Synthesis and properties of coumarin-derived organogelators

A new family of coumarin derivatives containing amide group with different alkyl chain lengths was synthesized and their properties as organogelators were evaluated. It was found that the organogelation abilities were not obviously affected by the alkyl spacer length of amide group. Helical morphologies formed either in nonpolar or high polar solvents by most of the gelators. Occurrence of reversible and stereoselective photodimerization of the gel formed by 4-(7′-coumarinoxy)-N-octadecylbutanamide (3a) in cyclohexane was confirmed by ¹H NMR, UV absorption, and fluorescence spectra. The photoreaction of the gel proceeded without any dissolution, but the drastic microscopic changes of gel morphologies accompanied with the irradiation were identified using SEM and AFM investigations.     

铝镓取代的钨硅杂多配合物位置异构体的合成表征及催化性能

合成了通式为Ｋ５－ｎＨｎ［α－，βｉ－ＳｉＷ１１Ｍ（Ｈ２Ｏ）Ｏ３９］·ｘＨ２Ｏ（Ｍ＝Ａｌ，Ｇａ，βｉ＝β１，β２，β３）的八种异构体。通过元素分析、红外光谱和紫外光谱、极谱和循环伏安、２７Ａｌ和１８３Ｗ核磁共振、Ｘ光电子能谱等方法进行了表征。所合成的各异构体在催化以Ｈ２Ｏ２为氧化剂的顺丁烯二酸环氧化反应中，β３异构体具有最高的催化活性     

A Study on Thermal Decomposition of K_3[Fe(CN)_6] and KFe[Fe(CN)_6] in Helium

K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2.     

Geometries and electronic structures of W4 and W clusters

Geometries and electronic structures of W₄ and W clusters were studied by use of density functional methods B3LYP, B3P86, B3PW91, BHLYP, BLYP, and MPW1PW91. The calculated results indicate that the three‐dimensional structure of singlet state with either D_2d symmetry (B3LYP, B3P86, B3PW91, BLYP, and MPW1PW91) or C_2v symmetry (BHLYP) is the ground state for the W₄ cluster. For the W cluster, the doublet state is preferred, and the most stable structure is also 3D with either D_2d symmetry (B3LYP, B3PW91, BHLYP, BLYP) or C_2v symmetry (B3P86 and MPW1PW91). The calculated electron affinity at B3P86 gives the best performance compared with experiment. For the dissociation channel, W + W₃ is suggested to be the possible route for the W₄ cluster. For the W cluster, W + W is the most likely route for dissociation, in agreement with experiment. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Simultaneous determination of carbohydrates and organic acids in beer and wine by ion chromatography

The simultaneous determination of mono-organic acids and carbohydrates by ion chromatography with both conductometric and pulsed amperometric detection is described. The carbohydrates, such as mannitol, arabinose, glucose, fructose, lactose, sucrose, raffinose, and maltose, as well as monoorganic acids including acetate, glycolate, formate, pyruvate, and fluoride are separated as anions by ion-exchange chromatography with 0.080 mol/L sodium hydroxide eluent at 1 mL/min within 12 min. Carbohydrates are determined by pulsed amperometric detection and mono-organic acids are determined by suppressed conductivity detection. The species in beverages are determined.     

Probing the intrinsic electronic structure of the cubane [4Fe-4S] cluster: nature's favorite cluster for electron transfer and storage

The cubane [4Fe-4S] is the most common multinuclear metal center in nature for electron transfer and storage. Using electrospray, we produced a series of gaseous doubly charged cubane-type complexes, [Fe4S4L4]2- (L = -SC2H5, -SH, -Cl, -Br, -I) and the Se-analogues [Fe4Se4L4]2- (L = -SC2H5, -Cl), and probed their electronic structures with photoelectron spectroscopy and density functional calculations. The photoelectron spectral features are similar among all the seven species investigated, revealing a weak threshold feature due to the minority spins on the Fe centers and confirming the low-spin two-layer model for the [4Fe-4S](2+) core and its "inverted level scheme". The measured adiabatic detachment energies, which are sensitive to the terminal ligand substitution, provide the intrinsic oxidation potentials of the [Fe4S4L4]2- complexes. The calculations revealed a simple correlation between the electron donor property of the terminal thiolate as well as the bridging sulfide with the variation of the intrinsic redox potentials. Our data provide intrinsic electronic structure information of the [4Fe-4S] cluster and the molecular basis for understanding the protein and solvent effects on the redox properties of the [4Fe-4S] active sites.     

钴(Ⅱ)-5-取代邻菲罗啉-α-氨基酸三元配合物的稳定性研究

本文在25.0±0.1℃,I=0.1mol·dm^-3KNO₃存在下,采用pH法测得了5-取代邻菲罗啉的质子化常数以及钴(Ⅱ)与5-取代邻菲罗啉、α-氨基酸的二元、三元配合物的稳定常数。结果表明三元配合物的稳定性与5-取代邻菲罗啉的质子化常数、取代基常数均存在直线自由能关系。并用三元配合物稳定性的表征值logK_M、△logK,讨论了三元配合物的稳定性,发现钴(Ⅱ)与配体5-取代邻菲罗啉之间也存在着d-p反馈π键。该π健的强度对三元配合物稳定性有着显著影响。     

Cellulose synthesis in maize: isolation and expression analysis of the cellulose synthase (CesA) gene family

Stalk lodging in maize results in significant yield losses. We have determined that cellulose per unit length of the stalk is the primary determinant of internodal strength. An increase in cellulose concentration in the wall might allow simultaneous improvements in stalk strength and harvest index. Cellulose formation in plants can be perturbed by mutations in the genes involved in cellulose synthesis, post-synthetic cellulose alteration or deposition, N-glycosylation, and some other genes with as yet unknown functions. We have isolated 12 members of the cellulose synthase (CesA) gene family from maize. The genes involved in primary wall formation appear to have duplicated relatively independently in dicots and monocots. The deduced amino acid sequences of three of the maize genes, ZmCesA10–12, cluster with the Arabidopsis CesA sequences that have been shown to be involved in secondary wall formation. Based on their expression patterns across multiple tissues, these three genes appear to be coordinately expressed. The remaining genes show overlapping expression to varying degrees with ZmCesA1, 7, and 8 forming one group, ZmCesA3 and 5 a second group, and ZmCesA2 and 6 exhibiting independent expression of any other gene. This suggests that the varying levels of coexpression may just be incidental except in the case of ZmCesA10–12, which may interact with each other to form a functional enzyme complex. Isolation of the expressed CesA genes from maize and their association with primary or secondary wall formation has made it possible to test their respective roles in cellulose synthesis through mutational genetics or transgenic approaches. This information would be useful in improving stalk strength.     

On the copolymerization of acrylates in the modified microemulsion process

Copolymerization of methyl methacrylate, methyl acrylate, butyl methacrylate, and butyl acrylate in turn was performed in the modified microemulsion polymerization process, i.e., continuous addition of monomer to a preemulsified system. It was found that the particle size of the copolymer microlatex did not change distinctly with the monomer composition. The estimation of emulsifier coverage on the microlatex particles indicated that the process switched from a traditional microemulsion to a normal seeded emulsion polymerization very soon after monomer dropping began. Therefore, a longer dropping time is needed to produce a microlatex with narrow dispersed particle size. Besides, in the modified microemulsion polymerization less emulsifier is needed to produce a stable microlatex. This behavior is related to the mechanism of normal seeded emulsion polymerization during monomer dropping.