Collisional redistribution of radiatively-excited levels of Tl and Ga atoms in an O2-acetylene-Ar flame

Several useful expressions for the population ratios of collisionally excited levels have been derived and different transitions of Tl and Ga atoms, seeded in a premixed atmospheric flame, have been excited in order to verify that the levels higher than the laser-excited level are populated approximately according to a Boltzmann equilibrium. This result confirms the possibility of using thermally assisted flourescence lines to measure local temperatures in flames. The Einstein spontaneous emission probability for the transition 6S_1/2→4P_3/2 at 2719.65Å of Ga has also been calculated (A_2719.65=0.41×10⁸s^-1) to fit the experimental point.     

Nanoporous Network Channels from Self‐Assembled Triblock Copolymer Supramolecules

Supramolecular complexes of a poly(tert‐butoxystyrene)‐block‐polystyrene‐block‐poly(4‐vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self‐assemble into a core–shell gyroid morphology with the core channels formed by the hydrogen‐bonded P4VP(PDP)complexes. After structure formation, PDP was removed using a simple washing procedure, resulting in well‐ordered nanoporous films that were used as templates for nickel plating.

     

Speeding up Exponentiation using an Untrusted Computational Resource

We present protocols for speeding up fixed-base variable-exponent exponentiation and variable-base fixed-exponent exponentiation using an untrusted computational resource. In the fixed-base protocols, the exponent may be blinded. In the variable-base protocols, the base may be blinded. The protocols are described for exponentiation in a cyclic group. We describe how to extend them to exponentiation modulo an integer where the modulus is the product of primes with single multiplicity. The protocols provide a speedup of over the square-and-multiply algorithm, where k is the bitlength of the exponent. One application of the protocols is to speed up exponentiation-based verification in discrete log-based signature and credential schemes. The protocols also allow signature verifiers to dynamically choose, for each message, the amount of work it would like to perform to verify the signature. This results in a work-security tradeoff. We introduce a fifth protocol to perform variable-base variable- exponent exponentiation, which also has this feature. Our model allows the trusted resource to perform computations in its idle time. The protocols facilitate the offloading of work to the offline stage, such that the work the trusted resource performs when it has to do an exponentiation is smaller. Our protocols are unconditionally secure.     

Absorption and scattering microscopy of single metal nanoparticles

Several recently developed detection techniques opened studies of individual metal nanoparticles (1-100 nm in diameter) in the optical far field. Eliminating averaging over the broad size and shape distributions produced by even the best of current synthesis methods, these studies hold great promise for gaining a deeper insight into many of the properties of metal nanoparticles, notably electronic and vibrational relaxation. All methods are based on detection of a scattered wave emitted either by the particle itself, or by its close environment. Direct absorption and interference techniques rely on the particle's scattering and have similar limits in signal-to-noise ratio. The photothermal method uses a photo-induced change in the refractive index of the environment as an additional step to scatter a wave with a different wavelength. This leads to a considerable improvement in signal-to-background ratio, and thus to a much higher sensitivity. We briefly discuss and compare these various techniques, review the new results they generated so far, and conclude on their great potential for nanoscience and for single-molecule labelling in biological assays and live cells.     

Electron–electron interaction induced spin thermalization in quasi-low-dimensional spin valves

We study the spin thermalization, i.e., the inter-spin energy relaxation mediated by electron–electron scattering in small spin valves. When one or two of the dimensions of the spin valve spacer are smaller than the thermal coherence length, the direct spin energy exchange rate diverges and needs to be regularized by the sample dimensions. Here we consider two model systems: a long quasi-1D wire and a thin quasi-2D sheet.     

Synthesis and characterization of long perylenediimide polymer fibers: from bulk to the single-molecule level

