Bruce Merrifield, trained as a biochemist, had to address three major challenges related to the development and acceptance of solid-phase peptide synthesis (SPPS). The challenges were (1) to reduce the concept of peptide synthesis on a insoluble support to practice, (2) overcome the resistance of synthetic chemists to this novel approach, and (3) establish that a biochemist had the scientific credentials to effect the proposed revolutionary change in chemical synthesis. How these challenges were met is discussed in this article.

We present a measurement of the branching fraction and photon energy spectrum for the decay B {yields} X{sub s}{gamma} using data from the BABAR experiment. The data sample corresponds to an integrated luminosity of 210 fb{sup -1}, from which approximately 680,000 B{bar B} events are tagged by a fully reconstructed hadronic decay of one of the B mesons. In the decay of the second B meson, an isolated high-energy photon is identified. We measure {Beta}(B {yields} X{sub s}{gamma}) = (3.66 {+-} 0.85{sub stat} {+-} 0.60{sub syst}) x 10{sup -4} for photon energies E{sub {gamma}} above 1.9 GeV in the B rest frame. From the measured spectrum we calculate the first and second moments for different minimum photon energies, which are used to extract the heavy-quark parameters m{sub b} and {mu}{sub {pi}}{sup 2}. In addition, measurements of the direct CP asymmetry and isospin asymmetry are presented.

Synthetic Cd{sub 1-x}Zn{sub x}Te or 'CZT' crystals are highly suitable for the room temperature-based spectroscopy of gamma radiation. Structural/morphological heterogeneities within CZT, such as secondary phases that are thought to consist of Te metal and have detrimental impacts on detector performance. In this study, we used electron and X-ray-based imaging techniques to examine heterogeneous properties of detector grade CZT. Using experimental analytical techniques rather than arbitrary theoretical definitions, our study identifies two dominant secondary phase morphologies. The first consists of numerous empty, 20 {micro} m wide, pyramidal bodies (tetrahedra) or 'negative' crystals with trace quantities of particulate residue that exist as 65 nm sized particles containing Si, Cd, Zn, and Te. The other consists of 20 {micro}m hexagonal-shaped bodies, which are composites of metallic Te layers that contain a teardrop-shaped core of amorphous and polycrystalline CdZnTe which finally surrounds an irregular-shaped void.

We provide a systematic analysis of nonnegative matrix factorization (NMF) relating to data clustering. We generalize the usual X = FG{sup T} decomposition to the symmetric W = HH{sup T} and W = HSH{sup T} decompositions. We show that (1) W = HH{sup T} is equivalent to Kernel K-means clustering and the Laplacian-based spectral clustering. (2) X = FG{sup T} is equivalent to simultaneous clustering of rows and columns of a bipartite graph. We emphasizes the importance of orthogonality in NMF and soft clustering nature of NMF. These results are verified with experiments on face images and newsgroups.

We report recent measurements for the branching fractions of charmless hadronic B decays obtained from data collected by the BABAR detector at the PEP-II asymmetric-energy collider at the Stanford Linear Accelerator Center.

The authors report the results of a study of the decays B{sup +} {yields} J/{psi}{omega}K{sup +} and B{sup 0} {yields} J/{psi}{omega}K{sub S}{sup 0} using 383 million B{bar B} events from {Upsilon}(4S) decays with the BABAR detector at the PEP-II asymmetric-energy e{sup +}e{sup -} storage rings. They observe evidence for Y(3940) {yields} J/{psi}{omega} with product branching fractions {Beta}(B{sup +} {yields} Y K{sup +}, Y {yields} J/{psi}{omega}) = (4.9 {+-} 1.0(stat) {+-} 0.5(syst)) x 10{sup -5} and {Beta}(B{sup 0} {yields} Y K{sup 0}, Y {yields} J/{psi}{omega}) = (1.5{sub -1.2}{sup +1.4}(stat){sub -0.2}{sup +0.2}(syst)) x 10{sup -5}. The measured mass and width are M(Y) = (3914.6{sub -3.4}{sup +3.8}(stat){sub -1.9}{sup +1.9}(syst)) MeV/c{sup 2} and {Lambda}(Y) = (33{sub -8}{sup +12}(stat){sub -5}{sup +5}(syst)) MeV, respectively.

The authors develop an embedded boundary finite difference technique for solving the compressible two- or three-dimensional Euler equations in complex geometries on a Cartesian grid. The method is second order accurate with an explicit time step determined by the grid size away from the boundary. Slope limiters are used on the embedded boundary to avoid non-physical oscillations near shock waves. They show computed examples of supersonic flow past a cylinder and compare with results computed on a body fitted grid. Furthermore, they discuss the implementation of the method for thin geometries, and show computed examples of transonic flow past an airfoil.

