Implementation of ISO Guide 34: Accreditation for reference material production

The National Analytical Reference Laboratory of the Australian Government Analytical Laboratories was initially accredited to ILAC Guide G 12:2000 in January 2000 and is currently accredited to ISO Guide 34 (2000) for the production of a range of pure organic substance reference materials. This paper discusses the practical challenges and rewards of developing and implementing a quality system for reference material production and discusses some of the barriers, and potential solutions, to more general implementation of third-party accreditation.     

A New Approach to the Synthesis of Cortical Steroids

A new bondset for cortical steroid synthesis is developed from the dual concepts of convergent assembly and multiple construction. A short synthesis on this bondset is presented in which the final bond construction by electrocyclization took an unwanted course. Stereocontrol is discussed separately.     

Crystal and molecular structures of three germylated steroids

Germylated steroids were studied by X-ray diffraction analysis for the first time. The conformational parameters of the molecules in the crystals are discussed. The three-center hypervalent O−Ge−Cl bonds are observed in two β-isomers. The geometric parameters of the hypervalent units are compared. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 116–122, January, 1999.     

Development of a liquid chromatography-tandem mass spectrometry method for the identification of natural androgen steroids and their conjugates in urine samples

An analytical procedure for the determination of natural steroids and their conjugates was developed and applied to bovine and human urine. Fifteen compounds (free and conjugated) after extraction by solid-phase were identified by liquid chromatography-tandem mass spectrometry (LC-MS-MS) in multiple reaction monitoring (MRM). Free and conjugated steroids were detected all together in the same chromatographic analysis respectively in positive and negative ionization. This procedure reveals to be time-saving, because it overcomes the need of further sample pre-treatment steps, such as enzymatic hydrolysis and derivatisation.The recovery for each compound was around 80%. Limit of detection of each steroid free or conjugated has been evaluated.     

Crystal structures of 4,11-pregnadiene-3,20-dione and 21-methyl-20-oxa-4-pregnene-3,20-dione

The structures of the title compounds were solved by direct methods and refined by anisotropic full-matrix least-squares methods. 4,11-Pregnadiene-3,20-dione, C₂₁H₂₈O₂(1) crystallizes in the monoclinic space groupP2₁ (Z=2). The unit cell parametersa, b, c (Å), and (°) were: 12.319(2), 7.700(2), 9.717(2), 109.41(2). TheA- andC-rings exhibit intermediate sofa-halfchair conformations. TheB-ring has a chair conformation and theD-ring assumes an intermediate envelope-half-chair conformation. The progesterone side chain has a typical conformation; the C16–C17–C20–O20 torsion angle is –15.1(4)°. 21-Methyl-20-oxa-4-pregnene-3,20-dione, C₂₁H₃₀O₃ (2) crystallizes in the orthorhombic space groupP2₁2₁2₁ (Z=4). The unit cell parametersa, b, c (Å) were: 12.926(2), 19.447(4), 7.313(1). The progesterone side chain has an unusual conformation; the C16–C17–C20–O20 torsion angle is 174.6(4)°. TheA-ring has a 1, 2-half-chair conformation, ringsB andC exhibit chair conformations and ringD is in a 13,14-half-chair conformation.     

Crystal and molecular structures of (20R)-20-aminopregn-5-en-3β-ol and (20S)-20-aminopregn-5-en-3β-ol hydrochloride

Two epimers of 20-aminopregn-5-en-3-ol differing in configuration at C(20) have been synthesized and their structures have been determined by single crystal X-ray diffraction methods. The (20R)-epimer (1) crystallized in the orthorhombic system, space group P2₁2₁2₁, with a = 9.0432(5) Å, b = 13.3446(7) Å, c = 15.1086(8) Å, and Z = 4. The (20S)-epimer hydrochloride hydrate (2 hydrate) crystallized in the monoclinic system, space group C2, with a = 31.0501(3) Å, b = 11.8221(1) Å, c = 11.9703(2) Å, = 98.5140(10)°, and Z = 8. The absolute configurations at the C(20) chiral centers for the title compounds were unequivocally established for the first time. The asymmetric unit cell of 2 hydrate contained two steroid molecules, A and B, two hydrochloride molecules, and two molecules of water. The crystal packing for both diastereomers was strongly influenced by the presence of intermolecular hydrogen bonding. The molecules of 1 were linked in a head-to-tail fashion via hydrogen bonds between the hydroxyl group of the ring A and the amino group of the side chain of the ring D. The two molecules A and B of 2 hydrate were held together in head-to-head and head-to-tail fashions by a three-dimensional network of hydrogen bonds involving chlorine ions, disordered water molecules, and hydroxyl–amino groups interactions.     

简易脑功能近红外光谱系统设计

功能近红外光谱(functional near-infrared spectroscopy, fNIRS)是一种无损的脑成像技术,经过20年的发展,已广泛应用于认知神经科学研究领域。基于神经血管耦合机制,与功能相关的大脑神经活动增强会引起局部脑血流量的升高,进而引发血液中氧合血红蛋白与脱氧血红蛋白浓度相应的变化,间接反映了大脑中神经激活程度。研制了一套基于多功能采集卡的单通道连续波fNIRS系统。在该系统中,选择激光二极管作为光源具有较好的单色性和较低的发散角,690和830 nm波长的组合有助于降低发色团之间的串扰。频分复用技术用于区分来自不同光源的信号,同时也消除了环境光、工频干扰等特定频率的噪声源。利用LabVIEW软件平台实现了光源的时序控制、自动增益调节、数字正交相干解调,以及数据可视化与存储等功能。屏气和心算实验结果表明,该系统可用于监测大脑局部血红蛋白浓度的实时变化,并可以检测与高级脑功能相关的激活。