Reduction of Cu(II) in matrix-assisted laser desorption/ionization mass spectrometry

The mechanisms of the reduction of Cu(II) in matrix-assisted laser desorption/ionization mass spectrometry (MALDI) are studied. In MALDI mass spectra, ions cationized by copper mostly contain Cu(I) even if Cu(II) salts are added to the sample. It was found that Cu(II) was reduced to Cu(I) by gas-phase charge exchange with matrix molecules, which is a thermodynamically favorable process. Under some conditions, large amounts of free electrons are present in the plume. Cu(II) can be even more efficiently reduced to Cu(I) by free electron capture in the gas phase. The matrices studied in this work are nicotinic acid, dithranol, and 2,5-dihydroxybenzoic acid.     

Propagation of light-pulses at a negative group-velocity

This paper deals with the apparent superluminal propagation of electromagnetic pulses in a linear dispersive medium. One specifically examines the possibility that the pulse leaving the medium may be nearly identical to the incident one (low distortion) and in significant advance of it (strongly negative group-delays). Favourable conditions are obtained in a dilute medium where the required anomalous dispersion originates in an ensemble of narrow absorption or gain lines. Analytical expressions of the advancement of the pulse centre-of-gravity and of the lowest order distortion are established from the transfer-function of the medium. The experiments already achieved with arrangements involving a single absorption-line or a gain-doublet are analysed in detail and compared. The considerable difficulties to overcome in order to attain advancements comparable to the pulse width without important distortion are pointed out. New and promising schemes involving a narrow dip in a gain profile or absorption-doublets are proposed. Received 4 July 2002 / Received in final form 8 November 2002 Published online 4 February 2003 RID="a" ID="a"e-mail: bruno.macke@univ-lille1.fr RID="b" ID="b"Unité Mixte de Recherche de l'Université et du CNRS (UMR 8523)     

Expansion of derivatives in one-dimensional dynamics

We study the expansion of derivatives along orbits of real and complex one-dimensional mapsf, whose Julia setJ _f attracts a finite setCrit of non-flat critical points. Assuming that for eachcεCrit, either |D f ⁿ(f(c))|→∞ (iff is real) orb _n·|Df ⁿ(f(c))|→∞ for some summable sequence {b _n} (iff is complex; this is equivalent to summability of |D f ⁿ(f(c))|⁻¹), we show that for everyxεJ _f\U _i f ⁻ⁱ(Crit), there existℓ(x)≤max _c ℓ(c) andK′(x)>0

On the computation of all extensions of a -adic field of a given degree

Let be a -adic field. It is well-known that has only finitely many extensions of a given finite degree. Krasner has given formulae for the number of extensions of a given degree and discriminant. Following his work, we present an algorithm for the computation of generating polynomials for all extensions of a given degree and discriminant.

     

Evolution of magnetic order in mechanically alloyed Al–1 at%Fe

The evolution of ferromagnetic order in high-energy ball-milled Al–1 at% Fe before the onset of a considerable Fe–Al solid solution phase has been investigated using ⁵⁷Fe Mössbauer and bulk magnetization studies. The unmilled sample does not exhibit bulk magnetic properties and an onset of bulk magnetization is observed only after 30 min of milling, when the grain size becomes comparable to the ferromagnetic exchange length. The Curie temperatures of all the samples are less than that of pure iron. The reduction in grain size is accompanied by an increase in coercivity and reduced remanence and a decrease in T_C. The effective magnetic moment per iron atom decreases with the development of a non-magnetic, Al-rich Fe–Al solution on longer milling. The clustering of Fe at grain boundaries is responsible for the observed bulk magnetic ordering. The systematic variation of the magnetic properties has been qualitatively correlated with the evolution of microstructure, reduction in grain size and enhanced inter-granular exchange coupling.     

Tunable microlens arrays using polymer network liquid crystal

A tunable-focus microlens array based on polymer network liquid crystal (PNLC) is demonstrated. The PNLC was prepared using an ultraviolet (UV) light exposure through a patterned photomask. The photocurable monomer in each of the UV exposed spot forms an inhomogeneous centro-symmetrical polymer network which acts as a lens when a homogeneous electric field is applied to the cell. The focal length of the microlens arrays is tunable with the applied voltage.     

Sufficient Conditions for Maximally Edge-connected and Super-edge-connected Digraphs Depending on the Size

Let D be a finite and simple digraph with vertex set V (D). The minimum degree δ of a digraph D is defined as the minimum value of its out-degrees and its in-degrees. If D is a digraph with minimum degree δ and edge-connectivity λ, then λ ≤ δ. A digraph is maximally edge-connected if λ=δ. A digraph is called super-edge-connected if every minimum edge-cut consists of edges incident to or from a vertex of minimum degree. In this note we show that a digraph is maximally edge-connected or super-edge-connected if the number of arcs is large enough.     

Molecular Photochemistry: Recent Developments in Theory

Photochemistry is a fascinating branch of chemistry that is concerned with molecules and light. However, the importance of simulating light‐induced processes is reflected also in fields as diverse as biology, material science, and medicine. This Minireview highlights recent progress achieved in theoretical chemistry to calculate electronically excited states of molecules and simulate their photoinduced dynamics, with the aim of reaching experimental accuracy. We focus on emergent methods and give selected examples that illustrate the progress in recent years towards predicting complex electronic structures with strong correlation, calculations on large molecules, describing multichromophoric systems, and simulating non‐adiabatic molecular dynamics over long time scales, for molecules in the gas phase or in complex biological environments.