Stability of the FID sensitivity during an analysis in capillary GC

The sensitivity of an FID may change when the carrier gas flow rate changes during a chromatographic run. Sample parts which are eluted at reduced FID sensitivity produce a reduced peak area, hence are discriminated as compared to other components. Sensitivity changes were studied for hydrogen as carrier gas. For the detector tested, differences in the carrier gas flow rates of 1 ml/min shifted the FID sensitivity by 1 to 5% (depending on the fuel gas supply). Thus the stability of the sensitivity is no longer ensured as soon as the carrier gas flow rate is changed manually or by an automatic programmer during an analysis. Sensitivity drifts may also occur during temperature programmed runs with a pressure regulated carrier gas supply since the gas flow through the capillary drops with increasing temperature. Such shifts in the response became noticeable as soon as relatively high carrier gas flow rates combined with long range temperature programmes were used. The typical patterns of such discriminations are shown, closing with a discussion on the possibilities for minimizing such undesired effects.     

Reduction of Chemical Reactions in Nitrogen and Nitrogen–Hydrogen Plasma Jets Flowing into Atmospheric Air

The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities than a specified cutoff sensitivity of 1%. Theactive reactions exert a significant influence on main plasma parameters,such as velocity, temperature, and species concentrations. The sensitivityanalysis for the specified systems shows that two NO reactions, known asZel'dovich reactions (N₂+ONO+N andNO+OO₂+N),⁽¹⁾ are both active in a nitrogenplasma jet. On the other hand, the latter is not active and may be omittedin a nitrogen–hydrogen plasma jet. A nitrogen–hydrogen plasmajet requires contribution of two active charge exchange reactions:N₂+N⁺N⁺ ₂+N andN+H+N+ +H, while only the former is needed in a nitrogen plasmajet. The dissociation reactions are all active in both plasma jets, exceptthe dissociation of OH.     

溴碘化银薄片乳剂颗粒中碘离子分布对潜影分散的影响

碘溴化银乳剂薄片颗粒的潜影分散与碘离子在颗粒中的分布有关。本文用交叉光楔曝光技术测定了由次潜影造成的潜影分散,并根据所测出的潜影分散度和乳剂的表面感光度,对内、表敏的分布作了分析。结果表明,碘离子分布在颗粒边缘的乳剂,其表面潜影分散度要比碘离子均匀分布的颗粒更甚,后者且表现出内、表敏度竞争的现象。     

Importance of the choice of assumptions and models in the estimation of analytical quality specifications

The validity of any model depends on its ability to imagine the situation or problem to which it is applied. Further, the assumptions made in relation to the model are determining for the actual outcome. Within the field of clinical biochemistry a lot of models for analytical quality specifications, based on a variety of concepts and ’clinical settings’, have been proposed. A hierarchical structure for application of these approaches and models has been agreed on at several occasions in 1999. In this hierarchy, the highest rank is given to evaluation of analytical quality specifications based on ’clinical settings’/’clinical outcome’ models, followed by specifications based on biological variation and on ’clinicians opinions’. This contribution, deals with the problems of combining random and systematic errors and the implications of application of different models to a variety of clinical settings. Received: 1 June, 2002 Accepted: 17 July 2002 Presented at the European Conference on Quality in the Spotlight in Medical Laboratories, 7–9 October 2001, Antwerp, Belgium     

Dynamic complexity of optimal paths and discount factors for strongly concave problems

We study the relationship between the dynamical complexity of optimal paths and the discount factor in general infinite-horizon discrete-time concave problems. Given a dynamic systemx _t+1=h(x _t ), defined on the state space, we find two discount factors 0 < ^{* **} < 1 having the following properties. For any fixed discount factor 0 < < ^*, the dynamic system is the solution to some concave problem. For any discount factor ^** < < 1, the dynamic system is not the solution to any strongly concave problem. We prove that the upper bound ^** is a decreasing function of the topological entropy of the dynamic system. Different upper bounds are also discussed.This research was partially supported by MURST, National Group on Nonlinear dynamics in Economics and Social Sciences. The author would like to thank two anonymous referees for helpful comments and suggestions.     

