Synthesis and applications of C2-symmetric guanidine bases

The preparation of the tetracyclic C₂-symmetric guanidinium salts 5 and 11-13 is reported together with their application to enantioselective transformations.     

Starburst dendrimer-supported pseudostationary phases for electrokinetic chromatography

Pseudo-stationary phases for electrokinetic chromatography were prepared by the alkylation of starburst dendrimers (SBDs). The SBD-supported pseudo-stationary phase with dodecyl groups showed higher efficiency than short-akyl derivatives, and maintained the hydrophobic property inthe presence of methanol. The dodecyl-modified SBD provided wide migration time windows ar high methanol content to effect the separation of sixteen aromatic hydrocarbons, the priority pollutants designated by EPA, in 65% methanol. The selectivity of polymer-supported pseudo-stationary phase can be varied simply by changing the length of the alkyl groups. The dodecyl SBD showed relatively similar selectivity as sodium dodecyl culfate micelle, whereas short alkyl derivatives showed preference towards rigid and planar compounds based on the rigid and planar compounds based on the rigid polymer backbones. The selectivity of SBD-supported pseudo-stationary phases was dominated by the chain length of the alkyl groups, with the minor effect of the structure of the core and the generation of SBD where alkyl groups were attached.     

碳十八键合锆胶固定相的制备与色谱性能评价

用诱导聚合胶体凝聚法（PICA）制得的二氧化锆微球与碳十八三乙氧基硅烷反应制备了碳十八键合锆胶固定相（ODZ），评价了该柱填料的色谱性能，并用此固定相分离了中性和碱性化合物。     

鞘磷脂和神经节苷脂对磷脂酰乙醇胺混合脂超分子体系液晶态立方相Im3m和Pn3m结构影响的研究

用磷脂酰乙醇胺(DEPE)、鞘磷脂(Sphingomyeline, Sph)、神经节苷脂(Gm1)和胆固醇(Chol)模拟了生物膜超分子体系液晶态结构, 通过用小角X射线衍射(SAXD)对混合脂体系液晶态结构进行了研究, 鉴定出了两种立方相: 即Im3m(Q²²⁹)和Pn3m(Q²²⁴)结构. 实验发现, 鞘磷脂的含量对DEPE膜的结构有一定的影响, 随着鞘磷脂浓度的增加, 混合脂体系的液晶态结构发生了由Im3m(Q²²⁹)到Pn3m(Q²²⁴)的变化. 神经节苷脂(Gm1)的含量对混合脂体系的液晶态结构也有一定的影响, 当神经节苷脂(Gm1)含量达到某一临界值时, 混合脂体系的液晶态结构发生了从Im3m(Q²²⁹)到Pn3m(Q²²⁴) 的变化. 当DEPE-Shp-Gm1超分子聚集体中含有胆固醇时, 胆固醇的极性头部(—OH)与磷脂酰乙醇胺(DEPE)、鞘磷脂(Shp)、神经节苷脂(Gm1)的极性头部通过氢键相互作用形成液晶态立方相Im3m(Q²²⁹)结构, 再通过疏水/亲水相互作用形成稳定的Pn3m (Q²²⁴)结构.     

Improvement in enzyme activity and stability by addition of low molecular weight polyethylene glycol to sodium bis(2-ethyl-L-hexyl)sulfosuccinate/isooctane reverse micellar system

