Self‐Assembly of Uranyl–Peroxide Nanocapsules in Basic Peroxidic Environments

A wide range of uranyl–peroxide nanocapsules have been synthesized using very simple reactants in basic media; however, little is known about the process to form these species. We have performed a density functional theory study of the speciation of the uranyl ions under different experimental conditions and explored the formation of dimeric species via a ligand exchange mechanism. We shed some light onto the importance of the excess of peroxide and alkali counterions as a thermodynamic driving force towards the formation of larger uranyl–peroxide species.     

Rapid initiation of reactions in Al/Ni multilayers with nanoscale layering

Research into nanoenergetic materials is enabling new capabilities for controlling exothermic reaction rates and energy output, as well as new methods for integrating these materials with conventional electronics fabrication techniques. Many reactions produce primarily heat, and in some cases it is desirable to increase the rate of heat release beyond what is typically observed. Here we investigate the Al-Ni intermetallic reaction, which normally propagates across films or foils at rates lower than 10 m/s. However, models and experiments indicate that local heating rates can be very high (10⁷ K/s), and uniform heating of such a multilayer film can lead to a rapid, thermally explosive type of reaction. With the hopes of using a device to transduce electrical energy to kinetic energy of a flyer plate in the timescale of 100's of nanoseconds, we have incorporated a Ni/Al nanolayer film that locally heats upon application of a large electrical current. We observed flyer plate velocities in the 2-6 km/s range, corresponding to 4-36 kJ/g in terms of specific kinetic energy. Several samples containing Ni/Al films with different bilayer thicknesses were tested, and many produced additional kinetic energy in the 1.1-2.3 kJ/g range, as would be expected from the Ni-Al intermetallic reaction. These results provide evidence that nanoscale Ni/Al layers reacted in the timescale necessary to contribute to device output.     

The Key Role of U28 in the Aqueous Self‐Assembly of Uranyl Peroxide Nanocages

For 11 years now, the structural diversity and aesthetic beauty of uranyl–peroxide capsules have fascinated researchers from the diverse fields of mineralogy, polyoxometalate chemistry, and nuclear fuel technologies. There is still much to be learned about the mechanisms of the self‐assembly process, and the role of solution parameters including pH, alkali template, temperature, time, and others. Here we have exploited the high solubility of the UO₂²⁺/H₂O₂/LiOH aqueous system to address the effect of the hydroxide concentration. Important techniques of this study are single‐crystal X‐ray diffraction, small‐angle X‐ray scattering, and Raman spectroscopy. Three key phases dominate the solution speciation as a function of time and the LiOH/UO₂²⁺ ratio: the uranyl–triperoxide monomer [UO₂(O₂)₃]^4?and the two capsules [(UO₂)(O₂)(OH)]₂₄^24?(U₂₄) and [(UO₂)(O₂)_1.5]₂₈^28?(U₂₈). When the LiOH/U ratio is around three, U₂₈ forms rapidly and this cluster can be isolated in high yield and purity. This result was most surprising and challenges the hypothesis that alkali templating is the most important determinant in the cluster geometry. Moreover, analogous experiments with KOH, NH₄OH, and TEAOH (TEA=tetraethylammonium) also rapidly yield U₂₈, which suggests that U₂₈ is the kinetically favored species. Complete mapping of the pH–time phase space reveals only a narrow window of the U₂₈ dominance, which is why it was previously overlooked as an important kinetic species in this chemical system, as well as others with different counterions.     

On the cohomology of generalized homogeneous spaces

We observe that work of Gugenheim and May on the cohomology of classical homogeneous spaces of Lie groups applies verbatim to the calculation of the cohomology of generalized homogeneous spaces , where is a finite loop space or a -compact group and is a ``subgroup' in the homotopical sense.

     

Quantitative analysis of two-dimensional gel-separated proteins using isotopically marked alkylating agents and matrix-assisted laser desorption/ionization mass spectrometry

We describe a simple approach for the relative quantification of individual proteins within a mixture. The method is based on the differential labelling of the mixtures by use of a commercially available acrylamide and deuterium-labelled [2,3,3'-d(3)]-acrylamide to alkylate proteins prior to two-dimensional (2-D) gel electrophoresis. The tryptic digests of the separated proteins were subjected to reflector matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) analysis and the relative peak heights of cysteine-containing peptides were used to quantify their precursor proteins. This approach was tested for the relative quantification of proteins within an artificial mixture of standard proteins and for proteins observed in a 2-D map of rat serum. A good correlation was found between the measured ratios derived from MALDI-TOF data and those theoretically calculated prior to 2-D analysis via known mixing ratios of the two alkylating reagents. The described procedure has proved to be effective for comparative measurements of protein abundances within the investigated mixtures.     

Hypernuclear fine structure in (9)(lambda)Be

With a germanium detector array (Hyperball), we observed two gamma-ray peaks corresponding to the two transitions (5/2(+)-->1/2(+) and 3/2(+)-->1/2(+)) in the (9)(Lambda)Be hypernucleus which was produced by the 9Be(K-,pi(-)) reaction. The energies of the gamma rays are 3029 +/- 2 +/- 1 keV and 3060 +/- 2 +/- 1 keV. The energy difference was measured to be 31.4(+2.5)(-3.6) keV, which indicates a very small Lambda-spin-dependent spin-orbit force between a Lambda and a nucleon. This is the smallest level splitting by far ever measured in a hypernucleus.     

Assessment of the kinetics and sites of reaction of some immobiline chemicals with proteins and peptides by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry

A number of proteins and peptides have been incubated with some Immobiline chemicals commonly used in the production of immobilised pH gradients for isoelectric focusing. After various incubation intervals, the resulting reaction mixtures were examined by matrix-assisted laser desorption/ionisation mass spectrometry. At pH 9-10, and after 15-h incubation time, no significant interaction was observed with the two of the investigated proteins which have no Cys residues in their sequences. On the other hand, intense multiple reaction channels were observed with sequences containing a number of Cys residues. The present measurements provide useful information on the kinetics of the reaction and its sensitivity to both the pK(a) of the Immobiline chemicals and the presence of Cys in the investigated sequences. Post source decay measurements on peptides with and without Cys in their sequences provided unambiguous evidence for the involvement of this residue in the reaction conducted at pH 9-10. Possible implications of some of the present deductions for isoelectric focusing separations on immobilised pH gradients are discussed.     

Correlation of speckle patterns generated by laser point source — Illuminated diffusers

In this paper it is shown that, when a ground-glass transilluminated by a diverging or converging beam is axially translated, there exists a particular plane in which the corresponding speckle pattern remains correlated. Consequently, under some experimental conditions on this incident beam and the geometry of the optical setup, a speckle pattern generated by a set of two parallel ground-glasses suffers no decorrelation when one of them is axially or laterally translated.