Isolation and absolute configuration determination of aliphatic sulfates as the Daphnia kairomones inducing morphological defense of a phytoplankton

2,6-Dimethylheptyl sulfate (1) and 6-methyloctyl sulfate (3) were isolated from Daphnia pulex as the Daphnia kairomones that induced morphological defense of a freshwater phytoplankton Scenedesmus gutwinskii var. heterospina (NIES-802). The absolute stereochemistry at C2 of 1 was determined by (1)H-NMR analysis of the (R)-MTPA ester of alcohol 2. The absolute configuration at C6 of 3 was determined by Ohrui's method applied to alcohol 4.     

Time-bandwidth problem in room temperature slow light

For many applications of slow or stopped light, the delay-time-bandwidth product is a fundamental issue. So far, however, slow-light demonstrations do not show a large delay-time-bandwidth product, especially in room temperature solids. Here we demonstrate that the use of artificial inhomogeneous broadening has the potential to solve this problem. A proof-of-principle experiment is done using slow light produced by two-beam coupling in a photorefractive crystal Ce:BaTiO3 where Bragg selection is used to provide the artificial inhomogeneity. Examples of how to generalize this concept for use with other room temperature slow-light solids are also given.     

Intercalation of cobaltammine complex ions into layered manganese oxide

The intercalation of Co(2+), [Co(NH(3))(6)](3+), and [Co(NH(3))(5)Cl](2+) ions into layered manganese oxide (birnessite) was studied by chemical, XRD, SEM, IR, and DTA-TG analyses. The intercalation reaction progressed by a 2:1 or 3:1 ion-exchange mechanism depending on the valence of the starting ions. The oxidation state of cobalt did not change with the intercalation reaction. The intercalation of [Co(NH(3))(6)](3+) ions resulted in an increase of basal spacing from 0.716 to 0.956 nm, giving a layered structure material consisting mainly of platelike particles. The chemical analysis results showed that the structure of [Co(NH(3))(6)](3+) ions was maintained in the interlayer. On the other hand, an H(2)O/NH(3) ligand exchange reaction progressed for the intercalation of [Co(NH(3))(5)Cl](2+) ions, resulting in an increase in the basal spacing from 0.716 to 0.956 nm.     

ESR study of linear aliphatic oligoesters under γ-irradiation. I. Paramagnetic species produced in the material by irradiation at 77°K

Paramagnetic species produced in a series of linear aliphatic oligoesters $ [\bond;{\rm O}\bond;({\rm CH}_{\rm 2} {\rm )}_m\bond;{\rm O}\bond;{\rm CO}\bond;({\rm CH}_{\rm 2} {\rm )}_n\bond;{\rm CO\rlap{--} ]}_P $ by γ-irradiation at 77°K was investigated by an ESR method. A predominant doublet observed immediately after γ-irradiation, which has hyperfine splitting of 20–23 gauss, is attributed to a radical anion III. Slight decay of this radical anion is observed by illuminating the sample with visible light at 77°K. A small amount of the radical anion is converted to double triplet, which is assigned to ? (ES)? CH? CH₂? (where ES denotes the ester group), from the result of heat treatment. The conformational angles for the two β-protons in the (6,2) oligoester are determined to be θ₁ = θ₂ = 30°.     

In situ STM imaging and direct electrochemistry of Pyrococcus furiosus ferredoxin assembled on thiolate-modified Au111 surfaces

