Carbon dioxide effects on luminol and 1,10-phenanthroline chemiluminescence

Luminol and 1,10-phenanthroline are widely used chemiluminescent (CL) reagents for the analysis of a wide range of metals and inorganic and organic complexes. While the fundamental mechanism for luminol and 1,10-phenantholine chemiluminescence is understood, the analytical application of these reagents is largely empirical and often poorly described mechanistically. For example, CL signals observed from metal-luminol systems are strongly dependent on the pH of the sample, even though the final pH of the reaction mixture is controlled to a narrow range by a buffer. Other investigators report significant changes in CL signal due to freshness and the acidity of reagents. Our work shows that many of these effects are due to dissolved CO2 present or formed in the analytical system. The hypothesis that carbon dioxide plays a pivotal role in enhancing luminol CL is supported by direct manipulation of CO2(aq) concentrations by the addition of CO2(g) or carbonic anhydrase. In contrast, Cu(II) analysis using the CL reagent 1,10-phenanthroline is completely quenched in the presence of CO2(aq). A plausible mechanism for these observations involves the reaction between superoxide, produced in these analytical systems, and CO2(aq) to form the peroxycarbonate radical, *C04-. The formation of *CO4- has very important analytical implications since this species appears to enhance or quench the CL signal from luminol and 1,10-phenanthroline, respectively.     

Electrokinetic stacking injection of neutral analytes under continuous conductivity conditions

In capillary electrokinetic chromatography, neutral analytes can be injected by electroosmotic flow directly from a sample matrix into a separation buffer containing an electrokinetic vector with an opposite mobility. Analytes are injected at the velocity of electroosmotic flow but are retained at the interface of the sample matrix co-ion and separation buffer micelle zones as analyte/micelle complexes. A simple electrokinetic chromatography system containing sodium dodecyl sulfate as the micellar agent with borate as the buffering electrolyte included in the separation buffer and in the sample matrix to provide continuous conductivity was investigated. Concentrations of the micelle, methanol, and borate in the separation buffer were explored to increase maximum injection length of neutral analytes. Reducing the analyte velocity in the separation buffer without substantially decreasing the velocity of the analyte during injection from the sample vial allowed greatly extended sample plug injection lengths. It is presently possible to inject sample solvent volumes equivalent to approximately 7 effective capillary lengths (180 cm) with a 50-microm-i.d. capillary (24.5 cm effective capillary length), total volume of sample injection approximately 3.5 microL Equations describing the injection process and maximum injection lengths for this mode of stacking in electrokinetic capillary chromatography are introduced. The result of this work leads to a postulated generalization of electrokinetic stacking injection maximums for electrophoretic processes, and the concept of orthogonal analyte stacking/injection systems is discussed.     

Ethics,data-dependent designs,and the strategy of clinical trials: time to start learning-as-we-go?

The seeds of modern clinical trials were unwittingly sown with the first use of randomization in a 1920s agricultural field experiment. The historical development of trials is briefly reviewed here, as are multifarious pressures and problems faced by those involved with clinical trials today. These challenges include recruitment difficulties, the emerging role of patient support groups, and legal threats over informed consent, to name three. Fundamentally, they reflect an overall shift towards patient-centred, individual ethics. I suggest many problems may be overcome by increased implementation of hitherto neglected, data-dependent designs for clinical trials. Over a dozen arguments against their use are countered, primarily through ethical considerations. Benefits and costs of refining clinical trials strategy are explored hypothetically under enhanced use of such 'learn-as-you-go' designs, in contrast to traditional, equal-allocation, fixed-sample-size and frequentist-based designs. These latter methods mirror crop field trials in which one cannot make scientific progress until after gathering objective data at harvest time. Some attempts to alleviate certain problems, such as Zelen randomization to boost recruitment, or over-reliance on 'large and simple trials' to detect moderate-sized treatment effects, are discussed and found inadequate. A proposal for wider discussion is made to assist the selective introduction of 'small and complex trials,' which could simultaneously expedite medical research, satisfy the concerns of regulators, statisticians, and doctors alike, and help address the growing demands of 21st-century patients.     

