Catalytic Formation of C−N Bonds: ICS Symposium Honoring Wolf Prize Laureates Stephen L. Buchwald and John F. Hartwig: May 29, 2019, Technion-Israel Institute of Technology,Haifa, Israel

This report covers two exciting events in the scientific landscape of the State of Israel: the traditional Wolf Prize Symposium of the ICS and the Wolf Prize Ceremony in the Knesset. The symposium, dedicated to the science of Stephen L. Buchwald and John F. Hartwig, highlighted the catalytic formation of C−N bonds. In a general sense, the two Wolf Prize laureates may be considered as molecular architects who produced efficient molecular-scale machines that make important molecules for the benefit of humanity. After receiving the Wolf Prize from Israel's President, Buchwald commented, “There are many who believe that support for research should focus exclusively on endeavors that have specific practical applications in mind. With this mindset, our work would have never been possible. Time and time again experience shows that it is exceedingly difficult to predict which scientific discoveries will lead to major advances. So often, it is the scientist following his or her own intellectual curiosity whose work leads to a breakthrough. I believe that basic curiosity-driven research and societal and economic progress are inextricably linked.” And Hartwig comments, “We all know the principles of science know no boundaries, but maybe less appreciated, or taken for granted, is that the assembly of research teams in many places knows no boundaries. If we recognize and nurture talent in people from all corners and all backgrounds we can address and maybe solve today's most important problems in health, energy, and environmental sustainability that are urgently facing us.”     

Plutonium recycling in hydride fueled PWR cores

The classic approach to the recycling of Pu in PWR is to use mixed U-oxide Pu-oxide (MOX) fuel. The mono-recycling of plutonium in PWR transmutes less than 30% of the loaded plutonium, providing only a limited reduction in the long-term radiotoxicity and in the inventory of TRU to be stored in the repository. The primary objective of this study is to assess the feasibility of plutonium recycling in PWR in the form of plutonium hydride, PuH₂, mixed with uranium and zirconium hydride, ZrH_1.6, referred to as PUZH, that is loaded uniformly in each fuel rod. The assessment is performed by comparing the performance of the PUZH fueled core to that of the MOX fueled core. Performance characteristics examined are transmutation effectiveness, proliferation resistance of the discharged fuel and fuel cycle economics. The PUZH loaded core is found superior to the MOX fueled core in terms of the transmutation effectiveness and proliferation resistance. For the reference cycle duration and reference fuel rod diameter and pitch, the percentage of the plutonium loaded that is transmuted in one recycle is 53% for PUZH versus 29% for MOX fuel. That is, the net amount of plutonium transmuted in the first recycle is 55% higher in cores using PUZH than in cores using MOX fuel. Relative to the discharged MOX, the discharged PUZH fuel has smaller fissile plutonium fraction - 45% versus 60%, 15% smaller minor actinides (MA) inventory and more than double spontaneous fission neutron source intensity and decay heat per gram of discharged TRU. Relative to the MOX fuel assembly, the radioactivity of the PUZH fuel assembly is 26% smaller and the decay heat and the neutron yield are only 3% larger. The net effect is that the handling of the discharged PUZH fuel assembly will be comparable in difficulty to that of the discharged MOX assembly while the proliferation resistance of the TRU of the discharged PUZH fuel is enhanced.     

Uranium-zirconium hydride fuel properties

Properties of the two-phase hydride U_0.3ZrH_1.6 pertinent to performance as a nuclear fuel for LWRs are reviewed. Much of the available data come from the Space Nuclear Auxiliary Power (SNAP) program of 4 decades ago and from the more restricted data base prepared for the TRIGA research reactors some 3 decades back. Transport, mechanical, thermal and chemical properties are summarized. A principal difference between oxide and hydride fuels is the high thermal conductivity of the latter. This feature greatly decreases the temperature drop over the fuel during operation, thereby reducing the release of fission gases to the fraction due only to recoil. However, very unusual early swelling due to void formation around the uranium particles has been observed in hydride fuels. Avoidance of this source of swelling limits the maximum fuel temperature to ∼650 °C (the design limit recommended by the fuel developer is 750 °C). To satisfy this temperature limitation, the fuel-cladding gap needs to be bonded with a liquid metal instead of helium. Because the former has a thermal conductivity ∼100 times larger than the latter, there is no restriction on gap thickness as there is in helium-bonded fuel rods. This opens the possibility of initial gap sizes large enough to significantly delay the onset of pellet-cladding mechanical interaction (PCMI). The large fission-product swelling rate of hydride fuel (3× that of oxide fuel) requires an initial radial fuel-cladding gap of ∼300 m if PCMI is to be avoided. The liquid-metal bond permits operation of the fuel at current LWR linear-heat-generation rates without exceeding any design constraint. The behavior of hydrogen in the fuel is the source of phenomena during operation that are absent in oxide fuels. Because of the large heat of transport (thermal diffusivity) of H in ZrH_x, redistribution of hydrogen in the temperature gradient in the fuel pellet changes the initial H/Zr ratio of 1.6 to ∼1.45 at the center and ∼1.70 at the periphery. Because the density of the hydride decreases with increasing H/Zr ratio, the result of H redistribution is to subject the interior of the pellet to a tensile stress while the outside of the pellet is placed in compression. The resulting stress at the pellet periphery is sufficient to overcome the tensile stress due to thermal expansion in the temperature gradient and to prevent radial cracking that is a characteristic of oxide fuel. Several mechanisms for reduction of the H/Zr ratio during irradiation are identified. The first is transfer of impurity oxygen in the fuel from Zr to rare-earth oxide fission products. The second is the formation of metal hydrides by these same fission products. The third is by loss to the plenum as H₂.The review of the fabrication method for the hydride fuel suggests that its production, even on a large scale, may be significantly higher than the cost of oxide fuel fabrication.     

