Electrochemiluminescent detection of metal cations using a ruthenium(II) bipyridyl complex containing a crown ether moiety

The effects of metal ions on the electrochemiluminescence (ECL) properties of (bpy)2Ru(AZA-bpy) (bpy = 2,2'-bipyridine; AZA-bpy = 4-(N-aza-18-crown-6-methyl-2,2'-bipyridine) have been investigated. The electrochemistry, photophysics and ECL of Ru(bpy)3(2+) in the presence of Pb2+, Hg2+, Cu2+, and K+ are reported. The anodic oxidation of Ru(bpy)3(2+) produces ECL in the presence of tri-n-propylamine (TPrA) in 50:50 (v/v) CH3CN:H2O solution. Increases in ECL efficiency (photons generated per redox event) up to 20-fold that depend on both the concentration and nature of the metal ion have been observed, making this an interesting system for electrochemiluminescence metal ion sensing.     

Cryogenic probe 13C NMR spectroscopy of urine for metabonomic studies

Cryogenic probe technology can significantly compensate for the inherently low sensitivity of natural abundance 13C NMR spectroscopy. This now permits its routine use in NMR spectroscopy of biofluids, such as urine or plasma, with acquisition times that enable a high throughput of samples. Metabonomic studies often generate numerous samples in order to characterize fully the time-dependent biochemical response to stimuli, but until now, they have been largely conducted using 1H NMR spectroscopy because of its high sensitivity and hence efficient data acquisition. Here, we demonstrate that information-rich 13C NMR spectra of rat urine can be obtained using appropriately short acquisition times suitable for biochemical samples when using a cryogenic probe. Furthermore, these data were amenable to automated pattern recognition analysis, which produced a profile of the metabolic response to the model hepatotoxin hydrazine that was consistent with earlier studies. Thus, a new source of detailed and complementary information is available to metabonomics using cryogenic probe 13C NMR spectroscopy.     

Management of Multi-Queue Switches in QoS Networks

The concept of Quality of Service (QoS) networks has gained growing attention recently, as the traffic volume in the Internet constantly increases, and QoS guarantees are essential to ensure proper operation of most communication-based applications. A QoS switch serves m incoming queues by transmitting packets arriving to these queues through one output port, one packet per time step. Each packet is marked with a value indicating its priority in the network. Since the queues have bounded capacities and the rate of arriving packets can be much higher than the transmission rate, packets can be lost due to insufficient queue space. The goal is to maximize the total value of transmitted packets. This problem encapsulates two dependent questions: buffer management, namely which packets to admit into the queues, and scheduling, i.e. which queue to use for transmission in each time step. We use competitive analysis to study online switch performance in QoS-based networks. Specifically, we provide a novel generic technique that decouples the buffer management and scheduling problems. Our technique transforms any single-queue buffer management policy (preemptive or non-preemptive) to a scheduling and buffer management algorithm for our general m queues model, whose competitive ratio is at most twice the competitive ratio of the given buffer management policy. We use our technique to derive concrete algorithms for the general preemptive and non-preemptive cases, as well as for the interesting special cases of the 2-value model and the unit-value model. We also provide a 1.58-competitive randomized algorithm for the unit-value case. This case is interesting by itself since most current networks (e.g. IP networks) do not yet incorporate full QoS capabilities, and treat all packets equally.     

On the design of woven convolutional encoders with outer warp row permutors

In this paper, permutor design aspects for woven convolutional encoders (WCEs) with outer warp (OW) are discussed. We show how the minimum distance of the overall code can be increased by considering all warp permutors together. A bound on the minimum distance of a code generated by a WCE with OW and designed permutors is presented that considerably exceeds those with known designs.     

Automated generation of a progress measure for the sweep-line method

In the context of Petri nets, we propose an automated construction of a progress measure which is an important pre-requisite for a state space reduction technique called the sweep-line method. Our construction is based on linear-algebraic techniques concerning the transition vectors of the Petri net under consideration. We further discuss the possible combination of the sweep-line method with other state space reduction techniques (partial order reduction, the symmetry method).     

Concept Evaluation Methodology for Extraterrestrial Habitats

The paper examines and compares structural concepts considered for use as habitats for lunar and Martian outposts. An evaluation methodology that allows numeric rating of concepts was previously developed and is upgraded herein. The methodology defines a number of important characteristics on which concepts are to be judged. In addition, weighting factors are assigned for the various characteristics considered in the evaluation system. These factors are presented as variables that depend on mission goals and timing aspects. An example evaluation is made for a specific scenario utilizing the developed methodology. The overall purpose of this work is not to provide an absolute rating, but rather to identify strengths and weaknesses of concepts. This approach should be invaluable in the development and selection of structural concepts for extraterrestrial habitats.     

Mitochondrial creatine kinase is a prime target of peroxynitrite-induced modification and inactivation

The reaction of peroxynitrite (PN) with sarcomeric mitochondrial creatine kinase (Mib-CK; EC 2.7.3.2) was observed at different stages of complexity (i) with purified Mi-CK, (ii) with enzyme bound on isolated mitoplasts, and (iii) within intact respiring mitochondria. Creatine-stimulated respiration was abolished by PN concentrations likely to be physiological and far before the respiratory chain itself was affected, thus demonstrating that Mi-CK is a prime target for inactivation by PN in intact mitochondria. The inactivation by PN of Mi-CK was reversed by 22% with 2-mercaptoethanol. More remarkable protective effects were noticed with the full set of CK substrates, e.g. 30 and 50% protection with MgATP plus creatine and MgADP plus phosphocreatine, respectively, but not with each substrate alone. These data indicate an involvement of the active-site Cys-278 residue of Mi-CK in this process. Furthermore, changes in endogenous tryptophan fluorescence intensity and spectral changes after reaction of Mi-CK with PN suggest additional modifications of Trp and Tyr residues. PN-inactivated Mi-CK can no longer be efficiently converted into dimers by incubation with reagents inducing a transition state analog complex at the active site. Thus, obviously, upon reaction of octameric Mi-CK with PN, the octamer-dimer equilibrium of Mi-CK is also affected. The consequences for cellular energy homeostasis and calcium handling are discussed.     

Augmentation techniques: are they out?

Basics of ligament augmentation are reviewed from the literature. As biomechanical in-vitro studies, animal experiments, and clinical studies show different designs and data, the results may be interpreted variably. Theoretically there is a positive effect of augmentation, but no significant improvement of clinical results is evident. The goal of our own prospective study was to check the healing capacity of a repaired and augmented ACL with respect to stability compared to a primary or secondary BTB ligament replacement with and without augmentation. 200 patients were allocated to 4 groups. In group I (G1) acute proximal ruptures were repaired arthroscopically and augmented with PDS II-cord. Patients in G2 received an acute and in G3 a late BTB ligament replacement. Additionally in G4 a late ligament replacement was augmented with a PDS II-cord. The clinical results reveal a comparative stability between G1 and G2, and gradually less stability in G3 and G4. Subjectively, knee function was felt best in G1 and G2 while being worst in G3 and G4. There is no significant difference in the mobility of knees between primary and secondary ligament replacement. An additional augmentation doesn't improve the knee stability. CLINICAL RELEVANCE: There is no positive effect of an augmentation technique of a biologic ligament replacement concerning stability, morbidity, complication rate, and costs. Very marginal freshly ruptured cruciate ligaments may be reinserted successfully by a biodegradable augmentation. Subjective feeling and functional stability may be at least equal to a primary ligament replacement. There are no advantages in knee mobility, when a secondary ligament replacement is performed.