The Anomalous Behavior of Solid 4^{4}He in Porous Vycor Glass

The low temperature properties of solid $^4$He contained in porous Vycor glass have been investigated utilizing a two-mode compound torsional oscillator. At low temperatures, we find period shift signals for the solid similar to those reported by Kim and Chan \cite{ref1}, which were taken at the time as evidence for a supersolid helium phase. The supersolid is expected to have properties analogous to those of a conventional superfluid, where the superfluid behavior is independent of frequency and the ratio of the superfluid signals observed at two different mode periods will depend only on the ratio of the sensitivities of the mode periods to mass-loading. In the case of helium studies in Vycor, one can compare the period shift signals seen for a conventional superfluid film with signals obtained for a supersolid within the same Vycor sample. We find, contrary to our own expectations, that the signals observed for the solid display a marked period dependence not seen in the case of the superfluid film. This surprising result suggests that the low temperature response of solid $^4$He in a Vycor is more complex than previously assumed and cannot be thought of as a simple superfluid.Comment: 4 pages, 5 figure

Probing Coherent Vibrations of Organic Phosphonate Radical Cations with Femtosecond Time-Resolved Mass Spectrometry

Organic phosphates and phosphonates are present in a number of cellular components that can be damaged by exposure to ionizing radiation. This work reports femtosecond time-resolved mass spectrometry (FTRMS) studies of three organic phosphonate radical cations that model the DNA sugar-phosphate backbone: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), and diisopropyl methylphosphonate (DIMP). Upon ionization, each molecular radical cation exhibits unique oscillatory dynamics in its ion yields resulting from coherent vibrational excitation. DMMP has particularly well-resolved 45 fs (732 ± 28 cm−1) oscillations with a weak feature at 610–650 cm−1, while DIMP exhibits bimodal oscillations with a period of ∼55 fs and two frequency features at 554 ± 28 and 670–720 cm−1. In contrast, the oscillations in DEMP decay too rapidly for effective resolution. The low- and high-frequency oscillations in DMMP and DIMP are assigned to coherent excitation of the symmetric O–P–O bend and P–C stretch, respectively. The observation of the same ionization-induced coherently excited vibrations in related molecules suggests a possible common excitation pathway in ionized organophosphorus compounds of biological relevance, while the distinct oscillatory dynamics in each molecule points to the potential use of FTRMS to distinguish among fragment ions produced by related molecules

X-shaped and Y-shaped Andreev resonance profiles in a superconducting quantum dot

The quasi-bound states of a superconducting quantum dot that is weakly coupled to a normal metal appear as resonances in the Andreev reflection probability, measured via the differential conductance. We study the evolution of these Andreev resonances when an external parameter (such as magnetic field or gate voltage) is varied, using a random-matrix model for the $N\times N$ scattering matrix. We contrast the two ensembles with broken time-reversal symmetry, in the presence or absence of spin-rotation symmetry (class C or D). The poles of the scattering matrix in the complex plane, encoding the center and width of the resonance, are repelled from the imaginary axis in class C. In class D, in contrast, a number $\propto\sqrt{N}$ of the poles has zero real part. The corresponding Andreev resonances are pinned to the middle of the gap and produce a zero-bias conductance peak that does not split over a range of parameter values (Y-shaped profile), unlike the usual conductance peaks that merge and then immediately split (X-shaped profile).Comment: Contribution for the JETP special issue in honor of A.F. Andreev's 75th birthday. 9 pages, 8 figure

Conserved Vibrational Coherence in the Ultrafast Rearrangement of 2-Nitrotoluene Radical Cation

2-Nitrotoluene (2-NT) is a good model for both photolabile protecting groups for organic synthesis and the military explosive 2,4,6-trinitrotoluene (TNT). In addition to the direct C−NO2 bond-cleavage reaction that initiates detonation in TNT, 2-NT undergoes an H atom attack reaction common to the photolabile 2-nitrobenzyl group, which forms the aci-nitro tautomer. In this work, femtosecond pump−probe measure- ments with mass spectrometric detection and density functional theory (DFT) calculations demonstrate that the initially prepared vibrational coherence in the 2-NT radical cation (2- NT+) is preserved following H atom attack. Strong-field adiabatic ionization is used to prepare 2-NT+, which can overcome a modest 0.76 eV energy barrier to H atom attack to form the aci-nitro tautomer as soon as ∼20−60 fs after ionization. Once formed, the aci-nitro tautomer spontaneously loses −OH to form C7H6NO+, which exhibits distinctly faster oscillations in its ion yield (290 fs period) as compared to the 2-NT+ ion (380 fs period). The fast oscillations are attributed to the coherent torsional motion of the aci-nitro tautomer, which has a significantly faster computed torsional frequency (86.9 cm−1) than the 2- NT+ ion (47.9 cm−1). Additional DFT calculations identify reaction pathways leading to the formation of the dissociation products C7H6NO+, C7H7+, and C6H6N+. Collectively, these results reveal a rich picture of coherently and incoherently driven dissociation pathways in 2-NT+

