Benefits of Important Industrial Tracer Applications in the GDR

Tracers can be used to label substances or objects in order to discriminate between them, to follow their movement, to record changes of concentration and distribution between phases, etc. The main advantages of tracer investigations are the contactless recording of signals without influencing the observed process (also under rigorous operation conditions), the high detection sensitivity, the large number of available tracer nuclides (problems of all branches of industry can be solved) and the fact that tracer investigation can be carried out on operating production units, so that they provide valuable checks of the validity of design and process data. The cost-to-benefit ratio can be as low as 1:50. In the following some selected examples of tracer applications carried out by the staff of the Central Institute of Isotope and Radiation Research and their benefits will be presented.     

Liquid Chromatographic Residue Analysis of Carbaryl Based on a Post-Column Catalytic Reactor Principle and Fluorigenic Labelling

Abstract

A method is described for the residue analysis of carbaryl in polluted water samples. The technique is based on catalytic hydrolysis of the carbaryl on anion exchangers followed by fluorescence detection of the α-naphthol or the OPA derivative of the methyl amine. A low cost 200 mesh Amberlite strong anion exchanger can be used for this purpose when coupled to the OPA reaction detector. Combining this approach with on-line preconcentration and clean-up on an 3P-18 loaded precolumn can provide a powerful tool for automated residue analysis of carbaryl (and other N-methyl carbamates) in polluted water sources. Recoveries in the order of 100% are reported. The reproducibility of the technique is better than 2% rel. st. dev. Detection limits are 0.4–2 ng per injection for carbaryl depending on the system and linearity of response is more than two orders of magnitude with r = 0.9998. The selectivity and sensitivity of this method permits residue analysis at the sub ppb concentration level in heavily polluted water samples. Data on hydrolysis yields and band broadening as a function of residence time and temperature in the reactor are given.     

优美图的一些性质

对于一个(p,q)-图G,如果存在一个单射.f:V(G)→{0,1,…,q},使得边标号集合{f(uv)| uv∈E(G)}={1,2,…,q},其中边标号为f(uv)=|f(u)-f(v)|,那么称G是优美图,并称.f是G的一个优美标号.通过研究若干优美图,得出一些优美图的性质.     

Novel long alkyl side chain benzo[a]phenoxazinium chlorides: synthesis, photophysical behaviour and DNA interaction

Several fluorescent benzo[a]phenoxazinium chlorides possessing a propyl-, octyl-, decyl-, dodecyl- or tetradecylamino at the 5-position of the heterocyclic moiety were efficiently synthesised. The absorption and emission maxima of all compounds lie in the range 627-638 nm and 654-678 nm, respectively, with good fluorescence quantum yields. Studies of their photophysical properties in ethanol allowed for the estimation of the acid-base dissociation constant, K_a, revealing an enhancement with the increase in the alkyl side-chain length. It is in the aqueous medium only that the acid form is observed as coexisting with H-aggregates. The solubility markedly decreased when the chain length increased. The residual ethanol (0.2% v/v) used to facilitate the solubilisation of the benzo[a]phenoxazinium dyes allow for the existence of the basic form in an aqueous solution, possibly through preferential solvation. Photophysical studies in the presence of DNA revealed that the compounds with an alkyl side chain of up to eight carbon atoms could intercalate between DNA nucleotides. Moreover, other forms of DNA binding were found to be operative, involving also the basic form of benzo[a]phenoxazinium dyes.     

Syntheses of High‐Valent fac‐[99mTcO3]+ Complexes and [3+2] Cycloadditions with Alkenes in Water as a Direct Labelling Strategy

Reported herein is a new concept for the labelling of biomolecules with small [^{99 m}TcO₃]⁺ complexes through a [3+2] cycloaddition with alkenes for radiopharmaceutical applications. We developed convenient reactions for the synthesis of small, water stable fac‐[TcO₃(tacn‐R)]⁺ complexes (⁹⁹Tc and ^99mTc, tacn=1,4,7‐triazacyclononane, R=H, ‐CH₂‐C₆H₅, ‐CH₂‐C₆H₄COOH). With alkenes, these high valent [^99mTcO₃]⁺ complexes undergo [3+2] cycloaddition with formation of the corresponding Tc^V–glycolato complexes. The ^99mTc^V and ^99mTc^VII complexes are stable at 37 °C in water and in the presence of serum proteins. Therefore, new opportunities in technetium chemistry are enabled with a high potential for medicinal and biological applications. In contrast to classical labelling, the presented strategy is ligand and not metal‐centred.     

