From chain collapse to new structures: spectroscopic properties of poly(3-thiophene acetic acid) upon binding by alkyl trimethylammonium bromide surfactants

The binding of cationic surfactants with varying alkyl chain length to a regiorandom conjugated polyanion, poly(3-thiophene acetic acid) (PTAA), is studied in an aqueous buffer by using absorption and emission spectroscopies, photon correlation spectroscopy, isothermal titration calorimetry, and cryogenic transmission electron microscopy. We study the mixed solutions as a function of composition ratio R of surfactant molecules to monomer units molar concentrations, at low polymer concentration and in a very wide composition range (10(-6) < R < 10(2)) below the critical micellar concentration. Upon surfactant binding, the molecularly dispersed chains first collapse progressively and then form new structures as the mixed aggregates get enriched in surfactant. The collapse leads to a strong decrease of the conjugation length and to a blue shift of the absorption spectra by 30 to 50 nm. The new structures are responsible for a new intense emission band at about 600 nm, red-shifted by nearly 130 nm from the initial emission maximum of the polymer (~472 nm). As the surfactant tail becomes shorter, the blue shift of the absorption spectra and the intensity raise of the new emission are delayed to larger composition ratios while their variations become smoother functions of the surfactant concentration. These particular spectroscopic properties of PTAA seem related to its unique combination of a strongly hydrophobic backbone, a large ratio of contour length to persistence length, and an overall good aqueous solubility. Our results show that such features are well suited to design a colorimetric biosensor at small composition ratio, and a fluorescent biomarker at large composition ratio.     

Microscopic model for superexchange interactions and photomagnetism in binuclear transition metal complexes

Recent experiments show that the superexchange interaction in molecular clusters containing transition metal ions A?=?Ni^II and B?=?W^V, Nb^IV or Mo^V in some cases is antiferromagnetic, contrary to the conventional superexchange rules. To understand this anomaly, we develop a quantum many-body model Hamiltonian and solve it exactly using a valence bond (VB) approach. We identify the various model parameters which control the ground state spin in different clusters of the A-B system. We present quantum phase diagrams that delineate the high and low-spin ground states in the parameter space. We fit the spin gap to a spin Hamiltonian and extract the effective exchange constant within the experimentally observed range, for reasonable parameter values. We also find a region of intermediate spin ground state in the parameter space, in clusters of larger size. The spin spectrum of the microscopic model cannot be reproduced by a simple Heisenberg exchange Hamiltonian. The above microscopic model is generic and can also be employed to explain photomagnetism in the MoCu₆ system. We solve the model for MoCu₆ and find that ground state is degenerate and is spanned by the S?=?0,?1,?2 and 3 manifolds with doubly occupied Mo site corresponding to Mo(IV) and singly occupied Cu sites corresponding to Cu(II) configurations. In each of these spin spaces, we observe that there exist charge-transfer (CT) states at ≈3?eV above the ground state which are dipole coupled to the ground state. The transition dipole in the S?=?3 manifold is the largest for the CT excitations. Coupled with the fact that the density of states of the S?=?3 manifold is sparse, compared to other spin manifolds, we expect that the S?=?3 CT excited state to be long-lived, thereby explaining the experimentally observed photomagnetism in the MoCu₆ system.     

Narrowing the length distribution of Ge nanowires

Synthesis of nanostructures of uniform size is fundamental because the size distribution directly affects their physical properties. We present experimental data demonstrating a narrowing effect on the length distribution of Ge nanowires synthesized by the Au-catalyzed molecular beam epitaxy on Si substrates. A theoretical model is developed that is capable of describing this puzzling behavior. It is demonstrated that the direction of the diffusion flux of sidewall adatoms is size dependent and has a major effect on the growth rate of differently sized nanowires. We also show that there exists a fundamental limitation on the maximum nanowire length that can be achieved by molecular beam epitaxy where the direction of the beam is close to the growth axis.     

Shape coexistence in light se isotopes: evidence for oblate shapes

Lifetimes of states in the ground-state bands of (70)Se and (72)Se were measured using the recoil-distance Doppler shift method. The results deviate significantly from earlier measurements, requiring a revision of the conclusions drawn from a recent Coulomb excitation experiment concerning the shape of (70)Se. The new results lead to a coherent picture of shape coexistence in the neutron-deficient selenium and krypton isotopes. The coexistence and evolution of oblate and prolate shapes in this mass region is for the first time consistently described by new Hartree-Fock-Bogolyubov-based configuration-mixing calculations which were performed using the Gogny D1S interaction.     

Feedback cooling of the normal modes of a massive electromechanical system to submillikelvin temperature

We apply a feedback cooling technique to simultaneously cool the three electromechanical normal modes of the ton-scale resonant-bar gravitational wave detector AURIGA. The measuring system is based on a dc superconducting quantum interference device (SQUID) amplifier, and the feedback cooling is applied electronically to the input circuit of the SQUID. Starting from a bath temperature of 4.2 K, we achieve a minimum temperature of 0.17 mK for the coolest normal mode. The same technique, implemented in a dedicated experiment at subkelvin bath temperature and with a quantum limited SQUID, could allow to approach the quantum ground state of a kilogram-scale mechanical resonator.     

3He spin-dependent cross sections and sum rules

We present a measurement of the spin-dependent cross sections for the 3He over -->(e over -->,e')X reaction in the quasielastic and resonance regions at a four-momentum transfer 0.1< or =Q2< or =0.9 GeV2. The spin-structure functions have been extracted and used to evaluate the nuclear Burkhardt-Cottingham and extended Gerasimov-Drell-Hearn sum rules for the first time. The data are also compared to an impulse approximation calculation and an exact three-body Faddeev calculation in the quasielastic region.     

Emission characterization of a single CdSe-ZnS nanocrystal with high temporal and spectral resolution by photon-correlation Fourier spectroscopy

We report a spectroscopic study of single colloidal CdSe/ZnS nanocrystals at low temperature. We use photon-correlation Fourier spectroscopy, a technique based on measuring the correlations of the intensities detected at the outputs of a Michelson interferometer. Spectral diffusion over a few microeV is evidenced, on a typical time scale of 200 micros. A time resolution as high as 20 micros is obtained, and an upper limit of 6.5 microeV emission linewidth is measured, corresponding to a coherence time of at least 200 ps, similar to the values for epitaxial quantum dots.     

Simulation of the thermal transfer during an eutectic melting of a binary solution

The main objective of this paper is to present a model for the heat transfer in the case of the melting of saline binary solution. This model is applied to calorimetry in order to determine the kinetics of the eutectic melting. The investigated cell containing the solution is a cylinder of a few mm³ in volume. By simulation, we could replicate the shape of the experimental thermogramms. The validation of the model permits determining some parameters which are inaccessible due to the small size of the cell, like the space-time evolution of the temperature inside the differential scanning calorimetry (DSC) sample.