Interstack Interactions in Potassium Bis(1,2-Cyclobutenedione 3,4-dithiolato) Palladate. Crystal Structure

Abstract

Potassium bis(1,2-cyclobutenedione 3,4-dithiolato) palladate (Pd(dithiosquarato)₂K₂) crystallizes in the monolinic system, space group P2₁/c, a = 8.046(2), b = 15.235(4), c = 6.289(1). The dithiosquarate entities are stacked in parallel columns separated by potassium cations and water molecules. π-interactions within a stack are evidenced by the short stacking distance (3.51 Å). Further interstack interactions involve close S…O or O…O interstack contacts. (～3.5 Å). As a result, the structural arrangement is nearly two-dimensional. Conductivity measurements carried out on pressed pellets show a semi-conductive behavior (σ = 2 × 10^?5 Ω^?1 cm¹).     

Stable Potential Windows for Long‐Term Electrocatalysis by Manganese Oxides Under Acidic Conditions

Efficient, earth‐abundant, and acid‐stable catalysts for the oxygen evolution reaction (OER) are missing pieces for the production of hydrogen via water electrolysis. Here, we report how the limitations on the stability of 3d‐metal materials can be overcome by the spectroscopic identification of stable potential windows in which the OER can be catalyzed efficiently while simultaneously suppressing deactivation pathways. We demonstrate the benefits of this approach using gamma manganese oxide (γ‐MnO₂), which shows no signs of deactivation even after 8000 h of electrolysis at a pH of 2. This stability is vastly superior to existing acid‐stable 3d‐metal OER catalysts, but cannot be realized if there is a deviation as small as 50‐mV from the stable potential window. A stable voltage efficiency of over 70 % in a polymer–electrolyte membrane (PEM) electrolyzer further verifies the availability of this approach and showcases how materials previously perceived to be unstable may have potential application for water electrolysis in an acidic environment.     

High-Field Detection of Biomarkers with Fast Field-Cycling MRI: The Example of Zinc Sensing

Many smart magnetic resonance imaging (MRI) probes provide response to a biomarker based on modulation of their rotational correlation time. The magnitude of such MRI signal changes is highly dependent on the magnetic field and the response decreases dramatically at high fields (>2 T). To overcome the loss of efficiency of responsive probes at high field, with fast-field cycling magnetic resonance imaging (FFC-MRI) we exploit field-dependent information rather than the absolute difference in the relaxation rate measured in the absence and in the presence of the biomarker at a given imaging field. We report here the application of fast field-cycling techniques combined with the use of a molecular probe for the detection of Zn²⁺ to achieve 166 % MRI signal enhancement at 3 T, whereas the same agent provides no detectable response using conventional MRI. This approach can be generalized to any biomarker provided the detection is based on variation of the rotational motion of the probe.     

Heat treatment effects on dielectric and physico-chemical properties of an epoxy polymer

Infrared (IR) spectroscopy, dielectric spectroscopy (DS), and thermally stimulated depolarization current (TSDC) have been used to study heat treatment effects on an epoxy-based polymer. Variations in physico-chemical and dielectric properties were examined for annealing temperatures between 55 and 170 °C. IR results have shown that heating causes both chain scission and thermal oxidation of the polymer, increasing thus the amount of trapped charges. The complex dielectric permittivity and the dielectric modulus have been analyzed, by means of DS, to highlight and separate charge relaxation phenomena from conduction contributions. Results indicate structural rearrangements, leading to a decrease of dipolar relaxation frequency (from 16 to 13.5 kHz) and an increase of the relaxation strength (around 20%). TSDC measurements have shown a current peak shift towards higher temperatures, and a significant intensity decrease, which is proportional to the quantity of released charges.     

An all-fiber frequency-shifted feedback laser for optical ranging; signal variation with distance

A recent paper [L.P. Yatsenko et al., Opt. Commun. 242 (2004) 581] provided a first-principles prediction for the optical ranging signals obtained when using a frequency-shifted feedback (FSF) laser system, seeded by a phase-modulated laser. Such a system has many useful advantages over other alternative FSF laser techniques. We report here experimental verification of that theory, specifically the variation of the amplitude modulation signal with both distance and modulation index of the seed laser. We describe the operation of an all-fiber FSF laser that uses an Er³⁺-doped active fiber as the gain medium. To improve the signal and minimize the noise we seed the FSF laser with a phase-modulated (PM) laser; the measurement of distance derives from a measurement of amplitude modulation within a narrow frequency interval. We demonstrate that the resulting system is capable of fast and precise measurements. With the bandwidth limitations of our current system we achieved an accuracy better than 0.1 mm. Although measurements based on interferometry offer the potential for much greater accuracy under carefully controlled conditions, the present method does not suffer from the presence of a material-dependent phase shift at the surface of the measured object.     