Fluorescence studies and semiempirical calculations on alkali ion indicators

Two newly synthesized cryptands act as sensitive Na⁺- and K⁺-selective indicators for cation concentrations above 20 M. The fluorescence properties change markedly upon cation binding. In addition, the free ligands exhibit a pronounced sensitivity to pH, which is considerably lower for the cation complexes. Time resolved fluorescence is characterized by a decay time of about 5 ns that is attributed to the diprotonated protolytic state of the uncomplexed ligands. Semiempirical calculations show the systematic influence of the nitrogen lone pairs or the N–H bond on the stability of the system. The cause of the strong fluorescence intensity increase observed upon protonation of the fluorescent cryptands may be attributed to an increase in the S₁–T _x energy gap as a consequence of bridgehead nitrogen protonation.This is a peer-reviewed conference proceeding article from the Third Conference on Methods and Applications of Fluorescence Spectroscopy, Prague, Czech Republic, October 18–21, 1993.     

PVP/CHI交联共混水凝胶的pH敏感性研究

制备戊二醛交联的PVP/CH I共混水凝胶,红外光谱佐证了凝胶网络的生成。pH敏感性实验表明,凝胶的溶胀率在pH=1.0的介质中最大,在pH=4.0的介质中次之,在中性或pH=9.0的碱性介质中最低,表明凝胶具有明显的pH敏感性。CH I含量、交联剂用量、CH I脱乙酰度均对凝胶的pH敏感性有影响,CH I含量40%、交联剂用量0.3%、CH I脱乙酰度99%的PVP/CH I凝胶pH敏感性较显著。介质pH值由1.0到7.0变化时,凝胶拉伸强度随着溶胀率的降低而增大。     

特征线法在求解非线性液相吸附色谱模型中的应用

本文应用特征线法求解非线性液相吸附色谱分离过程模型，论述了特征线法的原理和步骤，讨论了时间步长和空间步长对模型数值解的影响，并用色谱分离甘露醇和山梨醇以及分离蔗糖和还原糖的实验进行验证，用特征线法计算的理论流出曲线与实验流出线吻合较好。本文还分折了模型中各个参数的灵敏度，结果表明：吸附等温方程Q＝Ci*／（ai＋biCi*）中参数ai比参数bi以及总传质系数ki有更高的灵敏度。     

Increased electrochemical detector sensitivity by electrode surface modification

Summary Electrode surface modification by electrochemical pretreatment of glassy carbon electrodes was shown to enhance significantly the sensitivity of the electrodes for the detection of timolol and oxprenolol, but reduce slightly the sensitivity to prenalterol. This method may permit the detection of exprenolol and timolol with increased sensitivity, or may allow their detection at lower applied potentials than is presently possible. Electrode surface modification may prove to be a valuable aid to the detection of compounds that are considered to be outside the practical limits of electrochemical detection.     

Is it safe to have a laboratory test?

A recent US Institute of Medicine report indicated that up to 98,000 deaths and more than 1 million injuries occur each year in the United States due to medical errors. These include diagnostic errors, such as an error or delay in diagnosis, failure to employ indicated tests and the use of outmoded tests. Laboratory tests provide up to 80% of the information used by physicians to make important medical decisions, therefore it is important to determine how often laboratory testing mistakes occur, whether they cause patient harm, where they are most likely to occur in the testing process, and how to prevent them from occurring. A review of the literature and a US Quality Institute Conference in 2003 indicates that errors in laboratory medicine occur most often in the pre-analytical and post-analytical steps in the testing process, but most of the quality improvement efforts focus on improving the analytical process. Measures must be developed and employed to reduce the potential for mistakes in laboratory medicine, including better indicators for the quality of laboratory service. Users of laboratory services must be linked with the laboratorys information system to assist them with decisions about test ordering, patient preparation, and test interpretation. Quality assessment efforts need to be expanded beyond external quality assessment programs to encompass the detection of non-analytical mistakes and improving communication between the users of and providers of laboratory services. The actual number of mistakes in laboratory testing is not fully recognized, because no widespread process is in place to either determine how often mistakes occur or to systematically eliminate sources of error. We also tend to focus on mistakes that result in adverse events, not the near misses that cause no observable harm. The users of laboratory services must become aware of where testing mistakes can occur and actively participate in designing processes to prevent mistakes. Most importantly, healthcare institutions need to adopt a culture of safety, which is implemented at all levels of the organization. This includes establishing closer links between providers of laboratory services and others in the healthcare delivery system. This was the theme of a 2003 Quality Institute Conference aimed at making the laboratory a key partner in patient safety. Plans to create a permanent public–private partnership, called the Institute for Quality in Laboratory Medicine, whose mission is to promote improvements in the use of laboratory tests and laboratory services are underway.Presented at the 9th Conference on Quality in the Spotlight, 18–19 March 2004, Antwerp, Belgium.