Digital simulation as an aid to sample scheduling in a routine laboratory for liquid chromatography

A computer model is described to aid decision-making in a routine laboratory for liquid chromatography. The managerial demand was to reduce the delay times of the samples in the laboratory despite an increasing sample input. Knowledge derived from records on the laboratory and from the experience of the laboratory staff is used to develop a simulation model of the laboratory. The model is applied to study the effects of several factors on the performance of the laboratory in order to trace the bottlenecks.     

The pH-static enzyme sensor : An ISFET-based enzyme sensor,insensitive to the buffer capacity of the sample

An ISFET-based urea sensor is combined with a noble-metal electrode which provides continuous coulometric titration of the products of the enzymatic reaction. The sensor thus becomes independent of the buffer capacity of the sample; and because the enzyme is operating at a constant pH, the linear response range is expanded.     

Surface characterization of a cross‐linked cytochrome c film on cysteamine‐modified gold electrodes

The aim of the present paper is to characterize a cross‐linked horse heart cytochrome c (HHC) film on cysteamine‐modified gold electrodes. The HHC film was deposited using 1‐ethyl‐3‐(3‐dimethylaminopropyl)‐carbodiimide (EDC) as a coupling agent. Attenuated total reflection infrared (ATR‐IR) spectroscopic analyses were performed to characterize the newly formed surface on a qualitative and conformational level. The film thickness was measured using a noncontact optical surface profiler, while quantitative data and information on the heterogeneity of the film were obtained by means of synchrotron radiation X‐ray micro fluorescence (SR micro‐XRF). Results indicate that, in addition to electrochemical studies, spectroscopic analysis methods are essential to gain insight in the effect of immobilization strategies on protein conformations. The latter is of relevance in the development and optimization of biosensors. Copyright © 2009 John Wiley & Sons, Ltd.     

Enantioselective route to 3-vinylidene tetrahydropyrans and 3-vinylidene oxepanes based on a silyl-Prins cyclization

A general method has been developed for the asymmetric synthesis of 3-vinylidene tetrahydropyrans and 3-vinylidene oxepanes based on the Lewis acid-catalyzed intramolecular reactions of oxocarbenium ions with propargylsilanes. The observed excellent diastereoselectivity and a high asymmetric induction offer a new synthetic method with a wide scope and generality.     

The kalimantacin/batumin biosynthesis operon encodes a self-resistance isoform of the FabI bacterial target

BatG is a trans-2-enoyl-ACP reductase, encoded in?the kalimantacin/batumin (kal/bat) biosynthesis operon. It is not essential for the production of the kal/bat secondary metabolite. Instead, BatG is an isoform of FabI, conferring full resistance to target bacteria. It also complements FabI in its role in fatty acid biosynthesis. The identification of FabI as the antibacterial target is important to assess clinical potential of the kalimantacin/batumin antibiotics against Staphylococcus aureus.     

Identification of poliovirions and subviral particles by capillary electrophoresis

Poliovirions, purified from infected cell extracts with anion-exchange chromatography, can be analyzed and identified by CE in untreated fused silica capillaries using UV detection. Other subviral particles can be eluted as well from the same infected cell extract using a higher salt concentration buffer on the ion-exchange chromatography. Virions can be identified because of their conversion into empty capsids upon heating at 56°C. As a result of heating, the viral genome is released from the capsid. Here, we show that during this incubation some intermediate particles were found. The latter were identified by enzymatic peak shift analysis. The high salt concentration eluate subviral particles were analyzed with preincubation affinity CE together with their sensitivity for RNase and proteinase K treatment. Electropherograms of the higher salt concentration eluate display a mixture of at least four different subviral particles. One particle proved to have an [N1, H] antigenicity and was resistant to RNase and proteinase K digestion. The remaining particles were all sensitive to proteinase K treatment. This CE method proved to be valuable in the detection, identification and analysis of poliovirions and poliovirus particles offering an alternative powerful, cheap, fast and easy analysis method.     

Non-neural BOLD variability in block and event-related paradigms

Block and event-related stimulus designs are typically used in fMRI studies depending on the importance of detection power or estimation efficiency. The extent of vascular contribution to variability in block and event-related fMRI-BOLD response is not known. With scaling, the extent of vascular variability in the fMRI-BOLD response during block and event-related design tasks was investigated. Blood oxygen level-dependent (BOLD) contrast data from healthy volunteers performing a block design motor task and an event-related memory task requiring performance of a motor response were analyzed from the regions of interest (ROIs) surrounding the primary and supplementary motor cortices. Average BOLD signal change was significantly larger during the block design compared to the event-related design. In each subject, BOLD signal change across voxels in the ROIs had higher variation during the block design task compared to the event-related design task. Scaling using the resting state fluctuation of amplitude (RSFA) and breath-hold (BH), which minimizes BOLD variation due to vascular origins, reduced the within-subject BOLD variability in every subject during both tasks but significantly reduced BOLD variability across subjects only during the block design task. The strong non-neural source of intra- and intersubject variability of BOLD response during the block design compared to event-related task indicates that study designs optimizing for statistical power through enhancement of the BOLD contrast (for, e.g., block design) can be affected by enhancement of non-neural sources of BOLD variability.     

On the collision and preimage security of MDC-4 in the ideal cipher model

We present a collision and preimage security analysis of MDC-4, a 24-years-old construction for transforming an n-bit block cipher into a 2n-bit hash function. We start with MDC-4 based on one single block cipher, and prove that any adversary with query access to the underlying block cipher requires at least \(2^{5n/8}\) queries (asymptotically) to find a collision. For the preimage resistance, we present a surprising negative result: for a target image with the same left and right half, a preimage for the full MDC-4 hash function can be found in \(2^n\) queries. Yet, restricted to target images with different left and right halves, we prove that at least \(2^{5n/4}\) queries (asymptotically) are required to find a preimage. Next, we consider MDC-4 based on two independent block ciphers, a model that is less general but closer to the original design, and prove that the collision bound of \(2^{5n/8}\) queries and the preimage bound of \(2^{5n/4}\) queries apply to the MDC-4 compression function and hash function design. With these results, we are the first to formally confirm that MDC-4 offers a higher level of provable security compared to MDC-2.