Synthesis and mass spectrometry of benzoxazoline, dimethyloxazoline and 4-phenyloxazoline derivatives of polyunsaturated fatty acids

Cyclic nitrogen moieties have proved to be of great value for the mass spectrometric location of double bonds in polyunsaturated fatty acids. However, their synthesis has traditionally required long reaction times and/or high temperatures. Recently, we introduced a one-pot, high-yield, mild and efficient method for the synthesis of various fatty acid amide derivatives. We have now extended this procedure to include the synthesis of benzoxazoline, dimethyloxazoline and 4-phenyloxazoline analogs of a series of fatty acids containing 18 to 22 carbon atoms and 0 to 6 double bonds. A comparison of the mass spectral properties of the three derivatives of these saturated and unsaturated fatty acids is described.     

Nonthermal microwave effects revisited: on the importance of internal temperature monitoring and agitation in microwave chemistry

The concept of nonthermal microwave effects has received considerable attention in recent years and is the subject of intense debate in the scientific community. Nonthermal microwave effects have been postulated to result from a direct stabilizing interaction of the electric field with specific (polar) molecules in the reaction medium that is not related to a macroscopic temperature effect. In order to probe the existence of nonthermal microwave effects, four synthetic transformations (Diels-Alder cycloaddition, alkylation of triphenylphosphine and 1,2,4-triazole, direct amide bond formation) were reevaluated under both microwave dielectric heating and conventional thermal heating. In all four cases, previous studies have claimed the existence of nonthermal microwave effects in these reactions. Experimentally, significant differences in conversion and/or product distribution comparing the conventionally and microwave-heated experiments performed at the same measured reaction temperature were found. The current reevaluation of these reactions was performed in a dedicated reactor setup that allowed accurate internal reaction temperature measurements using a multiple fiber-optic probe system. Using this technology, the importance of efficient stirring and internal temperature measurement in microwave-heated reactions was made evident. Inefficient agitation leads to temperature gradients within the reaction mixture due to field inhomogeneities in the microwave cavity. Using external infrared temperature sensors in some cases results in significant inaccuracies in the temperature measurement. Applying the fiber-optic probe temperature monitoring device, a critical reevaluation of all four reactions has provided no evidence for the existence of nonthermal microwave effects. Ensuring efficient agitation of the reaction mixture via magnetic stirring, no significant differences in terms of conversion and selectivity between experiments performed under microwave or oil bath conditions at the same internally measured reaction temperatures were experienced. The observed effects were purely thermal and not related to the microwave field.     

Energy scavenging for long-term deployable wireless sensor networks

The coming decade will see the rapid emergence of low cost, intelligent, wireless sensors and their widespread deployment throughout our environment. While wearable systems will operate over communications ranges of less than a meter, building management systems will operate with inter-node communications ranges of the order of meters to tens of meters and remote environmental monitoring systems will require communications systems and associated energy systems that will allow reliable operation over kilometers. Autonomous power should allow wireless sensor nodes to operate in a "deploy and forget" mode. The use of rechargeable battery technology is problematic due to battery lifetime issues related to node power budget, battery self-discharge, number of recharge cycles and long-term environmental impact. Duty cycling of wireless sensor nodes with long "SLEEP" times minimises energy usage. A case study of a multi-sensor, wireless, building management system operating using the Zigbee protocol demonstrates that, even with a 1 min cycle time for an 864 ms "ACTIVE" mode, the sensor module is already in SLEEP mode for almost 99% of the time. For a 20-min cycle time, the energy utilisation in SLEEP mode exceeds the ACTIVE mode energy by almost a factor of three and thus dominates the module energy utilisation thereby providing the ultimate limit to the power system lifetime. Energy harvesting techniques can deliver energy densities of 7.5 mW/cm(2) from outdoor solar, 100 microW/cm(2) from indoor lighting, 100 microW/cm(3) from vibrational energy and 60 microW/cm(2) from thermal energy typically found in a building environment. A truly autonomous, "deploy and forget" battery-less system can be achieved by scaling the energy harvesting system to provide all the system energy needs. In the building management case study discussed, for duty cycles of less than 0.07% (i.e. in ACTIVE mode for 0.864 s every 20 min), energy harvester device dimensions of approximately 2 cm on a side would be sufficient to supply the complete wireless sensor node energy. Key research challenges to be addressed to deliver future, remote, wireless, chemo-biosensing systems include the development of low cost, low-power sensors, miniaturised fluidic transport systems, anti-bio-fouling sensor surfaces, sensor calibration, reliable and robust system packaging, as well as associated energy delivery systems and energy budget management.     

