Digital watermarking for DVD video copy protection

We illustrate the various issues that play a role in designing a copy-protection system for digital versatile disk (DVD) video as perceived by Millennium, one of the two contenders in the DVD-video copy-protection standardization activity. We present the Millennium watermark system, the systems proposed for DVD video copy protection by Philips, Macrovision, and Digimarc. We also address some specific system aspects, such as watermark detector location and copy generation control     

The Fluctuation Theorem as a Gibbs Property

Common ground to recent studies exploiting relations between dynamical systems and nonequilibrium statistical mechanics is, so we argue, the standard Gibbs formalism applied on the level of space-time histories. The assumptions (chaoticity principle) underlying the Gallavotti–Cohen fluctuation theorem make it possible, using symbolic dynamics, to employ the theory of one-dimensional lattice spin systems. The Kurchan and Lebowitz–Spohn analysis of this fluctuation theorem for stochastic dynamics can be restated on the level of the space-time measure which is a Gibbs measure for an interaction determined by the transition probabilities. In this note we understand the fluctuation theorem as a Gibbs property, as it follows from the very definition of Gibbs state. We give a local version of the fluctuation theorem in the Gibbsian context and we derive from this a version also for some class of spatially extended stochastic dynamics.     

A Combined Experimental/Quantum-Chemical Study of Tetrel,Pnictogen, and Chalcogen Bonds of Linear Triatomic Molecules

Linear triatomic molecules (CO₂, N₂O, and OCS) are scrutinized for their propensity to form perpendicular tetrel (CO₂ and OCS) or pnictogen (N₂O) bonds with Lewis bases (dimethyl ether and trimethyl amine) as compared with their tendency to form end-on chalcogen bonds. Comparison of the IR spectra of the complexes with the corresponding monomers in cryogenic solutions in liquid argon enables to determine the stoichiometry and the nature of the complexes. In the present cases, perpendicular tetrel and pnictogen 1:1 complexes are identified mainly on the basis of the lifting of the degenerate ν 2 bending mode with the appearance of both a blue and a red shift. Van ′t Hoff plots of equilibrium constants as a function of temperature lead to complexation enthalpies that, when converted to complexation energies, form the first series of experimental complexation energies on sp¹ tetrel bonds in the literature, directly comparable to quantum-chemically obtained values. Their order of magnitude corresponds with what can be expected on the basis of experimental work on halogen and chalcogen bonds and previous computational work on tetrel bonds. Both the order of magnitude and sequence are in fair agreement with both CCSD(T) and DFA calculations, certainly when taking into account the small differences in complexation energies of the different complexes (often not more than a few kJ mol⁻¹) and the experimental error. It should, however, be noted that the OCS chalcogen complexes are not identified experimentally, most probably owing to entropic effects. For a given Lewis base, the stability sequence of the complexes is first successfully interpreted via a classical electrostatic quadrupole–dipole moment model, highlighting the importance of the magnitude and sign of the quadrupole moment of the Lewis acid. This approach is validated by a subsequent analysis of the molecular electrostatic potential, scrutinizing the σ and π holes, as well as the evolution in preference for chalcogen versus tetrel bonds when passing to “higher” chalcogens in agreement with the evolution of the quadrupole moment. The energy decomposition analysis gives further support to the importance/dominance of electrostatic effects, as it turns out to be the largest attractive term in all cases considered, followed by the orbital interaction and the dispersion term. The natural orbitals for chemical valence highlight the sequence of charge transfer in the orbital interaction term, which is dominated by an electron-donating effect of the N or O lone-pair(s) of the base to the central atom of the triatomics, with its value being lower than in the case of comparable halogen bonding situations. The effect is appreciably larger for TMA, in line with its much higher basicity than DME, explaining the comparable complexation energies for DME and TMA despite the much larger dipole moment for DME.     

