Estimate on the Pathwise Lyapunov Exponent of Linear Stochastic Differential Equations with Constant Coefficients

In this article, we study the problem of estimating the pathwise Lyapunov exponent for linear stochastic systems with multiplicative noise and constant coefficients. We present a Lyapunov type matrix inequality that is closely related to this problem, and show under what conditions we can solve the matrix inequality. From this we can deduce an upper bound for the Lyapunov exponent. In the converse direction, it is shown that a necessary condition for the stochastic system to be pathwise asymptotically stable can be formulated in terms of controllability properties of the matrices involved.     

Temperature Controlled Sequential Gelation in Composite Microgel Suspensions

Depending on the volume fraction and interparticle interactions, colloidal suspensions can exhibit a variety of physical states, ranging from fluids, crystals, and glasses to gels. For microgel particles made of thermoresponsive polymers, both parameters can be tuned using environmental parameters such as temperature and ionic strength, making them excellent systems to experimentally study state transitions in colloidal suspensions. Using a simple two‐step synthesis it is shown that the properties of composite microgels, with a fluorescent latex core and a responsive microgel shell, can be finely tuned. With this system the transitions between glass, liquid, and gel states for suspensions composed of a single species are explored. Finally, a suspension of two species of microgels is demonstrated, with different transition temperatures, gels in a sequential manner. Upon increasing temperature a distinct core–sheath structure is formed with a primary gel composed of the species with lowest transition temperature, which acts as a scaffold for the aggregation of the second species.     

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.     

A note on the integrality gap of an ILP formulation for the periodic maintenance problem

We address the integrality gap of the integer linear program introduced by Grigoriev et al. (2006) [3] for the periodic maintenance problem. We prove that the integrality gap of this program is bounded by a constant.     

The stereocontrolled photoaddition of allene to cyclopent-1-ene-1-carboxaldehydes. A total synthesis of (±) steviol methyl ester and isosteviol methyl ester

The stereochemistry of the photoaddition of allene to hydroindenal 19 is explored. The stereochemistry is proven by conversion into steviol methyl ester 22b and isosteviol methyl ester 24.     

2,5-Dioxido-1,4-benzoquinonediimine (H2L2-), a hydrogen-bonding noninnocent bridging ligand related to aminated topaquinone: different oxidation state distributions in complexes [{(bpy)2Ru}2(mu-H2L)]n (n=0,+,2+,3+,4+) and [{(acac)2Ru}2(mu-H2L)]m (m=2-,-,0,+,2+)

The symmetrically dinuclear title compounds were isolated as diamagnetic [(bpy)2Ru(mu-H2L)Ru(bpy)2](ClO4)2 (1-(ClO4)2) and as paramagnetic [(acac)2Ru(mu-H2L)Ru(acac)2] (2) complexes (bpy=2,2'-bipyridine; acac- = acetylacetonate = 2,4-pentanedionato; H2L = 2,5-dioxido-1,4-benzoquinonediimine). The crystal structure of 22 H2O reveals an intricate hydrogen-bonding network: Two symmetry-related molecules 2 are closely connected through two NH(H2L2-)O(acac-) interactions, while the oxygen atoms of H2L2- of two such pairs are bridged by an (H2O)8 cluster at half-occupancy. The cluster consists of cyclic (H2O)6 arrangements with the remaining two exo-H2O molecules connecting two opposite sides of the cyclo-(H2O)6 cluster, and oxido oxygen atoms forming hydrogen bonds with the molecules of 2. Weak antiferromagnetic coupling of the two ruthenium(III) centers in 2 was established by using SQUID magnetometry and EPR spectroscopy. Geometry optimization by means of DFT calculations was carried out for 1(2+) and 2 in their singlet and triplet ground states, respectively. The nature of low-energy electronic transitions was explored by using time-dependent DFT methods. Five redox states were reversibly accessible for each of the complexes; all odd-electron intermediates exhibit comproportionation constants K(c)>10(8). UV-visible-NIR spectroelectrochemistry and EPR spectroscopy of the electrogenerated paramagnetic intermediates were used to ascertain the oxidation-state distribution. In general, the complexes 1n+ prefer the ruthenium(II) configuration with electron transfer occurring largely at the bridging ligand (mu-H2Ln-), as evident from radical-type EPR spectra for 13+ and (+. Higher metal oxidation states (iii, iv) appear to be favored by the complexes 2m; intense long-wavelength absorption bands and RuIII-type EPR signals suggest mixed-valent dimetal configurations of the paramagnetic intermediates 2+ and 2-.     