We summarize results of several successful dense plasma diagnostics experiments realized by combining two different kinds of table-top soft x-ray lasers with an amplitude division interferometer based on diffraction grating beam splitters. In the first set of experiments this robust high throughput diffraction grating interferometer (DGI) was used with a 46.9 nm portable capillary discharge laser to study the dynamics of line focus and point focus laser-created plasmas. The measured electron density profiles, which differ significantly from those expected from a classical expansion, unveil important two-dimensional effects of the dynamics of these plasmas. A second DGI customized to operate in combination with a 14.7 nm Ni-like Pd transient gain laser was used to perform interferometry of line focus laser-created plasmas with picosecond time resolution. These measurements provide valuable new benchmarks for complex hydrodynamic codes and help bring new understanding of the dynamics of dense plasmas. The instrumentation and methodology we describe is scalable to significantly shorter wavelengths, and constitutes a promising scheme for extending interferometry to the study of very dense plasmas such as those investigated for inertial confinement fusion.

An assessment of safety, design, and cost tradeoff issues for short (ten to fifty years) and longer (fifty to hundreds of years) interim dry storage of spent nuclear fuel in Zircaloy rods shall address potential failures of the Zircaloy cladding caused by the precipitation response of zirconium hydride platelets. If such assessment analyses are to be done rigorously, they will be necessarily complex because the precipitation response of zirconium hydride platelets is a stochastic functional of hydrogen concentration, temperature, stress, fabrication defect/texture structures, and flaw sizes of the cladding. Thus, there are, and probably always will be, zirhydride questions to analytically and experimentally resolve concerning the consistency, the completeness, and the certainty of models, data, the initial and the time-dependent boundary conditions. Some resolution of these questions will be required in order to have a defensible preference and tradeoffs decision analysis for assessing risks and consequences of the potential zirhydride induced cladding failures during dry storage time intervals. In the following brief discussion, one of these questions is posed as a consequence of an anomaly described in data reproducibility that was reported in the results of tests for hydrogen induced delayed cracking. The testing anomaly consisted of observing a significant …

We describe an algorithm for the numerical solution of a phase-field model (PFM) of microstructure evolution in polycrystalline materials. The PFM system of equations includes a local order parameter, a quaternion representation of local orientation and a species composition parameter. The algorithm is based on the implicit integration of a semidiscretization of the PFM system using a backward difference formula (BDF) temporal discretization combined with a Newton-Krylov algorithm to solve the nonlinear system at each time step. The BDF algorithm is combined with a coordinate projection method to maintain quaternion unit length, which is related to an important solution invariant. A key element of the Newton-Krylov algorithm is the selection of a preconditioner to accelerate the convergence of the Generalized Minimum Residual algorithm used to solve the Jacobian linear system in each Newton step. Results are presented for the application of the algorithm to 2D and 3D examples.

The aligned nanorods of Co{sub 3}O{sub 4} and nanoporous hollow spheres (NHS) of SnO{sub 2} and Mn{sub 2}O{sub 3} were investigated as the anodes for Li-ion rechargeable batteries. The Co{sub 3}O{sub 4} nanorods demonstrated 1433 mAh/g reversible capacity. The NHS of SnO{sub 2} and Mn{sub 2}O{sub 3} delivered 400 mAh/g and 250 mAh/g capacities respectively in multiple galvonastatic discharge-charge cycles. It was found that high capacity of NHS of metal oxides is sustainable attributed to their unique structure that maintains material integrity during cycling. The nanostructured metal oxides exhibit great potential as the new anode materials for Li-ion rechargeable batteries with high energy density, low cost and inherent safety.

The durability of natural glasses on geological time scales and ancient glasses for thousands of years is well documented. The necessity to predict the durability of high level nuclear waste (HLW) glasses on extended time scales has led to various thermodynamic and kinetic approaches. Advances in the measurement of medium range order (MRO) in glasses has led to the understanding that the molecular structure of a glass, and thus the glass composition, controls the glass durability by establishing the distribution of ion exchange sites, hydrolysis sites, and the access of water to those sites. During the early stages of glass dissolution, a 'gel' layer resembling a membrane forms through which ions exchange between the glass and the leachant. The hydrated gel layer exhibits acid/base properties which are manifested as the pH dependence of the thickness and nature of the gel layer. The gel layer ages into clay or zeolite minerals by Ostwald ripening. Zeolite mineral assemblages (higher pH and Al{sup 3+} rich glasses) may cause the dissolution rate to increase which is undesirable for long-term performance of glass in the environment. Thermodynamic and structural approaches to the prediction of glass durability are compared versus Ostwald ripening.

