n-Alkane hydroconversion on Zeogrid and colloidal ZSM-5 assembled from aluminosilicate nanoslabs of MFI framework type

n-Alkane hydroisomerisation and hydrocracking experiments reveal that ZSM-5 materials synthesized by self-assembly of nanoslabs show different molecular shape selectivity than ZSM-5 synthesized by hydrothermal methods.     

Magnetic anisotropy of the antiferromagnetic ring [Cr8F8Piv16

A new tetragonal (P42(1)2) crystalline form of [Cr8F8Piv16] (HPiv = pivalic acid, trimethyl acetic acid) is reported. The ring-shaped molecules, which are aligned in a parallel fashion in the unit cell, form almost perfectly planar, regular octagons. The interaction between the CrIII ions is antiferromagnetic (J = 12 cm(-1)) which results in a S = 0 spin ground state. The low-lying spin excited states were investigated by cantilever torque magnetometry (CTM) and high-frequency EPR (HFEPR). The compound shows hard-axis anisotropy. The axial zero-field splitting (ZFS) parameters of the first two spin excited states (S = 1 and S = 2, respectively) are D1 = 1.59(3) cm(-1) or 1.63 cm(-1) (from CTM and HFEPR, respectively) and D2 = 0.37 cm(-1) (from HFEPR). The dipolar contributions to the ZFS of the S = 1 and S = 2 spin states were calculated with the point dipolar approximation. These contributions proved to be less than the combined single-ion contributions. Angular overlap model calculations that used parameters obtained from the electronic absorption spectrum, showed that the unique axis of the single-ion ZFS is at an angle of 19.3(1) degrees with respect to the ring axis. The excellent agreement between the experimental and the theoretical results show the validity of the used methods for the analysis of the magnetic anisotropy in antiferromagnetic CrIII rings.     

Derivatives of 5-Aminolevulinic Acid for Photodynamic Therapy: Enzymatic Conversion into Protoporphyrin

In recent years, 5-aminolevulinic acid (ALA) has become a widespread agent for photodynamic therapy (PDT). In nucleated cells, ALA is converted into the endogenous photosensitizer protoporphyrin IX (PpIX). A major drawback of ALA is its low bioavailability. As a result, high doses of ALA must be administered in order to reach clinically relevant levels of PpIX. Moreover, only superficially located lesions can be treated as a result of the poor penetration of ALA into tissues. A possible solution for this problem may be provided by the prod rug concept. In the present study, prodrugs of ALA have been synthesized. These ALA prodrugs are shown to result in higher PpIX levels in cells than does ALA itself. Of a range of ester prodrugs of ALA, the ALA-pentyl ester elicits the highest fluorescence. Further-more, the enzymatic conversion of the derivatives into ALA and PpIX has been studied in lysed cells. Under these circumstances, the esters with the shorter alkyl chains induce the highest fluorescence. The alcohols that arise as side products from enzymatic conversion of the prodrugs are shown to have no influence on the experiments.     

Adsorption properties of the penicillin derivative DTPA on gold substrates.

Despite the large number of articles and patents dealing with penicillin and other beta-lactam antibiotics, there have been no reports about the self-assembly of such substances as monolayers on gold surfaces. The main reason stems from the high reactivity of the beta-lactam ring, which hinders the development of molecules possessing this entity together with a metal-anchoring function. Herein, we present the synthesis of a novel molecule, 6-[(R,S)-5-(1,2-dithiolan-3-yl)pentanoyl-amino]-penicillanic acid, which combines the beta-lactam ring and a metal-anchoring group. Using spectroscopic tools, we demonstrate the chemisorption of this compound on gold as self-assembled monolayers without any alteration of the penicillin pharmacophore and document its reactivity towards a penicillin-binding protein, BlaR-CTD. Our work is a preliminary step towards the development of new biosensors and well-ordered protein arrays, both based on the high affinity of penicillin for penicillin-binding proteins.     

Performance comparison of several priority schemes with priority jumps

In this paper, we consider several discrete-time priority queues with priority jumps. In a priority scheduling scheme with priority jumps, real-time and non-real-time packets arrive in separate queues, i.e., the high- and low-priority queue respectively. In order to deal with possibly excessive delays however, non-real-time packets in the low-priority queue can in the course of time jump to the high-priority queue. These packets are then treated in the high-priority queue as if they were real-time packets. Many criteria can be used to decide when packets of the low-priority queue jump to the high-priority queue. Some criteria have already been introduced in the literature, and we first overview this literature. Secondly, we propose and analyse a new priority scheme with priority jumps. Finally, we extensively compare all cited schemes. The schemes all differ in their jumping mechanism, based on a certain jumping criterion, and thus all have a different performance. We show the pros and cons of each jumping scheme.     

