Synthesis of a porphyrin-labelled carboranyl phosphate diester: a potential new drug for boron neutron capture therapy of cancer

A boron-rich, water-soluble porphyrin conjugate was synthesized by coupling of two carboranyl alcohols with 2-chlorophenoxyphosphorus dichloride, followed by conjugation to an amine-functionalized tetraphenyl-porphyrin via an amide linkage.     

First intermolecular cyclopropanation of Fischer dialkylaminocarbene complexes. Synthesis of 1-aminocyclopropanecarboxylic acid derivatives

[reaction: see text] The first cyclopropanation reaction of olefins with Fischer dialkylaminocarbene complexes is presented. The reaction yields 1-aminocyclopropanecarboxylic acid derivatives in a single step, usually with high diastereoselectivity. An approach to the asymmetric version of this reaction is also presented. The synthetic utility of the procedure is exemplified by the synthesis of both cycles of metanoproline in a single step. In addition, the synthesis of the first Fischer carbene containing a halocarbonyl group is reported.     

Square-wave voltammetric techniques for determination of psychoactive 1,4-benzodiazepine drugs

Direct square-wave voltammetry (SWV) and square-wave cathodic stripping voltammetry (SWCSV) at hanging mercury drop electrodes have been developed for determination of the psychoactive 1,4-benzodiazepine compounds clonazepam, bromazepam, midazolam, diazepam, medazepam, and flurazepam over a wide range of concentrations. Analysis was performed with better precision, lower detection limits, and much more rapidly than by previously reported voltammetric techniques.The applicability of both procedures is discussed. The methods were applied to the analysis of commercially available tablets with minimum sample manipulation. The accuracy of the results was accessed by comparison with those obtained by use of the methods described in official pharmacopoeias. A critical comparison with those procedures is also presented.     

Quantum chaos and 1/f noise

It is shown that the energy spectrum fluctuations of quantum systems can be formally considered as a discrete time series. The power spectrum behavior of such a signal for different systems suggests the following conjecture: The energy spectra of chaotic quantum systems are characterized by 1/f noise.     

Tracer studies on f-actin fluctuations

We present a study on the fluctuations of semiflexible actin filaments using fluorescence videomicroscopy, focusing on the end-to-end fluctuations of single filaments. In order to specifically measure the position of the polymer's ends, we developed a novel noninvasive method that consists of annealing short end tags to the filaments. This allows us to probe polymer fluctuations to a very high accuracy. We compared the distribution of the end-to-end distance with recent theoretical results, and found excellent agreement. We also studied the dynamics of the mean-square end-to-end distance deltaR2(t) and orientation of the ends, deltaTheta(2)(t), finding power laws t(3/4) and t(1/4), respectively. Scaling behavior for deltaR2(t) is observed over several decades in relaxation time in agreement with theoretical results.     

Rejuvenation and overaging in a colloidal glass under shear

We report the modifications of the microscopic dynamics of a colloidal glass submitted to shear. We use multispeckle diffusing wave spectroscopy to monitor the evolution of the spontaneous slow relaxation processes after the samples have been submitted to various straining. We show that high shear rejuvenates the system and accelerates its dynamics, whereas moderate shear over-ages the system. We analyze these phenomena within the frame of the Bouchaud's trap model.     

SU(2) instantons with boundary jumps and spin tunneling in magnetic molecules

Coherent state path integrals are shown in general to contain instantons with jumps at the boundaries, i.e., boundary points lying outside classical phase space. Inclusion of these instantons is shown to resolve the "missing quench paradox" in the magnetic molecule Fe8, i.e., the fact that the tunneling between the ground Zeeman states of this molecule is quenched at only four magnetic field values, instead of the ten that would be expected from the topological Berry phase between interfering instantons. An approximate formula is found for the location of the four remaining quenches.     

Probing the dark energy with quasar clustering

We show through Monte Carlo simulations that the Alcock-Paczyński test, as applied to quasar clustering, is a powerful tool to probe the cosmological density and equation of state parameters Omega(m0), Omega(x0), and w. By taking into account the effect of peculiar velocities upon the correlation function we obtain for the Two-Degree Field QSO Redshift Survey the predicted confidence contours for the cosmological constant (w = -1) and spatially flat (Omega(m0)+Omega(x0) = 1) cases. For w = -1, the test is especially sensitive to the difference Omega(m0)-Omega(Lambda0), thus being ideal to combine with cosmic microwave background results. For the flat case, it is competitive with future supernova and galaxy number count tests, besides being complementary to them.     

Quantum optical communication rates through an amplifying random medium

We study the competing effects of stimulated and spontaneous emission on the information capacity of an amplifying disordered waveguide. At the laser threshold the capacity reaches a "universal" limit, independent of the degree of disorder. Whether or not this limit is larger or smaller than the capacity without amplification depends on the disorder, as well as on the input power. Explicit expressions are obtained for heterodyne detection of coherent states, and generalized for an arbitrary detection scheme.     

Enhanced x-ray phase determination by three-beam diffraction

For decades, solving the phase problem of x-ray scattering has been a goal that, in principle, could be achieved by means of n-beam diffraction (n-BD). However, the phases extracted by the actual n-BD phasing techniques are not very precise, mainly due to systematic errors that are difficult to estimate. We present an innovative theoretical approach and experimental procedure that, combined, eliminate two major sources of error. It is a high precision phasing technique that provides the triplet-phase angle with an error of about 2 degrees.