Cooperation of reducing species for NO reduction over Ag/Al2O3 under oxidizing conditions

Summary The cooperation effect of reducing species for selective reduction of NO over Ag/Al₂O₃ has been investigated in the presence of excess oxygen. When the combinations of propene or propane and ethanol or methanol were used as reducing agents, NO reduction took place over a wider temperature range, compared with a single hydrocarbon as reducing agent.     

玻璃载体表面脱氧核糖核酸的固定及其化学发光检测

用硅烷化偶联剂把ＤＮＡ直接共价固定在载玻片表面，将辣根过氧化物酶标记的探针与之进行核酸杂交，杂交后用增强的化学发光检测。方法的检出限为７５ｐｇ。研究了ＤＮＡ分子固定在玻璃载体表面的各种条件，并建立了在玻璃载体表面进行核酸杂交的体系，为研究光纤ＤＮＡ生物传感器打下了基础。     

Modification of the halogen end groups of polystyrene prepared by ATRP

The stabilization modification of the halogen end groups of polystyrene prepared by atom transfer radical polymerization (ATRP) has been attempted. The reaction mechanism adopted is radical chain transfer reaction, and iso-propylbenzene is employed as not only the chain transfer agent but also the solvent. Moreover, Cu⁰ is used as the acceptor of the transformed halogen atom in some experiments. As evidenced by ¹H NMR analysis of the modified products, the halogen end group can really be converted into the much more stable carbon-hydrogen structure. When Cu⁰ is not used, the conversion of the halogen end groups rises rapidly during the early stage and the increase rate slows down after about 8 h reaction. In view of the influence of reaction temperature on the modification, the conversion increases almost exponentially with temperature in the range of 80-100 °C, and the increase rate slows down at higher temperature. ¹H NMR and SEC analyses prove that the modification reaction does not destroy the polymer backbone and the molecular weights remain almost the same as those of the unmodified samples. When Cu⁰ is introduced, the modification reaction proceeds much rapidly, the conversion of the halogen end groups rises almost linearly at the early stage and the nearly complete (>95%) dehalogenation of the polymeric chains is observed after only 12 h reaction. However, the molecular weights rise and the polydispersities become wider after the modification, which implies that the modification is accompanied with the couple termination of the polystyrene radicals besides chain transfer reaction. Furthermore, the couple termination can be restrained at some lower catalyst concentration. Indeed, the modified polymers show improved thermal stability, the initial weight loss temperatures is increased from 196 °C to 378 °C for the linear polystyrene and from 203 °C to 261 °C for the hyperbranched polystyrene.     

LC Determination of Curcumin in Dog Plasma for a Pharmacokinetic Study

A rapid, simple, and sensitive high-performance liquid chromatographic method for quantification of curcumin in dog plasma has been developed and validated. After addition of the internal standard (berberine), plasma was acidified and extracted with ethyl acetate. Analysis was performed on a C₁₈ column. The mobile phase was acetonitrile–5% acetic acid, 52:48 (v/v) and the flow rate 1.0 mL min^?1. The eluent was monitored at 425 nm. Chromatographic separation was achieved in less than 7 min and the calibration plot was linear over the concentration range 2–128 ng mL^?1. Intra- and inter-assay variability were less than 7.3%. The accuracy ranged from 98.7 to 105.0%. The method was successfully applied to a pharmacokinetic study of curcumin in dogs.     

用DCC/DMAP合成N-苄氧羰基氨基酸薄荷酯

以乙腈为溶剂, 用DCC/DMAP偶合法合成了5个N-苄氧羰基氨基酸薄荷酯, 产率90%～94%. 起始原料氨基酸包括: 甘氨酸, DL-蛋氨酸, β-丙氨酸, L-缬氨酸和L-脯氨酸. 给出了目标产物的氢谱、碳谱、红外光谱、质谱、高分辨质谱和元素分析数据.     