Generic singularities of the 3D-contact sub-Riemannian conjugate locus

In this paper, we extend and complete the classification of the generic singularities of the 3D-contact sub-Riemmanian conjugate locus in a neighborhood of the origin.     

Poset algebras over well quasi-ordered posets

A new class of partial order-types, class is defined and investigated here. A poset P is in the class iff the poset algebra F(P) is generated by a better quasi-order G that is included in L(P). The free Boolean algebra F(P) and its free distributive lattice L(P) have been defined in [ABKR]. The free Boolean algebra F(P) contains the partial order P and is generated by it: F(P) has the following universal property. If B is any Boolean algebra and f is any order-preserving map from P into a Boolean algebra B, then f can be extended to a homomorphism of F(P) into B. We also define L(P) as the sublattice of F(P) generated by P. We prove that if P is any well quasi-ordering, then L(P) is well founded, and is a countable union of well quasi-orderings. We prove that the class is contained in the class of well quasi-ordered sets. We prove that is preserved under homomorphic image, finite products, and lexicographic sum over better quasi-ordered index sets. We prove also that every countable well quasi-ordered set is in . We do not know, however if the class of well quasi-ordered sets is contained in . Additional results concern homomorphic images of posets algebras. The third author was supported by the following institutions: Israel Science Foundation (postdoctoral positions at Ben Gurion University 2000–2002), The Fields Institute (Toronto 2002–2004), and by The Nato Science Fellowship (University Paris VII, CNRS-UMR 7056, 2004).     

A Lock-and-Kill Anticancer Photoactivated Chemotherapy Agent†

Photosubstitutionally active ruthenium complexes show high potential as prodrugs for the photoactivated chemotherapy (PACT) treatment of tumors. One of the problems in PACT is that the localization of the ruthenium compound is hard to trace. Here, a ruthenium PACT prodrug, [Ru(3)(biq)(STF-31)](PF₆)₂ (where 3 = 3-(([2,2′:6′,2″-ter- pyridin]-4′-yloxy)propyl-4-(pyren-1-yl)butanoate) and biq = 2,2′-biquinoline), has been prepared, in which a pyrene tracker is attached via an ester bond. The proximity between the fluorophore and the ruthenium center leads to fluorescence quenching. Upon intracellular hydrolysis of the ester linkage, however, the fluorescence of the pyrene moiety is recovered, thus demonstrating prodrug cellular uptake. Further light irradiation of this molecule liberates by photosubstitution STF-31, a known cytotoxic nicotinamide phosphoribosyltransferase (NAMPT) inhibitor, as well as singlet oxygen via excitation of the free pyrene chromophore. The dark and light cytotoxicity of the prodrug, embedded in liposomes, as well as the appearance of blue emission upon uptake, were evaluated in A375 human skin melanoma cells. The cytotoxicity of the liposome-embedded prodrug was indeed increased by light irradiation. This work realizes an in vitro proof-of-concept of the lock-and-kill principle, which may ultimately be used to design strategies aimed at knowing where and when light irradiation should be realized in vivo.     

Ruthenium-based light-driven molecular machine prototypes: synthesis and properties

In the past years, many dynamic systems often referred to as "molecular machines" have been elaborated. They are generally set in motion by external stimuli like chemical, electrochemical, or photochemical reactions. Light irradiation seems particularly promising since the input signal can be switched on and off fast and readily on a very small place. In this tutorial review, we will highlight recent advances in the design and synthesis of various ruthenium(II) complexed rotaxanes, catenanes, scorpionates or macrocycles. In these compounds, one part of the system is set in motion by photochemically expelling a given chelate. We will discuss the behaviour of various topologically non-trivial systems like catenanes and rotaxanes as well as acyclic and macrocyclic models.