We have addressed here electron transfer (ET) of Pyrococcus furiosus ferredoxin (PfFd, 7.5 kDa) in both homogeneous solution using edge plane graphite (EPG) electrodes and in the adsorbed state by electrochemistry on surface-modified single-crystal Au111 electrodes, This has been supported by surface microscopic structures of PfFd monolayers, as revealed by scanning tunneling microscopy under potential control (in situ STM). Direct ET between PfFd in phosphate buffer solution, pH 7.9, and EPG electrodes is observed in the presence of promoters. Neomycin gives rise to a pair of redox peaks with a formal potential of ca -430 mV (vs SCE), corresponding to [3Fe-4S]1+/0. The presence of an additional promoter, which can be propionic acid, alanine, or cysteine, induces a second pair of redox peaks at approximately -900 mV (vs SCE) arising from [3Fe-4S]0/1-. A robust neomycin-PfFd complex was detected by mass spectrometry. The results clearly favor an ET mechanism in which the promoting effect of small organic molecules is through formation of promoter-protein complexes. The interaction of PfFd with small organic molecules in homogeneous solution offers clues to confine the protein on the electrode surface modified by the same functional group monolayer and to address diffusionless direct electrochemistry, as well as surface microstructures of the protein monolayer. PfFd molecules were found to assemble on either mercaptopropionic acid (MPA) or cysteine-modified Au111 surfaces in stable monolayers or submonolayers. Highly ordered (2 radical 3 x 5)R30 degrees cluster structures with six MPA molecules in each cluster were found by in situ STM. Individual PfFd molecules on the MPA layer are well resolved by in situ STM. Under Ar protection reversible cyclic voltammograms were obtained on PfFd-MPA/Au111 and PfFd-cysteine/Au111 electrodes with redox potentials of -220 and -201 mV (vs SCE), respectively, corresponding to the [Fe3S4]1+/0 couple. These values are shifted positively by 200 mV relative to homogeneous solution due to interactions between the promoting layers and the protein molecules. Possible mechanisms for such interactions and their ET patterns are discussed.     

Unprecedented Encapsulation of Carbonyl Guest with Designer Lewis Acid Receptor

A reaction chamber is formed by a cage compound in which a dicarbonyl guest molecule is encapsulated by two bowl-shaped aluminum tris(2,6-diphenylphenoxide) molecules through Lewis acid–base interactions (structure of complex with 1,4-dimethylpiperazine-2,5-dione depicted). The carbonyl compound held inside the molecular capsule is effectively protected against the approach of external nucleophiles. On the other hand, the chamber is large enough to allow Diels–Alder cycloadditions to take place under mild conditions and with high selectivity.     

一类时变非线性振动系统的同步控制方法

对于一类非自治的非线性振动系统，设计了控制方法并建立了相应的派生系统，使得派生系统能与原系统达到同步.利用Lyapunov稳定性理论证明了两个系统在一定条件下可以达到同步，给出了耦合参数的选择条件.对于含参数激励与强迫激励的Mathieu方程以及拟周期激励的Duffing方程进行了实际的仿真计算，证明了派生系统可以与原系统的拟周期、混沌运动快速实现同步. 关键词： 派生系统 同步 差别方程     

MCM-41分子筛的改性、表面结构与吸附性质的研究

用三甲基氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、四氯化硅与甲基碘改性高硅MCM-41中孔分子筛。XRD,^2^9SiMASNMR,^1^3CMASNMR,以及N~2、水与环己烷吸附的表征,显示改性不同程度地改变了分子筛的表面组成与结构,减小孔径,增加孔壁厚度,因而影响吸附行为,减小吸附容量。硅烷化减少了MCM-41的表面硅羟基含量,增加其疏水性。用CH~3I改性使孔径减小1.4nm,而硅羟基含量并未显著减少。硅烷化以及用CH~3I改性可提高MCM-41分子筛的热稳定性。SiCl~4的改性作用相对不明显。样品的水及环己烷吸附容量与其表面硅羟基含量呈现不同的线性关系,揭示高硅MCM-41分子筛表面吸附中心的本性。     

醋酸酯淀粉高取代度的测定

淀粉的乙酰化改性是扩大其应用的一个重要手段。测定醋酸酯淀粉取代度 (DegreeofSubstitution ,简称DS)的方法通常有酸碱滴定法、紫外法、核磁共振法及衰减全反射法[1 ] 等 ,后 3种方法需建立标准曲线 ,要求有一系列取代度的样品 ,实验操作较困难。所以实验室更多采用酸碱滴定法。实验室多采用乙醇为溶剂进行醋酸酯淀粉高取代度的测定[1～3] 。这种方法的缺点是皂化时间需 48～ 72h ,并且高取代度醋酸酯淀粉的溶解性不理想。本文对酸碱滴定法测定醋酸酯淀粉高取代度溶剂选择进行了探讨 ,以期建立一种快速、准确地测定醋酸酯淀粉高取代度的…