Chiral induction in quinoline-derived oligoamide foldamers: assignment of helical handedness and role of steric effects

Chiral groups attached to the end of quinoline-derived oligoamide foldamers give rise to chiral helical induction in solution. Using various chiral groups, diastereomeric excesses ranging from 9% to 83% could be measured by NMR and circular dichroism. Despite these relatively weak values and the fact that diastereomeric helices coexist and interconvert in solution, the right-handed or left-handed helical sense favored by the terminal chiral group could be determined unambiguously using X-ray crystallography. Assignment of chiral induction was performed in an original way using the strong tendency of racemates to cocrystallize, and taking advantage of slow helix inversion rates, which allowed one to establish that the stereomers observed in the crystals do correspond to the major stereomers in solution. The sense of chiral helical induction was rationalized on the basis of sterics. Upon assigning an Rs or Ss chirality to the stereogenic center using a nomenclature where the four substituents are ranked according to decreasing sizes, it is observed that Rs chirality always favors left-handed helicity and Ss chirality favors right-handed helicity (P). X-ray structures shed some light on the role of sterics in the mechanism of chiral induction. The preferred conformation at the stereocenter is apparently one where the bulkiest group should preferentially point away from the helix, the second largest group should be aligned with the helix backbone, and the smallest should point to the helix.     

High performance organic field-effect transistors based on amphiphilic tris(phthalocyaninato) rare earth triple-decker complexes

LB films of three amphiphilic tris(phthalocyaninato) rare earth triple-decker complexes with crown-ethers as hydrophilic heads and long alkyl chains as hydrophobic tails have been prepared and found to display very well ordered layer structures, as proved by pi-A isotherms, UV-vis and polarized absorption spectra, X-ray diffraction experiments, and microscopic morphology characterization. These LB films have been fabricated into field-effect transistor (FET) devices, which show carrier mobilities as high as 0.24-0.60 cm2 V-1 s-1, among the highest mobilities achieved thus far for all LB film-based OFETs.     

Influence of the water molecule on cation-pi interaction: ab initio second order Møller-Plesset perturbation theory (MP2) calculations

The influence of introducing water molecules into a cation-pi complex on the interaction between the cation and the pi system was investigated using the MP2/6-311++G method to explore how a cation-pi complex changes in terms of both its geometry and its binding strength during the hydration. The calculation on the methylammonium-benzene complex showed that the cation-pi interaction is weakened by introducing H(2)O molecules into the system. For example, the optimized interaction distance between the cation and the benzene becomes longer and longer, the transferred charge between them becomes less and less, and the cation-pi binding strength becomes weaker and weaker as the water molecule is introduced one by one. Furthermore, the introduction of the third water molecule leads to a dramatic change in both the complex geometry and the binding energy, resulting in the destruction of the cation-pi interaction. The decomposition on the binding energy shows that the influence is mostly brought out through the electrostatic and induction interactions. This study also demonstrated that the basis set superposition error, thermal energy, and zero-point vibrational energy are significant and needed to be corrected for accurately predicting the binding strength in a hydrated cation-pi complex at the MP2/6-311++G level. Therefore, the results are helpful to better understand the role of water molecules in some biological processes involving cation-pi interactions.     

Development and validation of a high-performance liquid chromatography-electrospray ionization-mass spectrometry assay for the determination of zaleplon in human plasma

In this paper, a sensitive and rapid chromatographic procedure using a selective analytical detection method (electrospray ionization-mass spectrometry in selected-ion monitoring mode) in combination with a simple and efficient sample preparation step is first presented for the determination of zaleplon in human plasma. The separation of the analyte, internal standard, and possible endogenous compounds are accomplished on a phenomenex Luna 5-microm C8(2) column (250- x 4.6-mm i.d.) with methanol-water (75:25, v/v) as the mobile phase. In order to optimize the mass detection of zaleplon, several parameters such as ionization mode, fragmentor voltage, m/z ratios of ions monitored, type of organic modifier, and eluent additive in the mobile phase are discussed. An internal standard is selected to guarantee the quantitative accuracy. Each analysis takes less than 6 min. The calibration curve of zaleplon in the range of 0.1-60.0 ng/mL in plasma is linear with a correlation coefficient of > 0.9992, and the detection limit (s/n = 3) is 0.1 ng/mL. The within- and between-day variations (relative standard deviation) in the zaleplon plasma analysis are less than 2.4% (n = 15) and 4.7% (n = 15), respectively. The application of this method is demonstrated for the analysis of zeleplon plasma samples in a Phase-I human pharmacokinetic study.     

