Die kalibrierfreie Bestimmung von Creatinin und Ammoniak durch coulometrische Mikrodurchflußtitration

Zu den entscheidenden Problemen des praxisnahen Biosensoreinsatzes zählen neben der Gewährleistung einer hohen Langzeitstabilität der Meßergebnisse die Erreichung einer z.B. für prozeß – und routineanalytische Anwendungen ausreichend hohen Genauigkeit. Diese Ziele sollten durch die Kombination weitgehend absolut, d.h. kalibrierfrei arbeitender Bestimmungsverfahren mit quantitativ arbeitenden Mikro-trennschritten und enzymatischen Analytkonversionen erreichbar sein. Dies wird am Beispiel der kalibrierfreien Bestimmung von Creatinin und Ammoniak demonstriert. Das vorgeschlagene Bestimmungsverfahren beruht auf der Kombination einer kalibrierfrei arbeitenden coulometrischen Mikrodurchflußtitration von Ammoniak mit der quantitativen, durch Creatininiminohydrolase (CIH) katalysierten Creatininumsetzung sowie der schnell arbeitenden gasdialytischen Abtrennung des freigegetzten Ammoniaks über eine mikroporöse Teflonmembran. Das abgetrennte Ammoniak wird mit elektrolytisch durch anodische Bromidoxydation erzeugtem Hypobromit amperometrisch titriert. Mit dem vorgeschlagenen coulometrischen Detektionsverfahren können sowohl Creatinin als auch Ammoniak im Konzentrationsbreich zwischen 10 mM und 0.5 mM mit relativen Standardabweichungen von < 0.5 % ( n = 4 ) bei Titrationszeiten ³ 40 s ohne Kalibrierung, d.h. praktisch „absolut“ bestimmt werden. Der zugängliche Creatininbestimmungsbereich liegt zwischen 10-6 M und 2 mM. Die Leistungsfähigkeit des Systems wurde bei der Analyse von verdünnten Urinproben demonstriert und erlaubt die Anwendung auf die langzeitstabile Analyse von Dialysaten. Ähnliche Ergebnisse wurden bei der kalibrierfreien Bestimmung von Harnstoff und L-Glutamin erreicht

Thermodynamics of quantum systems under dynamical control

In this review the debated rapport between thermodynamics and quantum mechanics is addressed in the framework of the theory of periodically-driven/controlled quantum-thermodynamic machines. The basic model studied here is that of a two-level system (TLS), whose energy is periodically modulated while the system is coupled to thermal baths. When the modulation interval is short compared to the bath memory time, the system-bath correlations are affected, thereby causing cooling or heating of the TLS, depending on the interval. In steady state, a periodically-modulated TLS coupled to two distinct baths constitutes the simplest quantum heat machine (QHM) that may operate as either an engine or a refrigerator, depending on the modulation rate. We find their efficiency and power-output bounds and the conditions for attaining these bounds. An extension of this model to multilevel systems shows that the QHM power output can be boosted by the multilevel degeneracy. These results are used to scrutinize basic thermodynamic principles: (i) Externally-driven/modulated QHMs may attain the Carnot efficiency bound, but when the driving is done by a quantum device ("piston"), the efficiency strongly depends on its initial quantum state. Such dependence has been unknown thus far. (ii) The refrigeration rate effected by QHMs does not vanish as the temperature approaches absolute zero for certain quantized baths, e.g., magnons, thous challenging Nernst's unattainability principle. (iii) System-bath correlations allow more work extraction under periodic control than that expected from the Szilard-Landauer principle, provided the period is in the non-Markovian domain. Thus, dynamically-controlled QHMs may benefit from hitherto unexploited thermodynamic resources

Very Singular Diffusion Equations-Second and Fourth Order Problems

This paper studies singular diffusion equations whose diffusion effect is so strong that the speed of evolution becomes a nonlocal quantity. Typical examples include the total variation flow as well as crystalline flow which are formally of second order. This paper includes fourth order models which are less studied compared with second order models. A typical example of this model is an H−1 gradient flow of total variation. It turns out that such a flow is quite different from the second order total variation flow. For example, we prove that the solution may instantaneously develop jump discontinuity for the fourth order total variation flow by giving an explicit example

What Do We Know About Neuropsychological Aspects Of Schizophrenia?

