Transition to the ultimate state of turbulent Rayleigh-Bénard convection

Measurements of the Nusselt number Nu and of a Reynolds number Re(eff) for Rayleigh-Bénard convection (RBC) over the Rayleigh-number range 10(12)?Ra?10(15) and for Prandtl numbers Pr near 0.8 are presented. The aspect ratio Γ≡D/L of a cylindrical sample was 0.50. For Ra?10(13) the data yielded Nu∝Ra(γ(eff)) with γ(eff)?0.31 and Re(eff)∝Ra(ζ(eff)) with ζ(eff)?0.43, consistent with classical turbulent RBC. After a transition region for 10(13)?Ra?5×10(14), where multistability occurred, we found γ(eff)?0.38 and ζ(eff)=ζ?0.50, in agreement with the results of Grossmann and Lohse for the large-Ra asymptotic state with turbulent boundary layers which was first predicted by Kraichnan.     

Chlorine and sulfur determination in extra-heavy crude oil by inductively coupled plasma optical emission spectrometry after microwave-induced combustion

In this study, microwave-induced combustion (MIC) of extra-heavy crude oil is proposed for further chlorine and sulfur determination by inductively coupled plasma optical emission spectrometry (ICP OES). Combustion was carried out under oxygen pressure (20 bar) in quartz vessels using ammonium nitrate (50 µl of 6 mol l^− 1 solution) as ignition aid. Samples were wrapped with polyethylene film and placed on a quartz holder positioned inside the quartz vessels. The need for an additional reflux step after combustion and the type and concentration of absorbing solution (water, 0.02 to 0.9 mmol l^− 1 H₂O₂, 10 to 100 mmol l^− 1 (NH₄)₂CO₃ or 0.1 to 14 mol l^− 1 HNO₃) were studied. The influence of sample mass, O₂ pressure and maximum pressure attained during the combustion process were investigated. Recoveries from 92 to 102% were obtained for Cl and S for all absorbing solutions. For comparison, Cl and S determination was also performed by ion chromatography (IC) using 25 mmol l^− 1 (NH₄)₂CO₃ as absorbing solution. Using MIC with a reflux step the agreement was better than 95% for certified reference materials of similar composition (crude oil, petroleum coke, coal and residual fuel oil). Microwave-assisted digestion and water extraction in high pressure closed vessels were also evaluated. Using these procedures the maximum recoveries were 30 and 98% for Cl and S, respectively, using microwave-assisted digestion and 70% for Cl and less than 1% for S by water extraction procedure. Limits of detection by ICP OES were 12 and 5 µg g^− 1 for Cl and S, respectively, and the corresponding values by IC were 1.2 and 8 µg g^− 1. Using MIC it was possible to digest simultaneously up to eight samples resulting in a solution suitable for the determination of both analytes with a single combustion step.     

单级高频脉冲管制冷机研究

采用单级高频脉冲管制冷机获得低于30 K的制冷温度是脉冲管应用的一个新方向.本文介绍了一套获得了26 K最低制冷温度的单级高频脉冲管制冷机,这是无多路旁通的单级高频脉冲管制冷机获得的最低温度.实验表明,即使对于惯性管作为主要调相结构的高频情况,双向进气方案在进一步调相和降低温度方面仍有很大作用.该工作为单级高频脉冲管制冷机在30～40 K温区的应用奠定了基础.该实验结果和模拟分析结果基本相符.通过和二级制冷机的比较说明了单级制冷机的优势,即较大的制冷量斜率.     

Sub-nanogram per litre detection of the emerging contaminant progesterone with a fully automated immunosensor based on evanescent field techniques

Progesterone is reasonably anticipated to be a human carcinogen based on sufficient evidence of carcinogenicity in experimental animals and it can be found in various surface waters which are partly used as drinking water resources. Therefore, immunoanalytical methods at a very low limit of detection (LOD) and a low limit of quantification (LOQ) are becoming more and more important for environmental analysis and especially for monitoring drinking water quality. Biosensors have suitable characteristics such as efficiency in allowing very fast, sensitive, and cost-effective detection. Here we describe a fully automated immunoassay for progesterone with a LOD in the sub-nanogram per litre range and a LOQ in the lower nanogram per litre range. In contrast to common analytical methods such as GC-MS or HPLC-MS, the biosensor used requires no sample pre-treatment and no sample pre-concentration. The basis of our sensitive assay is the antibody with a high affinity constant towards progesterone and the robust biosensor setup used.     

SnCl4-catalyzed reaction of o-benzoquinones and aryl acetylenes: an unprecedented one-pot synthesis of tropone derivatives

Highly substituted tropone derivatives were obtained as a result of SnCl4-catalyzed cycloaddition of 3-methoxy-substituted o-benzoquinones with aryl acetylenes and subsequent rearrangement of the adducts with concomitant decarbonylation.     

Technetium complexes with thioether ligands—III. Synthesis and structural characterization of cationic nitridotechnetium(V) complexes with thiacrown ethers

The first representative of a new class of TcN complexes with thiacrown ethers have been prepared by ligand exchange reaction of NBu₄[TcNCl₄] with 1,4,8,11-tetrathiacyclotetradecane (14S4), 1,5,9,13-tetrathiacyclohexadecane (16S4), 1,5,9,13-tetrathiacyclohexadecane-3,11-diole (16S4-(OH)₂) and 1,4,7,10,13,16-hexathiacyclooctadecane (18S6). The crystal structure of [TcNCl(14S4)]TcNCl₄ 1) consists of couples of independent cations with the metal in the oxidation state + 5 and hexavalent TcNCl₄⁻ anions. In the complex cation the metal is six-coordinated in a rather distorted octahedral geometry, being directly bound to four sulphur atoms from the macrocyclic ligand in the equatorial plane and to the nitrido atom and to one chlorine atom in the axial positions. The strong trans influence of the nitrido ligand causes an extreme lengthening of the Tc---Cl bond distance to 2.718 Å. The octahedral molecular structure of [TcNCl(18S6)]TcNCl₄ (3) is comparable with that of 1, but only four sulphur atoms of the thiacrown ether form the equatorial plane, two sulphur atoms remain non-coordinated, and the nitrido and Cl⁻ ligands are in axial positions. The most interesting feature in the structure of [TcNCl(16S4-(OH)₂)]Cl (5) is the observation of an exceptionally long Tc---N distance of 1.95 Å.     

The determination of the nitrogen content and nitrogen-15 abundance by means of the nitrogen gas generated from inorganic and organic materials

A method is described for the determination of the total nitrogen content, after conversion to nitrogen gas, of various types of samples before the mass-spectrometric analysis of the ¹⁵N abundance. The sample is burned with a mixture of copper oxide, copper and lime in a closed tube under vacuum (modified Dumas method). The gas is released into an evacuated chamber of known volume and the nitrogen pressure is used to determine the nitrogen content of the sample. The gas is then admitted into a mass spectrometer. In order to obtain complete combustion of the material and to generate pure nitrogen gas, various combustion temperatures, combustion times and oxidizing agents were compared.