Alkynes as masked ylides: gold-catalysed intermolecular reactions of propargylic carboxylates with sulfides

The in situ-generation of sulfur ylides by the gold-catalysed rearrangement of propargylic carboxylates in the presence of sulfides has resulted in highly efficient and novel transformations.     

Gas-phase fragmentation of half- and first-generation polyamidoamine dendrimers by electrospray mass spectrometry using a quadrupole ion trap

Polyamidoamine (PAMAM) dendrimers are nanopolymers that can bind with biomolecules such as DNA, drugs or proteins. In order to study these complexes, we first fragmented half- and first-generation PAMAM, G0.5 and G1, respectively, using a quadrupole ion trap (QIT) equipped with an electrospray ionisation source. For both G0.5 and G1 we observed a series of impurities that only can stem from synthesis defects and that are principally due to missing branches and intramolecular cyclisations. Fragmentations of G1 showed regularity in the product ions. These ions result from the loss of 60 Da, obtained by an intramolecular cyclisation, and from the loss of 114 Da, obtained by a four-centred hydrogen transfer or a retro-Michael reaction. The fragmentations stemmed either from competitive or from consecutive reactions, even though resonant fragmentation QIT was used. It is shown that the principal fragmentation reaction is a retro-Michael rearrangement for both G1 and G0.5. In addition, by fragmenting totally deuterated [G1-d28]Na+ we were able to establish fragmentation pathways.     

Coordination chemistry of tetra- and tridentate ferrocenyl polyphosphines: an unprecedented [1,1'-heteroannular and 2,3-homoannular]-phosphorus-bonding framework in a metallocene dinuclear coordination complex

PalladiumII and nickelII halide complexes of the ferrocenyl polyphosphines 1,1',2,3-tetrakis(diphenylphosphino)ferrocene (1), and 1,1',2-tris(diphenylphosphino)-4-tert-butylferrocene (5) were prepared and characterized by multinuclear NMR. The metallo-ligand 1, the palladium [Pd2Cl4(1)] (3b) and nickel [NiCl2(5)] (6) coordination complexes were additionally characterized by X-ray diffraction crystallography. The behavior of 1 toward coordination to nickel and palladium was surprisingly different because the coordination of a second metal center after the initial 1,2-phosphorus-bonding of nickel was markedly difficult. The preference of nickel for 1,2-P coordination on 1,1'-bonding was confirmed by the exclusive formation of 6 from 5. The changes noted between the solid state structure of the ligand 1 and the structure obtained for the dinuclear palladium complex 3b reveal the rotational flexibility of this tetraphosphine. This flexibility is at the origin of the unique framework for a metallocenic dinuclear metal complex in which both coexist a 1,1'-heteroannular chelating P-bonding and a 2,3-homoannular chelating P-bonding with two palladium centers. Some reported specimens of ferrocenyl polyphosphines of constrained geometry have previously revealed that phosphorus lone pair overlap can lead to very intense "through-space" 31P31P nuclear spin-spin coupling constants (JPP) ( J. Am. Chem. Soc. 2004, 126 (35), 11077-11087] in solution phase. In these cases, an internuclear distance between heteroannular phosphorus atoms below 4.9 A, with an adequate orientation of the lone-pairs in the solid state and in solution, was a necessary parameter. The flexibility of the new polyphosphines 1 and 5 does not allow that spatial proximity (internuclear distances between heteroannular phosphorus above 5.2 A in the solid state); accordingly the expected through-space nuclear spin-spin coupling constants were not detected in any of their coordination complexes nor in 1.     

Ground state of the kagomé-like S=1/2 antiferromagnet volborthite Cu3V2O7(OH)2 x 2H2O

The volborthite compound is one of the very few realizations of S=1/2 quantum spins on a highly frustrated kagomé-like lattice. Low-T SQUID measurements reveal a broad magnetic transition below 2 K which is further confirmed by a peak in the 51V nuclear spin relaxation rate (1/T1) at 1.4 K +/- 0.2 K. Through 51V NMR, the ground state (GS) appears to be a mixture of different spin configurations, among which 20% corresponds to a well defined short-range order, possibly of the sqrt(3) x sqrt(3) type. While the freezing involves all the Cu2+ spins, only 40% of the copper moment is actually frozen which suggests that quantum fluctuations strongly renormalize the GS.     