HeI photoelectron and valence synchrotron photoionization studies of the thioester molecule CH3C(O)SCH3: evidence of vibronic structure

One of the simplest thioester molecules, S-methyl thioacetate, CH 3C(O)SCH 3, has been investigated by HeI photoelectron spectroscopy (PES) and valence photoionization studies using synchrotron radiation in the same energy range. In the second series of experiments, total ion yield (TIY), photoelectron photoion coincidence (PEPICO), and partial ion yield (PIY) spectra were recorded. It was found that the photodissociation behavior of CH 3C(O)SCH 3 can be divided into three well-defined energy regions. Vibronic structure was observed in the valence synchrotron photoionization process, being associated with wavenumbers of 912, 671, 1288, 1690, and 1409 cm (-1) for the bands at 12.82, 13.27, 15.66, 15.72, and 17.42 eV, respectively. Evaluation of the PE spectrum in concert with the synchrotron photoionization measurements and complemented by high-level ab initio calculations thus provides unusually detailed insights into the valence ionization processes of this molecule.     

Electric dipole echoes in Rydberg atoms

We report the first observation of echoes in the electric dipole moment of an ensemble of Rydberg atoms precessing in an external electric field F. Rapid reversal of the field direction is shown to play a role similar to that of a pi pulse in NMR in rephasing a dephased ensemble of electric dipoles resulting in the buildup of an echo. The mechanisms responsible for this are discussed with the aid of classical trajectory Monte Carlo simulations.     

First observation of K{L}-->pi{+/-}e{-/+}nue{+}e{-}

This Letter is the first report of the K{L}-->pi{+/-}e{-/+}nue{+}e{-} decay. Based on 19 208+/-144 events, we determine the branching fraction, B(K{L}-->pi{+/-}e{-/+}nue{+}e{-}M_{e{+}e{-}}>5 MeV/c{2},E{e{+}e{-}}{*}>30 MeV)=(1.285+/-0.041)x10{-5}, and Gamma(K{e3ee}M{e{+}e{-}}>5 MeV/c{2})/Gamma(K{e3})=[4.57+/-0.04(stat)+/-0.14(syst)]x10{-5}. This ratio agrees with a theoretical prediction based on chiral perturbation theory (ChPT) calculated to O(p{4}). The measured kinematical distributions agree with those predicted by just ChPT O(p{4}), but show significant disagreement with ones predicted by leading-order ChPT.     

One-pot, multicomponent route to pyrazoloquinolizinones

[reaction: see text] An efficient synthesis of 5a-hydroxy-4,5,5a,6,7,8-hexahydropyrazolo[4,3-c]quinolizin-9-ones based on the three-component condensation of 5-aminopyrazoles, aromatic aldehydes, and cyclic 1,3-diketones is described. The multicomponent reaction is performed under strongly basic conditions applying controlled microwave heating in a sealed vessel and involves an unusual base-mediated ring-opening/recyclization of the cyclic 1,3-diketone moiety.     

Promoting helicity in carbohydrate-containing foldamers through long-range hydrogen bonds

A sensor system to probe the propensity of carbohydrates to induce helical structures through long-range hydrogen bonds, based on a C(2)-symmetric xylylene bis(thiourea) arrangement, is reported; the formation of intermolecular complexes with benzoate anion promotes helix uncoiling, the free energy of the process being related to helix stability.     

面向车载应用的高性能图形系统控制器

富士通高性能图形系统控制器产品整合了＂FR81S＂这款高性能的CPU内核,是集合彩色显示和视频输入及仪表控制等各种功能为一体的单一芯片解决方案。该系列产品可应用于汽车仪表板,除支持彩色液晶显示的MB91590系列外,富士通还推出了支持段型液晶显示的MB91570系列。     

编后感

《印制电路信息》杂志2010年增刊出版了。它是秋季PCB技术/信息论坛论文的专刊。它凝聚了我们印制电路行业广大管理人员、工程技术人员的智慧和汗水。是创新的结晶,更是我们