Isomer-specific influences on the composition of reaction intermediates in dimethyl ether/propene and ethanol/propene flame

This work provides experimental evidence on how the molecular compositions of fuel-rich low-pressure premixed flames are influenced as the oxygenates dimethyl ether (DME) or ethanol are incrementally blended into the propene fuel. Ten different flames with a carbon-to-oxygen ratio of 0.5, ranging from 100% propene (phi = 1.5) to 100% oxygenated fuel (phi = 2.0), are analyzed with flame-sampling molecular-beam mass spectrometry employing electron- or photoionization. Absolute mole fraction profiles for flame species with masses ranging from m/z = 2 (H2) to m/z = 80 (C6H8) are analyzed with particular emphasis on the formation of harmful emissions. Fuel-specific destruction pathways, likely to be initiated by hydrogen abstraction, appear to lead to benzene from propene combustion and to formaldehyde and acetaldehyde through DME and ethanol combustion, respectively. While the concentration of acetaldehyde increases 10-fold as propene is substituted by ethanol, it decreases as propene is replaced with DME. In contrast, the formaldehyde concentration rises only slightly with ethanol replacement but increases markedly with addition of DME. Allyl and propargyl radicals, the dominant precursors for benzene formation, are likely to be produced directly from propene decomposition or via allene and propyne. Benzene formation through propargyl radicals formed via unsaturated C2 intermediates in the decomposition of DME and ethanol is negligibly small. As a consequence, DME and ethanol addition lead to similar reductions of the benzene concentration.     

Er∶Yb∶YCOB晶体制备及其激光二极管抽运激光特性

研究了Er∶Yb∶YCa4O(BO3)3(简称Er∶Yb∶YCOB)的多晶制备和单晶生长,用提拉法生长出光学质量优良的Er∶Yb∶YCOB单晶,测量了其吸收光谱和荧光光谱,分析了其能级和泵浦原理,并进行了以激光二极管为抽运源的激光试验,实现了Er∶Yb∶YCOB晶体的在1.55μm附近110mW的激光输出,且斜效率达18.9;.     

Use of a small particle solid‐core packing for improved efficiency and rapid measurement of sirolimus and everolimus by LC‐MS/MS

Measurement of whole blood sirolimus and everolimus is required in order to optimize patient treatment following solid organ transplant. Assay by LC‐MS/MS is increasingly preferred; however efficient use of the instrument and short turnaround times are crucial. Use of a 1.6 µm solid‐core packing HPLC column (Cortecs) gave significant increases in efficiency, sensitivity and throughput compared with an existing method, following simple protein precipitation of small‐volume (20 μL) whole blood samples. Sirolimus, everolimus and the stable isotopic internal standard (¹³C₂D₄ – everolimus) eluted at around 0.8 min, and total analytical run time was 2.2 min, saving almost 4 min per sample compared with an existing method. Within‐assay imprecision (CV) was 3.3–8.5%, and between‐assay imprecision was 2.2–10.8%. Retrospective assay of external quality assurance samples and comparison of patient samples assayed in parallel showed only small differences (between +6.8 and ?1.9%) in results using the Cortecs column when compared with the existing method. No significant interferences or ion suppression were observed. Copyright © 2015 John Wiley & Sons, Ltd.     

Insertion/isomerization polymerization of 1,5-hexadiene: synthesis of functional propylene copolymers and block copolymers

Polymerization of 1,5-hexadiene with a bis(phenoxyimine) titanium catalyst system is reported. The microstructure of the polymer contains the expected methylene-1,3-cyclopentane units as well as the unexpected 3-vinyl tetramethylene units. A mechanism for formation of this polymer is proposed. This unusual reaction is also employed in the synthesis of vinyl-functional polypropylene copolymers and block copolymers with low polydispersity indices.