The synthesis and characterization of perylenediimide polyisocyanides is reported. In addition to short oligomers, our synthetic approach results in the formation of extremely long, well-defined, and rigid perylenediimide polymers. Ordering and close-packing of the chromophores in these long polymers is guaranteed by attachment to a polyisocyanide backbone with amino acid side chains. Hydrogen bonding interactions between those groups stabilize and rigidify the helical polymer structure. The rodlike nature of the synthesized long perylenediimide pendant polyisocyanides as well as the helical arrangement of the chromophores is demonstrated by means of atomic force microscopy. Remarkably, polymer fibers up to 1 mum in length have been visualized, containing several thousands of perylenediimide molecules. Circular dichroism spectroscopy reveals the chiral organization of the chromophore units in the polymer, whereas absorption and emission measurements prove the occurrence of excited-state interactions between those moieties due to the close packing of the chromophore groups. However, an intricate optical behavior is encountered in bulk as a result of the coexistence of short oligomers and long polymers of perylenediimide, a situation subsequently uncovered by means of single-molecule experiments. Individual long helical perylenediimide polyisocyanides exhibit a typical red-shifted fluorescence spectrum, which, together with depolarized emission continuously decreasing in time, demonstrate that fluorescence arises from multiple excimer-like species in the polymer. Upon continuous irradiation of these long polymers, a fast decay in fluorescence lifetime is observed, a situation explained by photoinduced creation of quenching sites. Radical/ion formation by intramolecular electron transfer between close-by perylenediimide moieties is the most probable mechanism for this process. Appropriate control of the electron-transfer process might open the possibility of applying these polymers as perylenediimide-based supramolecular nanowires.     

Perpendicular giant magnetoresistance of magnetic multilayers

The theoretical and experimental studies of the giant magnetoresistance effect in metallic magnetic multilayers with measuring current perpendicular to the interface planes are reviewed. Theoretical formalisms of electronic transport in the inhomogeneous electron gas are critically compared with emphasis on the perpendicular magnetoresistance in multilayers. The effects of interface roughness, potential steps at the interfaces, and realistic band structures are addressed. The experimental determination of the perpendicular resistance of metallic multilayers requires either low-resistance measurement techniques or microfabricated samples with enhanced resistances. The experimental methods known at present are discussed and, where possible, compared with each other.     

The orientation of porphins in n-alkane Shpolskii hosts

When a solution of a porphin in n-octane is slowly frozen the guests predominantly occupy a single site (A) in which the porphin has been shown to replace a number of host molecules displaced along the b-direction; if the solution is quickly frozen the optical spectra reveal the presence of a second site (B). In the present paper it is shown that the occurrence of these two types of sites, A and B, is a common phenomenon throughout the series from n-heptane (C₇) to n-decane (C ₁₀) as hosts and phenomenological criteria are formulated to distinguish between the two kinds of sites.

The orientation of palladiumporphin (PdP) in the A and B sites of a C₇ host is determined from Zeeman experiments on the S ₁← S ₀ and T ₀ →S ₀ transitions in a single crystal of C₇ doped with PdP. The porphin nuclei in the B sites replace a number of alkanes displaced along the a-axis. In the course of the experiments signals related to a third type of site, B', grew in intensity in the spectra. This site is coplanar with the B site and it differs from the latter by an in-plane rotation of the trapped molecule over 20°. The origins of the S ₁ ←S ₀ transition for the two types of site are assigned for H₂P, ZnP and PdP as solutes in C₇, C₈, C₉ and C₁₀ as hosts.

Finally, the Zeeman shifts observed in the S ₁ ←S ₀ transition of PdP in the three sites of C₇ yield an effective orbital angular momentum for PdP in the state S ₁ of (4·4 ± 0·1)?, in excellent agreement with previous determinations.     

Computational and NMR Studies on the Complexation of Lithium Ion to 8-Crown-4

Lithium ion selective crown ethers have been the subject of much research for a multitude of applications. Current research is aimed at structurally rigidifying crown ethers, as restructuring of the crown ether ring upon ion binding is energetically unfavorable. In this work, the lithium ion binding ability of the relatively rigid 8-crown-4 was investigated both computationally by density functional theory calculations and experimentally by ¹H and ⁷Li NMR spectroscopy. Although both computational and experimental results showed 8-crown-4 to bind lithium ion, this binding was found to be weak compared to larger crown ethers. The computational analysis revealed that the complexation is driven by enthalpy rather than entropy, illustrating that rigidity is only of nominal importance. To elucidate the origin of the favorable interaction of lithium ion with crown ethers, activation strain analyses and energy decomposition analyses were performed pointing to the favorable interaction being mainly electrostatic in nature. 8-crown-4 presents the smallest crown ether reported to date capable of binding lithium ion, possessing two distinct conformations from which it is able to do so.