Designing consumer interfaces for experiential tasks: an empirical investigation

In the early adoption phase of business-to-consumer (B2C) ecommerce, the tasks that proved most conducive to online consumer interaction typically were goal-directed, being clear in sequence and structure. A key challenge in ecommerce is the ability to design interfaces that support experiential tasks in addition to goal-directed tasks. Most of the ecommerce research on interface design, however, has focused on goal-directed tasks and has not addressed experiential tasks. Based on the literature from interface metaphors and mental models, this paper explores the use of tangible attributes derived from the physical business domain as a technique for designing an interface that effectively supports experiential tasks. A laboratory experiment was designed and conducted to test the impact of two types of interfaces and business domain familiarity when completing an experiential task. Because consumers need to retain and recall information to evaluate products/services or to make brand associations, retention/recall of information was measured on both the day of the treatment and after a 2-day lag. Results revealed that the interface based upon the business domain metaphor stimulated higher levels of retention and recall of information and thus provided the desired support for experiential tasks. Further, users with weaker domain familiarity showed the greatest improvement in retention and recall, particularly after a 2-day lag, when using the interface with the business domain metaphor design.     

Method for repetitive measurement of the electrostatic chargingtendency of liquid dielectrics

The construction of an apparatus for the measurement of the electrostatic charging tendency (ECT) of a dielectric liquid is described. A sealed reciprocating piston arrangement permits a liquid to be repetitively passed through a charge separating element. The use of a gold element is shown to minimize the effects of moisture and control temporal effects. The system is evaluated by testing samples of transformer oil drawn from the field. In general, the new system ranks the oils in the same way as a conventional assessment against a paper filter, although anomalies have been found which are an impediment to adoption     

Ophthalmic findings with partial trisomy (duplication) of the long arm of chromosome 7

BACKGROUND: The sensitivity of diagnostic imaging of processes in the parotid gland has been increased by improved spatial resolution, yet specificity remains unchanged. The purpose of this study was to determine whether the low-flow color duplex technique alters the specificity of B-mode ultrasonography. PATIENTS AND METHODS: Forty-one patients with tumors of the parotid gland were examined by color duplex echography as well as histologically. Twenty-eight of the 41 patients had benign tumors and 13 had malignant disease. In 17 of 41 patients, color duplex ultrasonography failed to detect any vascularization within the tumor. Histopathological examination showed that 3 of these 17 tumors were malignant and 14 of 17 were benign. Intranodal vascularization was detected in 24 cases. Ten of these patients were found to have malignant tumors of the parotid gland; 14 had benign parotid tumors. RESULTS: Our present findings show that marked intratumoral vascularization especially appears in malignant tumors. In contrast to lymph nodes, the location and texture of intranodal blood vessels do not provide information about the nature of the neoplasm. CONCLUSIONS: Low flow duplex ultrasonography does not increase the specificity of preoperative examination in tumors of the parotid gland.     

Epidemiology of giardiasis and cryptosporidiosis in Jamaica

We report the findings of a cross-sectional epidemiologic study of Giardia lamblia and Cryptosporidum infections in Jamaica. Three hundred twenty eight stool samples from patients less than one to 81 years of age were examined using formalin-ether concentration for G. lamblia, Zeihl-Neelsen staining for Cryptosporidium, and the Prospect rapid enzyme immunoassay (EIA; Alexon, Sunnyvale, CA) for parasite diagnosis. The Prospect Giardia rapid assay detected 17 cases of G. lamblia infection compared with six by formalin-ether concentration. However, the Prospect Cryptosporidum EIA did not increase the rate of detection of Cryptosporidum when compared with Zeihl-Neelsen staining. Cryptosporidum infections were most frequently diagnosed in children less than five years old and prevalence decreased with age. In contrast, the prevalence of giardiasis increased as children became older. There were no associations between the infections and stool consistency, clinical manifestations, or sex of the individuals. The contribution of the parasites to childhood morbidity will depend on accurate laboratory diagnosis.     

Flexible sigmoidoscopy training program for internal medicine residents

We examined the possibility of an association between the bacterial genotype of Escherichia coli O157:H7 and the likelihood of progression to neurological complications in childhood gastroenteritis-associated haemolytic uraemic syndrome (D+HUS). Bacterial stool isolates were available from 51 patients with HUS; 11 of these patients suffered a neurological complication. Bacteria were assessed for plasmid content, verotoxin (Shiga-like toxin) profile, verotoxin 2 subtype, and presence of the eaeA (effacement and attachment) marker. No association of bacterial genotype with central nervous system (CNS) manifestations was observed. Whilst the cause of CNS manifestations may be multifactorial, there is no evidence at present to implicate specific bacterial traits.