The activity and stability of Chromobacterium viscosum lipase (glycerolester hydrolase, EC 3.1.1.3)-catalyzed olive oil hydrolysis in sodium bis (2-ethyl-1-hexyl)sulfosuccinate (AOT)/isooctane reverse micelles is increased appreciably when low molecular weight polyethylene glycol (PEG 400) is added to the reverse micelles. To understand the effect of PEG 400 on the phase behavior of the reverse micellar system, the phase diagram of AOT/PEG 400/water/isooctane system was studied. The influences of relevant parameters on the catalytic activity in AOT/PEG 400 reverse micelles were investigated and compared with the results in the simple AOT reverse micelles. In the presence of PEG 400, the linear decreasing trend of the lipase activity with AOT concentration, which is observed in the simple AOT reverse micelles, disappeared. Enzyme entrapped in AOT/PEG reverse micelles was very stable, retaining>75% of its initial activity after 60 d, whereas the half-life in simple AOT reverse micelles was 38 d. The kinetics parameter maximum velocity (V _max)exhibiting the temperature dependence and the activation energy obtained by Arrhenius plot was suppressed significantly by the addition of PEG 400.     

Synthesis and Opto-Electronic Properties of Cholesteric Cellulose Esters

Cholesteric materials display unique optical properties which can be exploited in opto-electronic applications such as light emitting diodes. The key feature is the position of the wavelength of the emitted light relative to the one of the selective reflection band. We have synthesized a set of cellulose derivatives displaying the cholesteric phase with the aim to investigate the correlation between chemical structure and properties. Phase transition temperatures, the chain packing, the wavelength of selective reflection but also absorption and fluorescence spectra were investigated as a function of the degree of substitution (DS), the nature of lateral substituents, the composition of doped systems and blends of different cellulose derivatives. Investigated were furthermore the degree of circular polarization of the emitted light for guest–host systems and for cellulose systems with chromophores linked by covalent bonds to the cellulose backbone as well as their performance in light emitting diodes. The conclusion is that the optical properties can be accounted for on the basis of the model of a one-dimensional photonic crystal. The limiting factor with respect to opto-electronic applications is the poor control of the uniformity of the helix formation and orientation.     

Reversible Immobilization of Peptides: Surface Modification and In Situ Detection by Attenuated Total Reflection FTIR Spectroscopy

A generic method is described for the reversible immobilization of polyhistidine‐bearing polypeptides and proteins on attenuated total reflecting (ATR) sensor surfaces for the detection of biomolecular interactions by FTIR spectroscopy. Nitrilotriacetic acid (NTA) groups are covalently attached to self‐assembled monolayers of either thioalkanes on gold films or mercaptosilanes on silicon dioxide films deposited on germanium internal reflection elements. Complex formation between Ni²⁺ ions and NTA groups activates the ATR sensor surface for the selective binding of polyhistidine sequences. This approach not only allows a stable and reversible immobilization of histidine‐tagged peptides (His–peptides) but also simultaneously allows the direct in situ quantification of surface‐adsorbed molecules from their specific FTIR spectral bands. The surface concentrations of both NTA and His–peptide on silanized surfaces were determined to be 1.1 and 0.4 molecules nm^?2, respectively, which means that the surface is densely covered. A comparison of experimental FTIR spectra with simulated spectra reveals a surface‐enhancement effect of one order of magnitude for the gold surfaces. With the presented sensor surfaces, new ways are opened up to investigate, in situ and with high sensitivity and reproducibility, protein–ligand, protein–protein, protein–DNA interactions, and DNA hybridization by ATR–FTIR spectroscopy.     

Crystal structure of KAsUO<Subscript>6</Subscript>·<Subscript>3</Subscript>H<Subscript>2</Subscript>O at 100 and 293 K

The crystal structure of KAsUO₆·3H₂O was solved at 100 K and 293 K. KAsUO₆·3H₂O at T = 100 K: tetragonal, P4/ncc, a = 7.2037(6) Å, c = 17.811(2) Å; Z = 4, R1 = 0.0263, wR2 = 0.0546, for 618 independent reflections; at T = 293 K: tetragonal, P4/ncc, a = 7.1600(4) Å, c = 17.746(1) Å; Z = 4, R1 = 0.0263, wR2 = 0.0433 for 427 independent reflections. The results of X-ray analysis are compared with our previous data on heat capacity of this compound, and changes that take place in the structure at elevated temperature are considered.