一种简易的脑片图像的半自动区域划分及细胞计数方法

脑科学研究往往需要对实验动物不同脑区的分子表达、细胞数目及神经网络连接模式进行量化和比较分析,然而目前缺乏简便易行的规模化的脑区划分方法.本文基于Paxinos和Franklin的第二版小鼠图谱以及Photoshop和ImageJ等图像处理软件,发展了一种简易的脑片图像的半自动区域划分及细胞计数方法.首先,基于小鼠脑图谱可获得脑区划分所需的标准模版;然后,利用Photoshop软件对标准模版进行变形矫正,可实现小鼠脑切片图像的快速规模化半自动配准及区域分割;最后,利用ImageJ可实现对配准及分区后的脑片图像不同区域的半自动神经细胞计数和分析.此方法适用于脑片免疫组织化学分析、神经元分布模式检测和神经环路标记等研究,其操作简便、易于获取、并且不依赖于其他昂贵的商业化神经图像分析软件,能为条件有限的科研工作者提供极大便利.     

Split-root labelling to investigate 15N rhizodeposition by Pinus sylvestris and Picea abies*

We investigated the transfer of ¹⁵N into the soil via ¹⁵N uptake and release by tree roots, which involves the principles of the split-root technique. One half of the root system received an injection of (¹⁵NH₄)₂SO₄ and the other half equivalent amounts of (NH₄)₂SO₄ at ¹⁵N natural abundance level. ¹⁵N was transferred from one side of the root system (¹⁵N side) to the other side (¹⁴N side) and released into the soil. The method was conducted with Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies [L.] Karst). Two concentration levels of (NH₄)₂SO₄ were used, corresponding with annual N deposition in the Netherlands (30 kg N ha^–1) and a twelfth of that (2.5 kg N ha^?1). Samples were taken 3 and 6 weeks after labelling and divided into needles?+?stem, roots, rhizosphere and bulk soil. Already 3 weeks after labelling, Scots pine took up 23.7?% of the low and 9.1?% of the high amounts of ¹⁵N, while Norway spruce took up 21.5 and 32.1?%, respectively. Both species transported proportions of ¹⁵N to the rhizosphere (0.1–0.2?%) and bulk soil (0.3–0.9?%). The method is a useful tool to investigate the fate of root-derived N in soils, for example, for the formation of stable forms of soil organic matter.     

Elucidation of the Structure of Lignin–Carbohydrate Complexes in Ginkgo CW-DHP by 13C-2H Dual Isotope Tracer

To elucidate the chemical linkages between lignin and carbohydrates in ginkgo cell walls, ¹³C-²H-enriched cell wall-dehydrogenation polymers (CW-DHP) were selectively prepared with cambial tissue from Ginkgo biloba L. by feeding D-glucose-[6-²H₂], coniferin-[α-¹³C], and phenylalanine ammonia-lyase (PAL) inhibitor. The abundant detection of ¹³C and ²H confirmed that D-glucose-[6-²H₂] and coniferin-[α-¹³C] were involved in the normal metabolism of ginkgo cambial cells that had been effectively labelled with dual isotopes. In the ginkgo CW-DHP, ketal and ether linkages were formed between the C-α of lignin side chains and carbohydrates, as revealed by solid state CP/MAS ¹³C-NMR differential spectroscopy. Furthermore, the DMSO/TBAH ionic liquids system was used to fractionate the ball-milled CW-DHP into three lignin-carbohydrate complex (LCC) fractions: glucan–lignin complex (GL), glucomannan–lignin complex (GML), and xylan–lignin complex (XL). The XRD determination indicated that the cellulose type I of the GL was converted into cellulose type II during the separation process. The molecular weight was in the order of Ac-GL > Ac-GML > XL. The ¹³C-NMR and ¹H-NMR differential spectroscopy of ¹³C-²H-enriched GL fraction indicated that lignin was linked with cellulose C-6 by benzyl ether linkages. It was also found that there were benzyl ether linkages between the lignin side chain C-α and glucomannan C-6 in the ¹³C-²H-enriched GML fraction. The formation of ketal linkages between the C-α of lignin and xylan was confirmed in the ¹³C-²H-enriched XL fraction.