Synthesis of Metal‐Free Phthalocyanines in Functionalized Ammonium Ionic Liquids

A convenient, fast, efficient, and ecofriendly synthesis of metal‐free phthalocyanines from various substituted phthalonitriles in different hydroxyalkylammonium ionic liquids in the presence of 1,8‐diazabicyclo‐[5,4,0]‐undec‐7‐ene (DBU) is reported in moderate yields. The effect of concentration of DBU and temperature on the synthesis of phthalocyanine in N‐(2‐hydroxyethyl)‐N,N‐dimethylbutylammonium bromide ionic liquid has been examined, and the ionic liquid has been recovered and reused conveniently.     

Oxidative Addition of 4-Hydroxycoumarin to Alkenes. An Expeditious Entry to 2,3-Dihydro-4H-furo-[3,2-c][1]benzopyran-4-ones1

In the presence of one-electron metal oxidants (CAN, MAH), 4-hydroxycoumarin (1) adds to alkenes to give 2,3-dihydro-4H-furo[3,2-c][1]benzopyran-4-ones.     

Synthesis of 7‐Alkoxy/Hydroxy‐α‐methyltryptamines

Abstract

A simple method for the preparation of 7‐alkoxy/hydroxy‐α‐methyl‐DL‐tryptamines is reported. The key steps of the synthesis are the Japp–Klingemann coupling of 2‐piperidone‐3‐carboxylic acid 3 with diazonium salts 4, the Fischer‐type cyclization of hydrazones 5 to β‐carboline derivatives 6 and their hydrolysis to title compounds 8.     

Improved synthesis of (R)-7-hydroxycarvone from (S)-α-pinene

A three-step synthesis of (R)-7-hydroxycarvone (1), which is anticipated to be a valuable building block for the versatile preparation of natural products, is described. Optimization of the reaction conditions for photooxygenation and migration of (S)-α-pinene 2, tetrapropylammonium perruthenate (TPAP) oxidation of the generated alcohol, and a subsequent ring-opening reaction in the presence of Cu(OTf)₂ led to the synthesis of 1 with good reproducibility. The desired product 1 was thus obtained in 46% yield over three steps.     

Heteropoly acid catalyzed synthesis of 8-methyl-2-aryl/alkyl-3-oxabicyclo[3.3.1]non-7-ene derivatives through (3,5)-oxonium-ene reaction

A variety of aldehydes undergo a smooth coupling with (4-methylcyclohex-3-en-1-yl)methanol in the presence of 2 mol % of phosphomolybdic acid in dichloromethane to afford 3-oxabicyclo[3.3.1]non-7-ene in good yields through 3,5-oxonium-ene cyclization under mild conditions. The use of inexpensive, nontoxic, and readily available heteropoly acid catalyst makes this method simple, convenient, and environmental-friendly.     

A novel condition for capillary electrophoretic analysis of reductively aminated saccharides without removal of excess reagents

We have identified novel CE conditions for the separation of 7‐amino‐4‐methylcoumarin‐labeled monosaccharides and oligosaccharides from glycoproteins. Using a neutrally coated capillary and alkaline borate buffer containing hydroxypropylcellulose and ACN, saccharide derivatives form anionic borate complexes, which move from the cathode to the anode in an electric field and are detected near the anodic end. Excess labeling reagents and other fluorescent products remain at the cathodic end. Fluorimetric detection using an LED as a light source enables determination of monosaccharide derivatives with good linearity between at least 0.4 and 400 μM, may correspond to 140 amol to 140 fmol. The lower LOD (S/N = 5) is only 80 nM in the sample solution (ca. 28 amol). The results were comparable to reported values using fluorometric detection LC. The method was also applied to the analysis of oligosaccharides that were enzymatically released from glycoproteins. Fine resolution enables profiling of glycans in glycoproteins. The applicability of the method was examined by applying it to other derivatives labeled with nonacidic tags such as ethyl p‐aminobenzoate‐ and 2‐aminoacridone‐labeled saccharides.     