Exact and efficient computation of moments of free-form surface and trivariate based geometry

Two schemes for computing moments of free-form objects are developed and analyzed. In the first scheme, we assume that the boundary of the analyzed object is represented using parametric surfaces. In the second scheme, we represent the boundary of the object as a constant set of a trivariate function. These schemes rely on a pre-computation step which allows fast re-evaluation of the moments when the analyzed object is modified. Both schemes take advantage of a representation that is based on the B-spline blending functions.     

Effect of Various Treatments on the Optical Properties of Montmorillonite Suspensions

The light absorption spectra of Na, K, Ca and Ba-montmorillonite suspensions were studied in relation to the procedure of sample preparation. These procedures included different sequences of transformations from one homoionic form into another, as well as a drying stage during the preparation. The optical density was usually influenced by the method of preparation, indicating hysteresis effects in the transformation process. The data were interpreted in terms of tactoid formation and size. Transformation of monovalent into divalent clay suspensions resulted in small tactoids. Air drying of the clay before the transformation resulted in larger tactoids in both mono- and divalent clays. Negative adsorption of chloride in Ca-bentonite from two different preparations (which differed in their tactoid size) were in agreement with the light absorption measurements: the higher surface area was found in the suspension with the smaller tactoids. The data available in the literature on negative absorption of chloride on montmorillonite are discussed. It is suggested that the discrepancies in the experimental results of different investigators could be, at least partially, explained by the differences in the preparation procedure of the clay suspensions.     

DNA Lesions and Mammalian Cell Killing: Cause and Effect?

Although indirect, studies of repair mechanisms afford a useful approach to the questions: Where and what are the sensitive sites in a cell related to division? This approach has been used with mammalian cells based on the fact that sublethal damage must be accumulated to kill a cell and the observation that cells can repair sublethal damage. Actinomycin D was found to inhibit this repair, an observation which justified a focus upon nuclear DNA as the site of damage and repair. Sedimentation studies with alkaline gradients revealed two repair processes. Repair of single-strand breaks (also found by others) and repair to a complex of DNA, lipid, and protein. In cells sensitized to fluorescent light because of prior growth in the presence of 5-bromodeoxyuridine, the data suggest that single-strand breaks is the lethal lesion. In contrast, damage to a DNA-membrane structure appears a more likely target for X-ray cell killing.     

Ontogenesis of peripheral electromagnetic receptors in hornets

This article traces the ontogenesis of peripheral electromagnetic receptors (PER) in the cuticle of the Oriental hornet (Vespa orientalis). In the abdominal cuticle of adult hornets, the PERs are densely distributed throughout, but there are even more than 30 at the margins of the segments. These organelles develop as a network in the hornet cuticle immediately upon its completion. Briefly, from each basic cell of a PER grows a bulge towards the exterior, that is, towards the illuminated region of the cuticle. This bulge develops rapidly and as it grows it starts to push out and lift up the various layers of the cuticle, the while pressing them together. By a spiraling movement, the bulge insinuates itself between the layers, whereupon it dissolves and punctures its way through all the layers of the hypocuticle, via the endocuticle up to the exocuticle. The only cuticular layer that remains intact is the epicuticle, but even that undergoes change, assuming the shape of a smooth surface with a depression at its center. The indented part in the epicuticle is circular, approximately 2.5 microm in diameter and enables the entry of radiation (illumination) from the outside into the PER, which is located half-way down the cuticle, with the distance from the exterior to the base of the PER being approximately 25 microm. The numerous lamellae of the cuticle run parallel to one another, but in the region of the bulge they are either perpendicular or directed upwards. This ontogeny of the PERs lends the cuticle a sandwich-like shape, being radically perforated by the PERs bulges, yet covered at the top by the epicuticle and at the bottom by basal cells. The PERs also extend shoots into the cuticular layer and these further perforate the cuticle but also interlink the various PERs. From all the above, it is clear that the cuticle forms first and only subsequently does the network of PERs develop and interpenetrate its various layers.     

Synthesis and size-dependent properties of zinc-blende semiconductor quantum rods

Dimensionality and size are two factors that govern the properties of semiconductor nanostructures. In nanocrystals, dimensionality is manifested by the control of shape, which presents a key challenge for synthesis. So far, the growth of rod-shaped nanocrystals using a surfactant-controlled growth mode, has been limited to semiconductors with wurtzite crystal structures, such as CdSe (ref. 3). Here, we report on a general method for the growth of soluble nanorods applied to semiconductors with the zinc-blende cubic lattice structure. InAs quantum rods with controlled lengths and diameters were synthesized using the solution-liquid-solid mechanism with gold nanocrystals as catalysts. This provides an unexpected link between two successful strategies for growing high-quality nanomaterials, the vapour-liquid-solid approach for growing nanowires, and the colloidal approach for synthesizing soluble nanocrystals. The rods exhibit both length- and shape-dependent optical properties, manifested in a red-shift of the bandgap with increased length, and in the observation of polarized emission covering the near-infrared spectral range relevant for telecommunications devices.