Ar n HF van der Waals clusters revisited. I. New low-energy isomeric structures for n=6-13

New low-lying isomeric structures of Ar(n)HF clusters are reported for n=6-13. They were determined using simulated annealing and evolutionary programming, for pairwise additive intermolecular potential energy surfaces. New global minima were found for the clusters with n=7, 10, 11. The new lowest-energy structure of Ar(7)HF and several new local minima for n=6, 7 clusters have the HF bound on a threefold surface site, consistent with the recent spectroscopic data for Ar(n)HF clusters in helium nanodroplets. A new type of low-energy local minima were determined for n=9-13 clusters.     

微孔和介孔材料中的热化学

这篇论文综述了美国加州大学戴维斯分校科学院院士Navrotsky课题组多年来在多孔材料上取得的一系列热化学研究结果。讨论了热化学对微孔、介孔材料的结构稳定性和合成过程的影响。借助多种测热手段对影响骨架结构的热焓、热熵和自由能进行了系统的测量和计算。研究数据表明一系列纯硅分子筛、介孔材料和磷酸铝多孔材料同相应的石英相和块磷铝矿相相比能量上最多只高出15 kJ·mol-1。一系列纯硅分子筛的熵值比石英相高出3.2—4.2 J·K-1·mol-1；在0—12.6 J·K-1·mol-1范围内相对应的自由能几乎没有差别。因此，对不同微孔、介孔材料，其骨架结构在能量上是几乎没有区别的。另外，本文通过介绍一种新型测热方法——原位测热，揭示了分子筛合成过程中的动力学和成核/结晶机理。     

A visible-light activated [2 + 2] cycloaddition reaction enables pinpointing carbon–carbon double bonds in lipids

The precise location of C C bonds in bioactive molecules is critical for a deep understanding of the relationship between their structures and biological roles. However, the traditional ultraviolet light-based approaches exhibited great limitations. Here, we discovered a new type of visible-light activated [2 + 2] cycloaddition of carbonyl with C C bonds. We found that carbonyl in anthraquinone showed great reactivities towards C C bonds in lipids to form oxetanes under the irradiation of visible-light. Combined with tandem mass spectrometry, this site-specific dissociation of oxetane enabled precisely locating the C C bonds in various kinds of monounsaturated and polyunsaturated lipids. The proof-of-concept applicability of this new type of [2 + 2] photocycloaddition was validated in the global identification of unsaturated lipids in a complex human serum sample. 86 monounsaturated and polyunsaturated lipids were identified with definitive positions of C C bonds, including phospholipids and fatty acids even with up to 6 C C bonds. This study provides new insights into both the photocycloaddition reactions and the structural lipidomics.

A new visible-light activated [2 + 2] cycloaddition reaction was discovered and enabled pinpointing carbon–carbon double bonds in lipids.     

A novel catalytic heme cofactor in SfmD with a single thioether bond and a bis-His ligand set revealed by a de novo crystal structural and spectroscopic study

SfmD is a heme-dependent enzyme in the biosynthetic pathway of saframycin A. Here, we present a 1.78 Å resolution de novo crystal structure of SfmD, which unveils a novel heme cofactor attached to the protein with an unusual Hx_nHxxxC motif (n ∼ 38). This heme cofactor is unique in two respects. It contains a single thioether bond in a cysteine–vinyl link with Cys317, and the ferric heme has two axial protein ligands, i.e., His274 and His313. We demonstrated that SfmD heme is catalytically active and can utilize dioxygen and ascorbate for a single-oxygen insertion into 3-methyl-l-tyrosine. Catalytic assays using ascorbate derivatives revealed the functional groups of ascorbate essential to its function as a cosubstrate. Abolishing the thioether linkage through mutation of Cys317 resulted in catalytically inactive SfmD variants. EPR and optical data revealed that the heme center undergoes a substantial conformational change with one axial histidine ligand dissociating from the iron ion in response to substrate 3-methyl-l-tyrosine binding or chemical reduction by a reducing agent, such as the cosubstrate ascorbate. The labile axial ligand was identified as His274 through redox-linked structural determinations. Together, identifying an unusual heme cofactor with a previously unknown heme-binding motif for a monooxygenase activity and the structural similarity of SfmD to the members of the heme-based tryptophan dioxygenase superfamily will broaden understanding of heme chemistry.

The de novo crystal structure of SfmD reveals a novel c-type heme cofactor for promoting a monooxygenation reaction in the biosynthetic pathway of saframycin A.