Exciplex fluorescence emission from simple organic intramolecular constructs in non-polar and highly polar media as model systems for DNA-assembled exciplex detectors

Organic intramolecular exciplexes, N-(4-dimethylaminobenzyl)-N-(1-pyrenemethyl)amine (1) and N'-4-dimethylaminonaphthyl-N-(1-pyrenemethyl)amine (2), were used as model systems to reveal major factors affecting their exciplex fluorescence, and thus lay the basis for developing emissive target-assembled exciplexes for DNA-mounted systems in solution. These models with an aromatic pyrenyl hydrocarbon moiety as an electron acceptor appropriately connected to an aromatic dimethylamino electron donor component (N,N-dimethylaminophenyl or N,N-dimethylaminonaphthyl) showed strong intramolecular exciplex emission in both non-polar and highly polar solvents. The effect of dielectric constant on the maximum wavelength for exciplex emission was studied, and emission was observed for 1 and 2 over the full range of solvent from non-polar hydrocarbons up to N-methylformamide with a dielectric constant of 182. Quantum yields were determined for these intramolecular exciplexes in a range of solvents relative to that for Hoechst 33,258. Conformational analysis of 1 was performed both computationally and via qualitative 2D NMR using (1)H-NOESY experiments. The results obtained indicated the contribution of pre-folded conformation(s) to the ground state of 1 conducive to exciplex emission. This research provides the initial background for design of self-assembled, DNA-mounted exciplexes and underpins further development of exciplex-based hybridisation bioassays.     

Validity of phase space theory for atom-diatom insertion reactions

Phase space theory (PST) is applied to the calculation of state-resolved integral and differential cross sections for the complex-forming atom-diatom insertion reactions A + H(2) --> AH(2) --> AH + H with A = C((1)D), S((1)D), O((1)D), and N((2)D). In the asymptotic channels, vibration motion is quantized while rotation and translation motions are treated classically. The approach is compared to exact quantum scattering calculations and quantum statistical models. Given the simplicity of PST, the agreement with the previous much more refined treatments is very satisfying. Although PST is a well-established theory, this work is, to our knowledge, the first such systematic comparison of its predictions with accurate quantum scattering and quantum statistical calculations.     

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).