Freezing transition in the Ising model without internal contours

We consider the low temperature Ising model in a uniform magnetic field h > 0 with minus boundary conditions and conditioned on having no internal contours. This simple contour model defines a non-Gibbsian spin state. For large enough magnetic fields (h >: h _c ) this state is concentrated on the single spin configuration of all spins up. For smaller values (h≤h _c ), the spin state is non-trivial. At the critical point h _c ≠ 0 the magnetization jumps discontinuously. Freezing provides also an example of a translation invariant weakly Gibbsian state which is not almost Gibbsian. Received: 10 November 1998     

2-Nitroimidazole Based PET Tracers: Development of a General Synthetic Approach and Fluorination Methodology

2-Nitroimidazole based PET tracers are widely used for non-invasive hypoxic tumor diagnosis. In this context, we report here a general method based on a central Mitsunobu reaction to easily access 2-nitroimidazole precursors. Optimization of fluorination conditions is described and successfully applied to the radiofluorination of the 2-nitroimidazole precursors. Moreover, the radiosynthesis of a new potential hypoxia PET tracer is also described. Finally, this article presents a SFC analytical method allowing both an easy monitoring of the fluorination reactions and the measurement of partition coefficients (logP).     

Dynamic covalent assembly of stimuli responsive vesicle gels

We describe the reversible formation of stimuli-responsive vesicle gels from polymerised dynamic covalent surfactants, by simple mixing of soluble surfactant precursors in water under ambient conditions.     

Detection of diazepam in urine,hair and preserved oral fluid samples with LC-MS-MS after single and repeated administration of Myolastan® and Valium®

Sedative agents are used to facilitate sexual assault due to their ability to render the victim passive, submissive and unable to resist. The primary pharmacological effect of the benzodiazepine tetrazepam is muscle relaxation, whereas the benzodiazepine diazepam acts on the central nervous system (CNS) exerting mainly sedation effects. Therefore, contrary to tetrazepam, diazepam is an often-abused drug, which can potentially be used as a date-rape drug. In this study, we describe the detection of low amounts of diazepam in Myolastan (Sanofi-Synthelabo S.A., Brussels, Belgium) and Epsipam (Will-Pharma, Wavre, Belgium) 50 mg tablet preparations by LC-MS-MS, GC-FID and HPLC-DAD. Considering the important forensic implication of this finding, a study was conducted with volunteers receiving a single or repeated dosage of Myolastan. Urine, hair and preserved oral fluid samples were analysed using a previously described sensitive and specific LC-MS-MS detection method allowing for the simultaneous quantification of tetrazepam, diazepam, nordiazepam, oxazepam and temazepam. This study demonstrates that diazepam can be observed in urine samples even after a single dose of Myolastan. In addition, maintaining therapy for 1 week results in the detection of both diazepam and nordiazepam in urine samples and of diazepam in the first hair segment. Importantly, comparing urine and hair samples after a single intake of diazepam versus the single and 1 week administration of Myolastan shows that the possible metabolic conversion of tetrazepam to diazepam is a more plausible explanation for the detection of diazepam in biological samples after the intake of Myolastan. As such, these results reveal that the presence of diazepam and/or nordiazepam in biological samples from alleged drug-facilitated assault cases should be interpreted with care.     

Near-Infrared BODIPY-Acridine Dyads Acting as Heavy-Atom-Free Dual-Functioning Photosensitizers

Boron dipyrromethene (BODIPY) dyes represent a particular class within the broad array of potential photosensitizers. Their highly fluorescent nature opens the door for theragnostic applications, combining imaging and therapy using a single, easily synthesized chromophore. However, near-infrared absorption is strongly desired for photodynamic therapy to enhance tissue penetration. Furthermore, singlet oxygen should preferentially be generated without the incorporation of heavy atoms, as these often require additional synthetic efforts and/or afford dark cytotoxicity. Solutions for both problems are known, but have never been successfully combined in one simple BODIPY material. Here, we present a series of compact BODIPY-acridine dyads, active in the phototherapeutic window and showing balanced brightness and phototoxic power. Although the donor–acceptor design was envisioned to introduce a charge transfer state to assist in intersystem crossing, quantum-chemical calculations refute this. Further photophysical investigations suggest the presence of exciplex states and their involvement in singlet oxygen formation.