γ—Mo2N合成过程中的热变化及中间产物的研究

采用ＤＴＡ技术，通过改变升温速率研究了γ－Ｍｏ２Ｎ合成过程中的热变化，并经ＸＲＤ，ＢＥＴ及ＩＲ测试，对ＤＴＡ曲线中的谱峰进行归属，考察了中间产物，ＤＴＡ结果表明，在ＭｏＯ３和ＮＨ３程序升温反应过程中有放热峰及吸热峰出现，且随升温速率的长高，放热峰面积与吸热峰面积之比逐渐减小，结合ＸＲＤ及ＩＲ结果可知，ＤＴＡ曲线听放热峰可归属为由ＭｏＯ３变化为ＭｏＯ２的还原峰，吸热峰则归属为由ＭｏＯ２变化为Ｍｏ２Ｎ     

Rhodium-catalyzed asymmetric hydrogenation of functionalized olefins using monodentate spiro phosphoramidite ligands

Novel chiral monodentate phosphorus ligands, SIPHOS, were conveniently synthesized from 1,1'-spirobiindane-7,7'-diol. The Rh complexes of SIPHOS can catalyze the hydrogenation of alpha-dehydroamino esters in mild conditions, providing alpha-amino acid derivatives in up to 99% ee. Enamides and beta-dehydroamino esters can also be hydrogenated in good to excellent enantioselectivities (up to 99% and 94% ee, respectively). The SIPHOS ligand with smaller alkyl groups on the N-atom afforded higher enantioselectivity. The X-ray analysis of single crystal showed that the structure of Rh/SIPHOS catalyst is [Rh(COD)((S)-SIPHOS-Me)(2)](+), which clarified the configuration of the catalyst with the monodentate chiral phosphorus ligand in Rh-catalyzed asymmetric hydrogenation. A positive nonlinear effect in the relationship of the optical purities of ligand and product was observed in the hydrogenation of dehydroamino acid derivatives. The kinetic study of hydrogenation showed that the reaction is zero order in the concentration of substrate and first order in the concentration of Rh catalyst and the hydrogenation pressure. The rate of hydrogenation decreased when the Rh/L ratio changed from 1:1 to 1:4.     

Silicone-modified starch/protein microparticles: protecting biopolymers with a hydrophobic coating

Silicone-coated starch/protein (human serum albumin, HSA) microparticles were prepared by precipitation of a starch/HSA/DMSO/water (water-in-oil) emulsion into acetone containing a silicone: the silicone polymer was either unfunctionalized (SiMe₃ terminated, PDMS) or functionalized at its termini with Si(OEt)₃ groups (TES-PDMS). The microparticles of approximate diameter 2–7 μm were highly hydrophobic with advancing contact angles 115°. Over several minutes, however, the contact angle decreased to ca. 40–70°. Soxhlet extraction with water led to degradation of the microparticles, irrespective of the nature of their silicone coating, as evidenced by release of the protein from them. Intraperitoneal (IP) or gastric administration of the two different particles to mice, however, showed a clear difference between the two silicones. The microparticles coated with either PDMS or TES-PDMS led to very different immune responses. Oral administration of the microparticles prepared with functionalized silicone elicited a significant production of antibodies, whereas the particles prepared with the unfunctionalized silicone (PDMS) were only weakly active. By contrast, the IP results demonstrated that particles coated with PDMS elicited an immune response that was established much more rapidly than with the particles modified with TES-PDMS. It is proposed that the TES-PDMS forms a physically adhering film or covalent bond to the protein molecules, which serves to protect the microparticle from biological degradation in the gut and/or facilitates the microparticle/protein interaction with the immune system.     

FI－ICP－AES在线稀释间接测定表面活性剂─十二烷基苯磺酸钠

基于十二烷基苯磺酸钠（ＤＢＳ）与无机钠盐在无水乙醇中溶解度的差异，用乙醇选择提取ＤＢＳ，经水适当稀释，通过用ＦＩ－ＩＣＰ－ＡＥＳ测定其中的钠，从而间接测定ＤＢＳ的含量。     

激光解吸电离质谱法分析富勒烯

论述了用激光解吸电离谱法分析富勒烯。因在电离过程中富勒分子不发生裂解，因此这种方法可直接用于富勒烯混合物的分析而勿需任何预分离。还给出了用本法分析较大、较稳定富勒烯分子的质谱图。     

Novel one-dimensional tubelike and two-dimensional polycatenated metal-organic frameworks

Two novel metal-organic frameworks (MOFs) [Zn(TITMB)(OAc)](OH).8.5H(2)O (1) and [Ag(TITMB)N(3)].H(2)O (2) [TITMB = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, OAc = acetate anion] were synthesized and their structures were determined by X-ray crystallography. Complex 1 crystallizes in tetragonal space group P(-)4 with a = 23.2664(7) and c = 11.9890(3) A and Z = 8. 1 has a one-dimensional tubelike structure with large inner pore size of approximately 17 A. Complex 2 crystallizes in monoclinic space group C2 with a = 20.7193(10), b = 11.5677(8), and c = 12.2944(6) A, beta = 125.5770(10) degrees, and Z = 4. 2 consists of two-dimensional honeycomb networks that interpenetrate each other to generate a polycatenated structure. In these two complexes, both zinc(II) and silver(I) atoms are four-coordinated with the same tetrahedral coordination geometry. The topologies of 1 and 2 are predominated by the conformations of TITMB, which are cis, trans, trans in 1 and cis, cis, cis in 2, respectively.