离子液体与绿色化学：为了今天还是为了未来？

离子液体因绿色化学的兴起而成名。本文结合作者自己8年来的研究工作评述了离子液体特别是在化学合成、化学反应领域的最新进展。主要分4个方面：离子液体改变了载体/模版的概念;离子液体研究促进了液相反应的研究;离子液体推动了相分离技术的进步;离子液体推动了绿色化学的发展。     

Tunable self-assembled peptide amphiphile nanostructures

Peptide amphiphiles are capable of self-assembly into a diverse array of nanostructures including ribbons, tubes, and vesicles. However, the ability to select the morphology of the resulting structure is not well developed. We examined the influence of systematic changes in the number and type of hydrophobic and hydrophilic amino acids on the self-assembly of amphiphilic peptides. Variations in the morphology of self-assembled peptides of the form X(6)K(n) (X = alanine, valine, or leucine; K = lysine; n = 1-5) are investigated using a combination of transmission electron microscopy and dynamic light scattering measurements. The secondary structures of the peptides are determined using circular dichroism. Self-assembly is controlled through a combination of interactions between the hydrophobic segments of the peptide molecules and repulsive forces between the charged segments. Increasing the hydrophobicity of the peptide by changing X to a more lipophilic amino acid or decreasing the number of hydrophilic amino acids transforms the self-assembled nanostructures from vesicles to tubes and ribbons. Changes in the hydrophobicity of the peptides are reflected in changes in the critical micelle concentration observed using pyrene probe fluorescence analysis. Self-assembled materials formed from cationic peptide amphiphiles of this type display promise as carriers for insoluble molecules or negatively charged nucleic acids in drug or gene delivery applications.     

Synthesis and insecticidal activities of novel spin‐labeled derivatives of camptothecin

Continuing our search for natural product based compounds for the control of Brontispa longissima larvae, eight spin‐labeled camptothecin derivatives 7a–h and the intermediate 2 were first tested for their insecticidal activities against fifth‐instar larvae of Brontispa longissima. Among all the tested compounds, especially compounds 7a and 2 showed promising insecticidal activities with the corrected mortality rates of 69.55% and 74.07% against fifth‐instar larvae of B. longissima, respectively. The different insecticidal activity ranges of these compounds indicated that the variation of the structures of l ‐amino acids in these compounds markedly affected the activity profiles of this compound class, and some important SAR information has been revealed from it. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:687–691, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20734     

A Nitrite Biosensor Based on the Direct Electron Transfer of Hemoglobin Immobilized on Carboxyl‐Functionalized Multiwalled Carbon Nanotubes/Polyimide Composite

The high electrically conductive carboxyl‐functionalized multiwalled carbon nanotubes (COOH‐MWCNTs) were used to combine with nonconducting polyimide (PI) to generate a PI/COOH‐MWCNTs membrane. PI served as a matrix to entrap COOH‐MWCNTs and hemoglobin (Hb). COOH‐MWCNTs can improve the conductivity of the composite. The direct electrochemistry measurement indicated that the PI/COOH‐MWCNTs composite enhanced the immobilization of Hb significantly. Besides, the Hb/PI/COOH‐MWCNTs/GCE biosensor possessed excellent electrocatalytic activity for the detection of nitrite. Therefore, PI is a good matrix for Hb immobilization and it has application in sensor construction. This work is promising in the development of sensitive biosensors based on PI/COOH‐MWCNTs composite film.     

Use of dimethyl carbonate as a solvent greatly enhances the biaryl coupling of aryl iodides and organoboron reagents without adding any transition metal catalysts

The coupling reaction of aryl iodides with arylboronic acids to give biaryl compounds can be efficiently performed without adding a transition metal catalyst. The key to success is the use of dimethyl carbonate as a solvent. This finding provides a new strategy for constructing a biaryl linkage.     

Cyclization reactions of homopropargyl azide derivatives catalyzed by PtCl4 in ethanol solution: synthesis of functionalized pyrrole derivatives

[Structure: see text] PtCl4-catalyzed cyclization reactions of homopropargyl azide derivatives to pyrrole rings were investigated. Using ethanol as solvent with 2,6-di-tert-butyl-4-methylpyridine as the base was found to be the best set of conditions for effecting this ring-closing reaction. These reaction conditions can be applied to the preparation of functionalized pyrrole derivatives, with no effect on the functional groups.     

Picolinyl ester fragmentation mechanism studies with application to the identification of acylcarnitine acyl groups following transesterification

Acyl picolinyl esters provide excellent data to identify the structures of acyl groups. However, the mechanisms for the formation of fragment ions from picolinyl esters are unsettled. Proposed structures for fragment ions have focused on long-chain groups and may not accommodate results from medium- and short-chain acyl groups. Using deuterium-labeled organic acids, we have investigated the mechanisms for the formation of fragment ions. Based on these studies, we propose a new mechanism that is consistent with the experimental data. We then tested the mechanisms by analyzing selected acylcarnitines. Transesterification of acylcarnitines was performed by reaction with 3-pyridylcarbinol and potassium tert-butoxide in dichloromethane to produce acyl picolinyl esters. The picolinyl esters were separated and detected by gas chromatography/electron ionization-mass spectrometry. Each mass spectrum contained a series of peaks with m/z differences of 12, 13, or 14 u depending on the acyl group's chemical structure. The position of an unsaturated bond or branched methyl in the acyl group of acylcarnitine can be readily determined.     

Semilocal convergence of a modified multi-point Jarratt method in Banach spaces under general continuity condition

The semilocal convergence for a modified multi-point Jarratt method for solving non-linear equations in Banach spaces is established with the third-order Fréchet derivative of the operator under a general continuity condition. The recurrence relations are derived for the method, and from this, we prove an existence-uniqueness theorem, and give a priori error bounds. The R-order of the method is also analyzed with the third-order Fréchet derivative of the operator under different continuity conditions. Numerical application on non-linear integral equation of the mixed type is given to show our approach.     

Structural characterization and high‐temperature compressive creep of PTFE‐based composites filled with inorganic nanoparticles

The PTFE‐based nanocomposites with various contents of inorganic nanoparticles (n‐AlN and n‐Si₃N₄) were prepared by cold compaction followed by free sintering. The results of scanning electron microscopy, differential scanning calorimetry, and X‐ray diffraction show that PTFE spherulite formed in the nanocomposites. When 2 wt% inorganic nanoparticles were added into the PTFE matrix, the crystallinity increased from 34.3% to 42.1% and 43.2%, respectively. Moreover, the interplanar distances for each crystal plane were enlarged and the grain sizes were smaller than that of pure PTFE. In addition, the mechanical and high‐temperature compressive creep properties were investigated. The results indicate that the introduction of inorganic nanoparticles largely increased the high‐temperature compressive creep resistance, and the maximal reduction of percentage of creep strain was up to 68%. The tensile strengths of the nanocomposites increased with increasing filler content when it was no more than 2%, and then decreased with the further increase of the filler content, whereas the elongations at break showed a reverse tendency. Copyright © 2011 John Wiley & Sons, Ltd.