experimental results agree well with an adsorption model that considers the combined effects of entropic force, electrostatic interaction, and gravity. These findings have implications for the development and evaluation of new formulations for surfactant replacement therapy.     

Polyketide chain length control by chain length factor

Bacterial aromatic polyketides are pharmacologically important natural products. A critical parameter that dictates product structure is the carbon chain length of the polyketide backbone. Systematic manipulation of polyketide chain length represents a major unmet challenge in natural product biosynthesis. Polyketide chain elongation is catalyzed by a heterodimeric ketosynthase. In contrast to homodimeric ketosynthases found in fatty acid synthases, the active site cysteine is absent from the one subunit of this heterodimer. The precise role of this catalytically silent subunit has been debated over the past decade. We demonstrate here that this subunit is the primary determinant of polyketide chain length, thereby validating its designation as chain length factor. Using structure-based mutagenesis, we identified key residues in the chain length factor that could be manipulated to convert an octaketide synthase into a decaketide synthase and vice versa. These results should lead to novel strategies for the engineered biosynthesis of hitherto unidentified polyketide scaffolds.     

甲壳胺接枝聚合反应的研究

本文是以过硫酸钾为引发剂，研究甲基丙烯酸甲酯（ＭＭＡ）与甲壳胺的接枝聚合反应．通过对不同脱乙酰度（ｄａ）甲壳胺（ＣＴＳ）的接枝聚合反应条件实验，研究了反应时间，温度，引发剂浓度和单体浓度对接枝聚合反应的影响，从中得到优选的反应条件．在相同条件下，比较不同脱乙酰度甲壳胺及Ｎ－取代甲壳胺的接枝聚合反应结果，表明：甲壳胺中氨基参与了接枝聚合反应的引发过程．     

密胺-脲甲醛树脂合成工艺放大研究

以密胺－脲甲醛树脂合成的小试工艺条件为依据，完成了放大试验过程的工艺研究。研究结果与小试研究的工艺条件相吻合。     

A modification to an enzymatic method for the preparation of (α-32P) ATP with a high specific activity

A modification of the procedure reported byJohnson andWalseth ¹ for the preparation of (-³²P)ATP:(-³²P)GTP with a specific activity of more than 5000 Ci/mmol was made firstly, then it was used as the phosphate donor in the reaction catalyzed by the polynucleotide kinase, to transfer its radioactive phosphate to the 5-position of the 3-AMP, resulting (5-³²P)3-ADP. After that, (5-³²P)3-ADP was hydrolysed to (5-³²P)AMP under the catalysis of Nuclease P1, the late was then phosphorylated to produce (-³²P)ATP by the action of myokinase and pyruvate kinase. By this method, we firstly prepared (-³²P)ATP with a specific activity of more than 4000 Ci/mmol which was measured by HPLC analysis.     

Synthesis and Second‐Order Nonlinearities of Chiral Prolinol‐Substituted Chromophores

A new series of thiophene‐ and furan‐containing chromophores with a chiral prolinol donor and a sulfone acceptor has been synthesized. The UV‐vis absorptions, second‐order nonlinear optical properties, and X‐ray crystal structures are described.     

Design,Synthesis, and Characterization of Photolabeling Probes for the Study of the Mechanisms of the Antiviral Effects of Ribavirin

Ribavirin, the only small molecule available so far for treating hepatitis‐C‐virus infection, was recently used in an emergency context to treat patients with severe acute respiratory syndrome (SARS) in the early stages of the disease. To study the mechanisms responsible for the antiviral effects of ribavirin by using a photolabeling approach, we designed, synthesized, and characterized the azidotriazole nucleosides 1 and 2 as photolabeling probes of ribavirin. These probes were synthesized either by performing nucleophilic substitution of the corresponding bromotriazole nucleoside with NaN₃ (Scheme 2) or by directly coupling the azidotriazole with the protected ribose sugar (Scheme 4). The azidotriazole nucleosides 1 and 2 showed a fast, clear‐cut photochemical reaction, which suggests that they are promising candidates for use in photolabeling studies.