Message passing interface and multithreading hybrid for parallel molecular docking of large databases on petascale high performance computing machines

A mixed parallel scheme that combines message passing interface (MPI) and multithreading was implemented in the AutoDock Vina molecular docking program. The resulting program, named VinaLC, was tested on the petascale high performance computing (HPC) machines at Lawrence Livermore National Laboratory. To exploit the typical cluster‐type supercomputers, thousands of docking calculations were dispatched by the master process to run simultaneously on thousands of slave processes, where each docking calculation takes one slave process on one node, and within the node each docking calculation runs via multithreading on multiple CPU cores and shared memory. Input and output of the program and the data handling within the program were carefully designed to deal with large databases and ultimately achieve HPC on a large number of CPU cores. Parallel performance analysis of the VinaLC program shows that the code scales up to more than 15K CPUs with a very low overhead cost of 3.94%. One million flexible compound docking calculations took only 1.4 h to finish on about 15K CPUs. The docking accuracy of VinaLC has been validated against the DUD data set by the re‐docking of X‐ray ligands and an enrichment study, 64.4% of the top scoring poses have RMSD values under 2.0 Å. The program has been demonstrated to have good enrichment performance on 70% of the targets in the DUD data set. An analysis of the enrichment factors calculated at various percentages of the screening database indicates VinaLC has very good early recovery of actives. © 2013 Wiley Periodicals, Inc.     

纳米金标记抗体增强SPR检测大肠杆菌O157∶H7

将金纳米粒子(AuNPs)标记的大肠杆菌O157∶H7(E.coli O157∶H7)的多克隆抗体(PAb)作为二抗,采用氨基偶联法将PAb固定在传感器表面作为一抗,通过三明治方法用双通道表面等离子体子共振(SPR)传感器对E.coli O157∶H7进行检测,并与SPR直接法检测进行了比较.结果表明,直接法的检出限为103cfu/mL,线性范围为103～109cfu/mL;AuNPs增强三明治法的检出限为10 cfu/mL,线性范围为10～1010cfu/mL,灵敏度比直接法提高了100倍,且具有更宽的检测范围.本方法不仅检测时间短,而且具有良好的选择性和重现性.     

Photochromic reverse mode polymer dispersed liquid crystals

Control of light intensity and colour are two of the major features required in the realization of smart windows. We designed a bi‐functional polymer dispersed liquid crystal (PDLC) film in order to satisfy such requirements, i.e. it is able both to modulate the optical transmission, if an external electric field is applied, and to change colour if exposed to sunlight. A monomer/liquid crystal mixture was doped with a small amount of photochromic material and homeotropically aligned by means of rough surfaces. A transparent and pale pink coloured film was achieved after photopolymerization. Such a film changes colour upon exposure for some seconds to sunlight or ultraviolet radiation in a persistent but reversible manner. In addition, the film appears transparent without the application of an electric field (OFF state) and becomes opaque on application of a driving voltage of about 75?V (ON state), and thus the film operates in reverse mode with respect to conventional PDLCs.     

Application of Non-Destructive X-Ray Fluorescence Spectrometry to the Analysis of Suspended Matter in Sea Water

Abstract

In the framework of remote sensing studies concerning coastal transport of pollution in the Northern Adriatic Sea, a method has been developed for the quantitative determination of sulphur, iron, titanium, calcium, phosphorus, silicon, aluminium, magnesium in suspended matter of sea water.

The suspended material was collected by filtering on millipore membrane filters with pore width of 0.45 μ and directly analysed by X-ray spectroscopy. For calibration dried solution and particulate standard samples were used. Limits of sensitivity and precision of the method are reported.

Correlations between the concentration of these elements and the total suspended matter/chlorophyll are discussed.

The aim is to study the geochemical composition of particulate matter and its variations within the geographical site of the sea basin and the seasonal conditions. The approach is to consider aluminium and the other elements normalized on Al. On the basis of a matrix correlation analyses of some sets of data chosen in the restricted area for investigation, some hypothesis on superficial distribution of clay, carbonate, iron hydrous oxides and other mineral detrites, are taken into account. The results confirm the complex situation existing in the offshore area of the Venice lagoon from a geochemical point of view.

The suspended matter seem to be argillaceous in the Southern part of the investigated area and semi-argillaceous with hydrous oxides and carbonates in the Northern part which is influenced by the Piave river.