New chemistries based upon liquid cyclohexasilane (Si{sub 6}H{sub 12} or CHS) have been used as precursors to silicon-containing electronic materials. Spin-coating of CHS-based inks with subsequent UV light and/or thermal treatment yielded amorphous silicon (a-Si:H) films. While initial ink chemistries gave a-Si:H with high resistivity (i.e., > 10{sup 6} {Omega}.cm), several doping strategies are under development to address this limitation. In this contribution, the current status of solution processed rectifying diodes and field effect transistors fabricated from CHS-based inks will be presented. Additionally, a new printing approach termed collimated aerosol beam direct write (CAB-DW{sup TM}) was developed that allows the deposition of printed Ag lines 5 {mu}m in width. A status update will be given where CHS-based inks have been used to CAB-DW silicon-based features with linewidths <10 {mu}m. Assuming silicon thin film materials with good electrical properties will be developed, there may be significant cost advantages associated with the ability to controllably deposit the semiconductor in a metered fashion.

We report a systematic neutron diffraction study on the coexistence of long-range magnetic order and superconductivity in heavy fermion compounds CeRhl-,M,Ins (M=Ir,Co). In addition to the incommensurate antiferromagnetic component in pure CeRhIn5, new type of antiferromagnetic component is found to concur with appearance of superconductivity in the Ir and Co alloy series. There is no detectable effect of the superconducting transition on magnetic order parameters. We compare those results with similar studies we performed on CeRhIn:, under pressure. We also discuss possible theoretical scenarios.

At concentrations below 60%, wet hydrofluoric acid (HF) is extremely corrosive to steels, stainless steels and reactive metals, such as titanium, zirconium, and tantalum. In fact, only a few metallic materials will withstand wet HF at temperatures above ambient. Among these are the nickel-copper (Ni-Cu) and nickel-chromium-molybdenum (Ni-Cr-Mo) alloys. Previous work has shown that, even with these materials, there are complicating factors. For example, under certain conditions, internal attack and stress corrosion cracking (SCC) are possible with the Ni-Cr-Mo alloys, and the Ni-Cu materials can suffer intergranular attack when exposed to wet HF vapors. The purpose of this work was to study further the response of the Ni-Cr-Mo alloys to HF, in particular their external corrosion rates, susceptibility to internal attack and susceptibility to HF-induced SCC, as a function of alloy composition. As a side experiment, one of the alloys was tested in two microstructural conditions, i.e. solution annealed (the usual condition for materials of this type) and long-range ordered (this being a means of strengthening the alloy in question). The study of external corrosion rates over wide ranges of concentration and temperature revealed a strong beneficial influence of molybdenum content. However, tungsten, which is used as a partial replacement …

A large variety of corrosion resistant alloys are used regularly in the chemical process industry (CPI). The most common family of alloys include the iron (Fe)-based stainless steels, nickel (Ni) alloys and titanium (Ti) alloys. There also other corrosion resistant alloys but their family of alloys is not as large as for the three groups mentioned above. All ranges of corrosive environments can be found in the CPI, from caustic solutions to hot acidic environments, from highly reducing to highly oxidizing. Stainless steels are ubiquitous since numerous types of stainless steels exist, each type tailored for specific applications. In general, stainless steels suffer stress corrosion cracking (SCC) in hot chloride environments while high Ni alloys are practically immune to this type of attack. High nickel alloys are also resistant to caustic cracking. Ti alloys find application in highly oxidizing solutions. Solutions containing fluoride ions, especially acid, seem to be aggressive to almost all corrosion resistant alloys.

Colleagues of mine have asked me few times why we have today so much interest in Fixed-Field Alternating-Gradient (FFAG) accelerators when these were invented a long time ago, and have always been ignored since then. I try here to give a reply with a short history of FFAG accelerators, at least as I know it. I take also the opportunity to clarify few definitions.

We propose a microscopic CFT description of magnetically charged black holes in IIA compactifications on elliptic fibrations based on the Fourier-Mukai transform. The physical derivation of this model involves a chain of string duality transformations including the 4D/5D black hole correspondence. We compute the asymptotic behavior of the microstate degeneracy in a certain limit of large charges and show that it agrees with the macroscopic entropy formula. An interesting aspect of this setup is that the attractor points are situated deep in a hybrid phase of the quantum Kaehler moduli space.