Comparison of laser ion acceleration from the front and rear surfaces of thin foils

The comparative efficiency and beam characteristics of high-energy ions generated by high-intensity short-pulse lasers (approximately 1-6 x 10(19) W/cm2) from both the front and rear surfaces of thin metal foils have been measured under identical conditions. Using direct beam measurements and nuclear activation techniques, we find that rear-surface acceleration produces higher energy particles with smaller divergence and a higher efficiency than front-surface acceleration. Our observations are well reproduced by realistic particle-in-cell simulations, and we predict optimal criteria for future applications.     

Unconditional security of a three state quantum key distribution protocol

Quantum key distribution (QKD) protocols are cryptographic techniques with security based only on the laws of quantum mechanics. Two prominent QKD schemes are the Bennett-Brassard 1984 and Bennett 1992 protocols that use four and two quantum states, respectively. In 2000, Phoenix et al. proposed a new family of three-state protocols that offers advantages over the previous schemes. Until now, an error rate threshold for security of the symmetric trine spherical code QKD protocol has been shown only for the trivial intercept-resend eavesdropping strategy. In this Letter, we prove the unconditional security of the trine spherical code QKD protocol, demonstrating its security up to a bit error rate of 9.81%. We also discuss how this proof applies to a version of the trine spherical code QKD protocol where the error rate is evaluated from the number of inconclusive events.     

Magnetotransport at domain walls in BiFeO3

Domain walls in multiferroics can exhibit intriguing behaviors that are significantly different from the bulk of the material. We investigate strong magnetoresistance in domain walls of the model multiferroic BiFeO3 by probing ordered arrays of 109° domain walls with temperature- and magnetic-field-dependent transport. We observe temperature-dependent variations in the transport mechanism and magnetoresistances as large as 60%. These results suggest that by locally breaking the symmetry of a material, such as at domain walls and structural interfaces, one can induce emergent behavior with properties that deviate significantly from the bulk.     

Some properties of buyback and other related schemes in a newsvendor-product supply chain with price-sensitive demand

A manufacturer wholesaling to a retailer a ‘newsvendor-type’ product such as a seasonal/fashion good or a perishable food item is considered here. It is known that such a manufacturer/retailer channel has difficulties in fully realizing the market's profit potential. We study a theoretical construct of such a channel and present practically useful results for a manufacturer trying to design more profitable pricing schemes. Specifically, we consider a ‘dominant’ manufacturer supplying a newsvendor-type product to a retailer. The retail market volume varies with the unit retail price according to a stochastic demand curve. We study the design and performance of ‘price-only’, ‘buyback’ and ‘manufacturer-imposed retail price’ schemes. All these schemes have been considered in earlier works. The first part of this paper studies some important but previously overlooked aspects of price-only and buyback schemes. We show that the performance of these schemes is strongly and somewhat counter-intuitively affected by the specific form of demand curve and of demand randomization. Thus, we identify hitherto neglected factors that must be carefully considered when designing pricing schemes for actual implementation. The second part of this paper demonstrates the practicality and merit of using buyback in conjunction with a manufacturer-imposed retail price—an arrangement overlooked in the literature because it is widely mistaken as illegal. Overall, the paper shows how a manufacturer can better realize the market's potential by: (i) modifying slightly the well-known buyback arrangement; and (ii) carefully modelling certain hitherto neglected aspects of the price/demand relationship—a conclusion quite contrary to what one might surmise from the current theoretical literature.     

Combined Designs and Labour Programming

In this paper, the problem of labour scheduling is solved using Combinatorial analysis with Combined designs; characteristic applications to scheduling industrial labour, itinerary distribution and supervision are given.