A beta-lactone route to chiral gamma-substituted alpha-amino acids: application to the concise synthesis of (S)-alpha-azidobutyro lactone and a natural amino acid

[reaction: see text] Beta-lactones are useful synthetic intermediates allowing access to a number of functional arrays. In this report, enantiomerically pure 4-trichloromethyl-2-oxetanone is shown to be a versatile amino acid synthon leading to a variety of gamma-substituted alpha-amino acid precursors. The utility of this methodology was demonstrated by the concise synthesis of a protected homoserine equivalent, alpha-azidobutyro lactone, and a naturally occurring alpha-amino acid from the seeds of Blighia unijugata.     

Bis(isoquinoline N-oxide) pincers as a new type of metal cation dual channel fluorosensor

[structure: see text] A new type of donor-spacer-acceptor podand system has been synthesized and proved as an efficient dual channel fluorosensor for Li+, Mg2+, and Ca2+. The known ability for the N-oxide function to bind Lewis acids is the key step in the appearance of a new emitting charge-transfer (CT) excited state. The occurrence of this CT state for alkaline earth (Mg2+ and Ca2+) and not for alkaline metals (Li+) provided a new type of dual channel fluorosensors.     

Self-organization of chalcogen-containing cyclic alkynes and alkenes to yield columnar structures

Close contacts between chalcogen atoms in cyclic dienes and diynes are used to create columnar structures in the solid state. Rigid and fairly planar cycles with chalcogen centers are the preconditions for forming those columnar structures.     

Halophilic reactions of a stable silylene with chloro and bromocarbons

A number of disilanes have been synthesized from a stable silylene, 1 (N,N'-di-tert-butyl-1,3-diaza-2-silacyclopent-4-en-2-ylidene), and a variety of halocarbons. It is proposed that disilane formation is a result of an initial halophilic interaction between the silylene and halocarbon. Formation of disilanes from 1 and CCl4, 2a, CHCl3, 2b, CH2Cl2, 2c, benzyl chloride, 2d, and bromobenzene, 5, are described here. An X-ray crystal structure of 2b was determined.     

Luminescence lifetime-based sensor for cyanide and related anions

A new Ru(II) complex is described which serves as a luminescence lifetime-based sensor for fluoride and cyanide anions (KF = 640 000 mol-1, KCN = 430 000 mol-1). This chromophore displays observable changes in its UV-vis and steady-state luminescence spectra upon cyanide binding. Prior to cyanide addition, this complex exhibits a single-exponential lifetime (tau = 377 +/- 20 ns). With increasing cyanide concentrations, the intensity decays are composed of two exponentials: long tau (320-370 ns) and short tau (13-17 ns). The average lifetimes shorten as a function of cyanide concentration since the fractional intensity shifts from an initial dominant long lifetime component to the short lifetime component. This work represents the first example of a direct method for the luminescence lifetime-based sensing of anions.     

Supramolecular assembly on surfaces: manipulating conductance in noncovalently modified mesoscale structures

Molecules capable of complementary hydrogen bonding were used to control the noncovalent self-assembly and electronic properties of a chemically well-defined surface mesostructure. In this work, we patterned a footprint region for molecular assembly on a surface and used moieties featuring complementary recognition to tune the current-voltage properties of the patterned region. With the appropriate functionalities on the complementary moieties, we were able to increase and decrease the observed conductance in surface-bound mesoscale structures imaged by scanning tunneling microscopy (STM).     

Effective temperature in driven vortex lattices with random pinning

We study numerically correlation and response functions in nonequilibrium driven vortex lattices with random pinning. From a generalized fluctuation-dissipation relation, we calculate an effective transverse temperature in the fluid moving phase. We find that the effective temperature decreases with increasing driving force and becomes equal to the equilibrium melting temperature when the dynamic transverse freezing occurs. We also discuss how the effective temperature can be measured experimentally from a generalized Kubo formula.     

Singularity in the thermal boundary resistance between superfluid (4)He and a solid surface

We report new measurements in four cells of the thermal boundary resistance R between copper and (4)He below but near the superfluid-transition temperature T(lambda). For 10(-7)< or =t identical to 1-T/T(lambda))< or =10(-4) fits of R = R(0)t(-x(b))+R(B) to the data yielded x(b) approximately equal to 0.18, whereas a fit to theoretical values based on the renormalization-group theory yielded x(b) = 0.23. Alternatively, a good fit of the theory to the data could be obtained if the amplitude of the prediction was reduced by a factor close to 2. The results raise the question whether the boundary conditions used in the theory should be modified.     

Spin disorder scattering in magnetic metallic alloys

Anomalous behavior of the resistivity at or just below the Néel temperature in antiferromagnetic metals is usually attributed to the formation of superzone gaps. However, we find that RMn12-xFex alloys which have no such gaps exhibit a similarly anomalous resistivity. We show that electron scattering by substitutional spin disorder can account for such behavior of itinerant magnets. This mechanism, which has not been studied before, leads to a relaxation rate that is proportional to x(12-x)m(2), where m is the staggered magnetization. Together with spin fluctuations, phonon, and impurity scattering, it accounts well for the resistivity data we obtain for HoMn12-xFex, for 0< or =x< or =9, in the temperature range of 4 to 400 K.