Explosive and chemical threat detection by surface-enhanced Raman scattering: A review

Acts of terror and warfare threats are challenging tasks for defense agencies around the world and of growing importance to security conscious policy makers and the general public. Explosives and chemical warfare agents are two of the major concerns in this context, as illustrated by the recent Boston Marathon bombing and nerve gas attacks on civilians in the Middle East. To prevent such tragic disasters, security personnel must be able to find, identify and deactivate the threats at multiple locations and levels. This involves major technical and practical challenges, such as detection of ultra-low quantities of hazardous compounds at remote locations for anti-terror purposes and monitoring of environmental sanitation of dumped or left behind toxic substances and explosives. Surface-enhanced Raman scattering (SERS) is one of todays most interesting and rapidly developing methods for label-free ultrasensitive vibrational “fingerprinting” of a variety of molecular compounds. Performance highlights include attomolar detection of TNT and DNT explosives, a sensitivity that few, if any, other technique can compete with. Moreover, instrumentation needed for SERS analysis are becoming progressively better, smaller and cheaper, and can today be acquired for a retail price close to 10,000 US$. This contribution aims to give a comprehensive overview of SERS as a technique for detection of explosives and chemical threats. We discuss the prospects of SERS becoming a major tool for convenient in-situ threat identification and we summarize existing SERS detection methods and substrates with particular focus on ultra-sensitive real-time detection. General concepts, detection capabilities and perspectives are discussed in order to guide potential users of the technique for homeland security and anti-warfare purposes.     

Synthesis, crystal structures, and hydrogen-storage properties of Eu(AlH4)2 and Sr(AlH4)2 and of their decomposition intermediates, EuAlH5 and SrAlH5

Complex Eu(AlH(4))(2) and Sr(AlH(4))(2) hydrides have been prepared by a mechanochemical metathesis reaction from NaAlH(4) and europium or strontium chlorides. The crystal structures were solved from powder X-ray diffraction data in combination with solid-state (27)Al NMR spectroscopy. The thermolysis pathway was analyzed in detail, allowing identification of new intermediate EuAlH(5)/SrAlH(5) compounds. Rehydrogenation experiments indicate that the second decomposition step is reversible.     

Catalytic α-allylation of unprotected amino acid esters

Catalytic α-allylation of unprotected amino acid esters to produce α-quaternary α-allyl amino acid esters is reported. Catalytic loadings of picolinaldehyde and Ni(II) salts induce preferential reactivity at the enolizable α-carbon of amino acid esters over the free nitrogen with electrophilic palladium π-allyl complexes. Fourteen examples are given. Additionally, the use of chiral ligands to access enantioenriched α-quaternary amino acid esters from racemic precursors is demonstrated by the enantioselective synthesis of α-allyl phenylalanine methyl ester from racemic phenylalanine methyl ester.     

Cremona maps defined by monomials

Cremona maps defined by monomials of degree 2 are thoroughly analyzed and classified via integer arithmetic and graph combinatorics. In particular, the structure of the inverse map to such a monomial Cremona map is made very explicit as is the degree of its monomial defining coordinates. As a special case, one proves that any monomial Cremona map of degree 2 has inverse of degree 2 if and only if it is an involution up to permutation in the source and in the target. This statement is subsumed in a recent result of L. Pirio and F. Russo, but the proof is entirely different and holds in all characteristics. One unveils a close relationship binding together the normality of a monomial ideal, monomial Cremona maps and Hilbert bases of polyhedral cones.     

Quantitative characterization of critical nanoclusters nucleated on large single molecules

First order phase transitions involve nucleation, formation of nanoscale regions of a new phase within a metastable parent phase. Using the heterogeneous nucleation theorem we show how clusters formed by nucleation on single molecules evolve from the gas phase and determine the critical size beyond which condensation starts to form aerosol particles. Our experiments reveal the activation of molecules into droplets to happen via formation of critical clusters substantially larger than the seed molecule. The nanosized critical clusters were found to be well predicted by the Kelvin-Thomson relation pointing directly to the key step in the phase transition.     

Electrodynamics of Abrikosov vortices: the field theoretical formulation

Electrodynamic phenomena related to vortices in superconductors have been studied since their prediction by Abrikosov, and seem to hold no fundamental mysteries. However, most of the effects are treated separately, with no guiding principles.We demonstrate that the relativistic vortex worldsheet in spacetime is the object that naturally conveys all electric and magnetic information, for which we obtain simple and concise equations. Breaking Lorentz invariance leads to down-to-earth Abrikosov vortices, and special limits of these equations include for instance dynamic Meissner screening and the AC Josephson relation. On a deeper level, we explore the electrodynamics of two-form sources in the absence of electric monopoles, in which the electromagnetic field strength itself acquires the characteristics of a gauge field. This novel framework leaves room for unexpected surprises.     

Soft spin wave near nu=1: evidence for a magnetic instability in Skyrmion systems

The ground state of the two-dimensional electron gas near nu=1 is investigated by inelastic light scattering measurements carried down to very low temperatures. Away from nu=1, the ferromagnetic spin wave collapses and a new low-energy spin wave emerges below the Zeeman gap. The emergent spin wave shows soft behavior as its energy increases with temperature and reaches the Zeeman energy for temperatures above 2 K. The observed softening indicates an instability of the two-dimensional electron gas towards a magnetic order that breaks spin rotational symmetry. We discuss our findings in light of the possible existence of a Skyrme crystal.