Application of a neuropsychological perspective to the study of schizophrenia has established a number of important facts about this disorder. Some of the key findings from the existing literature are that, while neurocognitive impairment is present in most, if not all, persons with schizophrenia, there is both substantial interpatient heterogeneity and remarkable within-patient stability of cognitive function over the long-term course of the illness. Such findings have contributed to the firm establishment of neurobiologic models of schizophrenia, and thereby help to reduce the social stigma that was sometimes associated with purely psychogenic models popular during parts of the 20th century. Neuropsychological studies in recent decades have established the primacy of cognitive functions over psychopathologic symptoms as determinants of functional capacity and independence in everyday functioning. Although the cognitive benefits of both conventional and even second generation antipsychotic medications appear marginal at best, recognition of the primacy of cognitive deficits as determinants of functional disability in schizophrenia has catalyzed recent efforts to develop targeted treatments for the cognitive deficits of this disorder. Despite these accomplishments, however, some issues remain to be resolved. Efforts to firmly establish the specific neurocognitive/neuropathologic systems responsible for schizophrenia remain elusive, as do efforts to definitively demonstrate the specific cognitive deficits underlying specific forms of functional impairment. Further progress may be fostered by recent initiatives to integrate neuropsychological studies with experimental neuroscience, perhaps leading to measures of deficits in cognitive processes more clearly associated with specific, identifiable brain systems

Ecological feedback in quorum-sensing microbial populations can induce heterogeneous production of autoinducers

Autoinducers are small signaling molecules that mediate intercellular communication in microbial populations and trigger coordinated gene expression via "quorum sensing". Elucidating the mechanisms that control autoinducer production is, thus, pertinent to understanding collective microbial behavior, such as virulence and bioluminescence. Recent experiments have shown a heterogeneous promoter activity of autoinducer synthase genes, suggesting that some of the isogenic cells in a population might produce autoinducers, whereas others might not. However, the mechanism underlying this phenotypic heterogeneity in quorum-sensing microbial populations has remained elusive. In our theoretical model, cells synthesize and secrete autoinducers into the environment, up-regulate their production in this self-shaped environment, and non-producers replicate faster than producers. We show that the coupling between ecological and population dynamics through quorum sensing can induce phenotypic heterogeneity in microbial populations, suggesting an alternative mechanism to stochastic gene expression in bistable gene regulatory circuits

Regulation of antibiotic production in Actinobacteria: new perspectives from the post-genomic era

The antimicrobial activity of many of their natural products has brought prominence to the Streptomycetaceae, a family of Gram-positive bacteria that inhabit both soil and aquatic sediments. In the natural environment, antimicrobial compounds are likely to limit the growth of competitors, thereby offering a selective advantage to the producer, in particular when nutrients become limited and the developmental programme leading to spores commences. The study of the control of this secondary metabolism continues to offer insights into its integration with a complex lifecycle that takes multiple cues from the environment and primary metabolism. Such information can then be harnessed to devise laboratory screening conditions to discover compounds with new or improved clinical value. Here we provide an update of the review we published in NPR in 2011. Besides providing the essential background, we focus on recent developments in our understanding of the underlying regulatory networks, ecological triggers of natural product biosynthesis, contributions from comparative genomics and approaches to awaken the biosynthesis of otherwise silent or cryptic natural products. In addition, we highlight recent discoveries on the control of antibiotic production in other Actinobacteria, which have gained considerable attention since the start of the genomics revolution. New technologies that have the potential to produce a step change in our understanding of the regulation of secondary metabolism are also described

Thermal conductivity measurements of road construction materials in frozen and unfrozen state

A series of thermal conductivity measurements for various materials was performed in a large climate chamber. The size of the chamber allowed the preparation of relatively large samples in a controlled thermal environment. Three types of thermal sensors were used: (1) two needle probes; (2) a grid of temperature sensors, evenly distributed inside the sample; (3) two additional thermal probes, which were simplified versions of an instrument originally developed for measuring thermal properties of the ice/dust mixture expected to exist at the surface of a comet nucleus. They consist of a series of individual temperature sensors integrated into a glass fibre rod. Each of these sensors can be operated in an active (heated) or passive (only temperature sensing) mode. The following sample materials were used: fine-grained reddish sand, coarse-grained moist sand, gravels with various grain size distributions from < 1 cm up to about 6 cm, and for comparison and calibration pure water (with convection suppressed by adding agar-agar), compact ice, and compact granite. Of particular interest are the measurements with composite samples, like stones embedded in an agar-agar matrix. We describe the evaluation methods and present the results of the thermal conductivity measurements