Laboratory guidelines and standards in clinical and forensic toxicology

An overview is given of the existing standards and guidelines for analytical toxicology. Details about guidelines concerning forensic toxicology, clinical toxicology, point-of-care testing, and an area of overlap are provided. Guidelines and standards exist for forensic toxicological analysis in general and for specific situations, e.g., workplace drug testing and driving under the influence of drugs and alcohol. For workplace drug testing, detailed guidelines exist in the U.S.A., Australia, and Europe describing for example the methods used, their cut-off and the process of sample handling. Some governments describe the methods and quality requirements for blood alcohol testing for driving under the influence of alcohol in detail in their laws. In the area of clinical toxicology, guidelines not only focus on the analytical aspects of analysis but also on the timeliness of results. According to the US- and UK-based practice guidelines for the emergency department, the turn-around time should be 1 or 2 h, respectively, for a specific set of analytes. Guidelines are either being developed now or already available (e.g., workplace drug testing, breath alcohol analysis) for point-of-care testing in analytical toxicology. In the context of brain death and sexual assault cases, specific demands need to be imposed because of the unique aspects of drug analysis in these situations (variety of drugs used, low concentrations). Many guidelines and standards are available and it is up to every laboratory to choose the best ones depending on the area of activity and the legal and regulatory environment.Presented at the 10th Conference Quality in the Spotlight, March 2005, Antwerp, Belgium     

Learning from Peptides to Access Functional Precision Polymer Sequences

Functional precision polymers based on monodisperse oligo(N‐substituted acrylamide)s and oligo(2‐substituted‐α‐hydroxy acid)s have been synthesized. The discrete sequences originate from a direct translation of side‐chain functionality sequences of a peptide with well‐studied properties. The peptide was previously selected to solubilize the photosensitizer meta‐tetra(hydroxyphenyl)chlorin. The resulting peptidomimetic formulation additives preserve the drug solubilization and release characteristics of the parent peptide. In some cases, superior properties are obtained, reaching up to 40 % higher payloads and 27‐times faster initial drug release.     

α-Unsaturated 3-Amino-1-carboxymethyl-β-lactams as Bacterial PBP Inhibitors: Synthesis and Biochemical Assessment

Innovative monocyclic β-lactam entities create opportunities in the battle against resistant bacteria because of their PBP acylation potential, intrinsically high β-lactamase stability and compact scaffold. α-Benzylidene-substituted 3-amino-1-carboxymethyl-β-lactams were recently shown to be potent PBP inhibitors and constitute eligible anchor points for synthetic elaboration of the chemical space around the central β-lactam ring. The present study discloses a 12-step synthesis of ten α-arylmethylidenecarboxylates using a microwave-assisted Wittig olefination as the crucial reaction step. The library was designed aiming at enhanced β-lactam electrophilicity and extended electron flow after enzymatic attack. Additionally, increased β-lactamase stability and intermolecular target interaction were envisioned by tackling both the substitution pattern of the aromatic ring and the β-lactam C4-position. The significance of α-unsaturation was validated and the R39/PBP3 inhibitory potency shown to be augmented the most through decoration of the aromatic ring with electron-withdrawing groups. Furthermore, ring cleavage by representative β-lactamases was ruled out, providing new insights in the SAR landscape of monocyclic β-lactams as eligible PBP or β-lactamase inhibitors.     

Unraveling the Composition of Rembrandt's Impasto through the Identification of Unusual Plumbonacrite by Multimodal X‐ray Diffraction Analysis

Rembrandt (1606–1669) is renowned for his impasto technique, involving his use of lead white paint with outstanding rheological properties. This paint was obtained by combining lead white pigment (a mixture of cerussite PbCO₃ and hydrocerussite Pb₃(CO₃)₂(OH)₂) with an organic binding medium, but the exact formulation used by Rembrandt remains a mystery. A powerful combination of high‐angle and high‐lateral resolution x‐ray diffraction was used to investigate several microscopic paint samples from four Rembrandt masterpieces. A rare lead compound, plumbonacrite (Pb₅(CO₃)₃O(OH)₂), was detected in areas of impasto. This can be considered a fingerprint of Rembrandt's recipe and is evidence of the use of an alkaline binding medium, which sheds a new light on Rembrandt's pictorial technique.