The Taiwan-America Occultation Survey (TAOS) aims to determine the number of small icy bodies in the outer reach of the Solar System by means of stellar occultation. An array of 4 robotic small (D=0.5 m), wide-field (f/1.9) telescopes have been installed at Lulin Observatory in Taiwan to simultaneously monitor some thousand of stars for such rare occultation events. Because a typical occultation event by a TNO a few km across will last for only a fraction of a second, fast photometry is necessary. A special CCD readout scheme has been devised to allow for stellar photometry taken a few times per second. Effective analysis pipelines have been developed to process stellar light curves and to correlate any possible flux changes among all telescopes. A few billion photometric measurements have been collected since the routine survey began in early 2005. Our preliminary result of a very low detection rate suggests a deficit of small TNOs down to a few km size, consistent with the extrapolation of some recent studies of larger (30-100 km) TNOs.

At the Savannah River Site (SRS), there remains approximately 35 million gallons of High Level Waste (HLW) that was mostly created from Purex and SRS H-Area Modified (HM) nuclear fuel cycles. The waste is contained in approximately forty-nine tanks fabricated from commercially available carbon steel. In order to minimize general corrosion, the waste is maintained as very-alkaline solution. The very-alkaline chemistry has caused hydrated metal oxides to precipitate and form a sludge heel. Over the years, the sludge waste has aged, with some forming a hardened crust. To aid in the removal of the sludge heels from select tanks for closure the use of oxalic acid to dissolve the sludge is being investigated. Developing an optimized process strategy based on laboratory analyses would be prohibitively costly. This research, therefore, demonstrates that a chemical equilibrium based software program can be used to develop an optimized process strategy for oxalic acid cleaning of the HLW tanks based on estimating resultant chemistries, minimizing resultant oxalates sent to the evaporator, and minimizing resultant solids sent to the Defense Waste Processing Facility (DWPF).

We study the relative ability of several models of the X-ray absorption spectrum to capture the Franck-Condon structure apparent from an experiment on gaseous nitrogen. In doing so, we adopt the Born-Oppenheimer approximation and a constrained density functional theory method for computing the energies of the X-ray-excited molecule. Starting from an otherwise classical model for the spectrum, we systematically introduce more realistic physics, first by substituting the quantum mechanical nuclear radial density in the bond separation R for the classical radial density, then by adding the effect of zero-point energy and other level shifts, and finally by including explicit rovibrational quantization of both the ground and excited states. The quantization is determined exactly, using a discrete variable representation. We show that the NEXAFS spectrum can be predicted semiquantiatively within this framework. We also address the possibility of non-trivial temperature dependence in the spectrum. Finally, we show that it is possible to improve the predicted spectrum by using constrained DFT in combination with more accurate potentials.

A hard/soft SmCo{sub 5}/Fe nanocomposite magnetic bilayer system has been fabricated on X-ray transparent 100-200 nm thin Si{sub 3}N{sub 4} membranes by magnetron sputtering. The microscopic magnetic domain pattern and its behavior during magnetization reversal in the hard and soft magnetic phases have been individually studied by element specific magnetic soft x-ray microscopy at a spatial resolution of better than 25nm. We observe that the domain patterns for soft and hard phases switch coherently throughout the full hysteresis cycle upon applying external magnetic fields. We derived local M(H) curves from the images for Fe and SmCo5 separately and found switching for both hard and soft phases same.

Biodiesel is a mixture of long chain fatty acid methyl esters derived from fats and oils. This research study presents opposed-flow diffusion flame data for one large fatty acid methyl ester, methyl decanoate, and uses the experiments to validate an improved skeletal mechanism consisting of 648 species and 2998 reactions. The results indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular weight oxygenated compounds such as carbon monoxide, formaldehyde, and ketene.

Hyper-thermal species have been used to produce carbon-based films with mechanical and tribological properties that have greatly expanded the applications of amorphous carbon coatings. Tetragonally bonded amorphous carbon films have properties that approach that of diamond in several ways. The major drawback, namely intrinsic stresses, preventing the production of thick ta-C films has been overcome by heat treating these films, and presently several micrometer-thick films of ta-C are regularly produced. Yet another area where superhard coatings are of great interest is for wear applications at elevated temperatures, namely around 500 degrees C and above. Such temperatures may be environment temperatures, or localized (flash) temperatures resulting for instance from wear. For this applications, doping the ta-C with elements that are covalently bonded to C (such as Si and B) offers a promising alternative. In this article, I will discuss some treatments that have allowed expanding the applications of pure ta-C, and the incorporation of Si and B on ta-C films. Film properties are presented and discussed.