Analysis of γ‐globulin mobility on routine clinical CE equipment: Exploring its molecular basis and potential clinical utility

A study was conducted on the variability of γ‐globulin mobility in serum protein electrophoresis and its molecular basis. We found that the migration time of γ‐globulins can be reproducibly determined (CV=1.1%) on clinical CE equipment. Moreover, we found a significant difference (p<0.001) in the migration of γ‐globulins between chronic liver disease patients (n=98) and a healthy reference group (n=47). Serum immunoglobulins were purified from these patients' sera using protein L ‐agarose and their glycosylation was studied using CE on a DNA sequencer. This glycomics approach revealed that several non‐sialylated N‐glycans show a moderate Pearson correlation coefficient (r=0.2–0.4) with the migration time of γ‐globulins. Their sialylated structures correlate negatively (r=?0.2 to ?0.3). Immunoglobulins are significantly more sialylated in the healthy reference group compared with the patients (p<0.001). We estimated that sialylation heterogeneity contributes about 36% to the molecular variance (carbohydrates and amino acid composition) that affects the electrophoretic mobility of immunoglobulins. This is the first report on the migration time of γ‐globulins on a clinical CE instrument and its potential clinical value to the routinely analyzed serum protein CE profiles.     

Reducing measurement time for a laser Doppler vibrometer using regressive techniques

In the last decade the laser Doppler vibrometer (LDV) has become a widely spread instrument for measuring vibrations. It often offers accurate measurements with a high spatial resolution. However, the measurement time of the LDV and especially for the scanning LDV is long. Therefore, reducing the measurement time is an attractive objective. A way to achieve this is to use a single sine excitation (on a resonance frequency). However, this technique has two major drawbacks: the inability to provide information on the damping and a operational deflection shape that can differ from the true mode shape. In this article two methods will be introduced to reduce measurement time without these defaults. In the first method introduced in this article a narrow band multisine is used as excitation signal and the measured vibration signal in the time domain is represented by a model using sines and cosines with these fixed narrow band frequencies. The coefficients of those sines and cosines are then estimated on a global scale by means of a least-squares estimator. An important advantage of this particular technique is that one does not have to measure a full period of the signal, reducing time. The second method accelerates the measurement time for scanning LDV measurements. Using the time domain sequence from each previous scan point and a limited number of time samples from the current scan point, the full time domain sequence of the current scan point can be estimated. Both these methods are a key benefit for in-line quality control, which can have upwards of 1000 spatial measurement locations. The proposed techniques will be validated on both simulations and experiments of varying complexity.     

Acoustic source identification using a scanning laser Doppler vibrometer

This paper shows how a scanning laser Doppler vibrometer (LDV), an instrument designed to measure vibrations of structures or objects, can be used in a non-traditional fashion to identify acoustical sources. This is achieved by measuring the changes in the optical path induced by local fluctuation of the air refraction index to which the LDV is sensitive. The acoustical signal used is sinusoidal and may be recovered by scanning at a uniform rate over a subject area (continuous scan) parallel to the source axis and demodulating this signal. Due to the fact that the measured scan area is in fact a line integral over a measurement volume between the laser head and a rigid object needed to reflect the laser beam, multiple view planes around the axis of the acoustic source are usually measured. These are then passed through a tomographic algorithm, thereby reconstructing the full sound field. In this article however, only one view plane is measured, but the acoustic source is placed on a rotating surface with fixed rotational frequency, thereby imposing a modulation on the measured spectrum. Demodulation will allow reconstruction of the three-dimensional sound field.     

Determination of ephedrine and related compounds in pharmaceutical preparations by ion chromatography with direct conductivity detection

An ion chromatographic method with conductivity detection for the simultaneous determination of ephedrine, pseudoephedrine and norephedrine was developed. A mixture of 2.0 mmol/L HNO3 and 2% (v/v) acetonitrile was used as eluent. The three ephedrine-like compounds were separated and determined within 20 min. The linear ranges were 0.08-50 microg/mL for ephedrine, 0.08-40 microg/mL for pseudoephedrine and 0.06-40 microg/mL for norephedrine. The detection limits were 0.03 microg/mL for ephedrine and pseudoephedrine, and 0.02 microg/mL for norephedrine. The method has been applied successfully to the determination of these sympathomimetics in pharmaceutical preparations and in Ephedra herbs.