Sensitivity of Ru(bpy)_2dppz^(2+) Luminescence to DNA Defects

The luminescent characteristics of Ru(bpy)_2dppz^(2+) (dppz = dipyrido[3,2-a:2′,3′-c]phenazine), a DNA light switch, were investigated in the presence of oligonucleotides containing single base mismatches or an abasic site. In water, the ruthenium luminescence is quenched, but, bound to well matched duplex DNA, the Ru complex luminesces. Here we show that with DNAs containing a defect, rac-, Δ-, and Λ-Ru(bpy)_2dppz^(2+) exhibit significant luminescent enhancements above that with well matched DNA. In the presence of a single base mismatch, large luminescent enhancements are evident for the Δ-Ru isomer; the Λ-isomer shows particularly high luminescence bound to an oligonucleotide containing an abasic site. Similar increases are not evident with two common DNA-binding organic fluorophores, ethidium bromide and TO-PRO-3. Titrations with hairpin oligonucleotides containing a variable mismatch site show correlation between the level of luminescent enhancement and the thermodynamic destabilization associated with the mismatch. This correlation is reminiscent of that found earlier for a bulky rhodium complex that binds mismatched DNA sites through metalloinsertion, where the complex binds the DNA from the minor groove side, ejecting the mismatched bases into the major groove. Differential quenching studies with minor and major groove quenchers and time-resolved emission studies support this metalloinsertion mode for the dppz complex at the defect site. Certainly these data underscore the utility of Ru(bpy)_2dppz^(2+) as a sensitive luminescent reporter of DNA and its defects

Probing Coherent Vibrations of Organic Phosphonate Radical Cations with Femtosecond Time-Resolved Mass Spectrometry

Organic phosphates and phosphonates are present in a number of cellular components that can be damaged by exposure to ionizing radiation. This work reports femtosecond time-resolved mass spectrometry (FTRMS) studies of three organic phosphonate radical cations that model the DNA sugar-phosphate backbone: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), and diisopropyl methylphosphonate (DIMP). Upon ionization, each molecular radical cation exhibits unique oscillatory dynamics in its ion yields resulting from coherent vibrational excitation. DMMP has particularly well-resolved 45 fs (732 ± 28 cm−1) oscillations with a weak feature at 610–650 cm−1, while DIMP exhibits bimodal oscillations with a period of ∼55 fs and two frequency features at 554 ± 28 and 670–720 cm−1. In contrast, the oscillations in DEMP decay too rapidly for effective resolution. The low- and high-frequency oscillations in DMMP and DIMP are assigned to coherent excitation of the symmetric O–P–O bend and P–C stretch, respectively. The observation of the same ionization-induced coherently excited vibrations in related molecules suggests a possible common excitation pathway in ionized organophosphorus compounds of biological relevance, while the distinct oscillatory dynamics in each molecule points to the potential use of FTRMS to distinguish among fragment ions produced by related molecules

Expressive Stream Reasoning with Laser

An increasing number of use cases require a timely extraction of non-trivial knowledge from semantically annotated data streams, especially on the Web and for the Internet of Things (IoT). Often, this extraction requires expressive reasoning, which is challenging to compute on large streams. We propose Laser, a new reasoner that supports a pragmatic, non-trivial fragment of the logic LARS which extends Answer Set Programming (ASP) for streams. At its core, Laser implements a novel evaluation procedure which annotates formulae to avoid the re-computation of duplicates at multiple time points. This procedure, combined with a judicious implementation of the LARS operators, is responsible for significantly better runtimes than the ones of other state-of-the-art systems like C-SPARQL and CQELS, or an implementation of LARS which runs on the ASP solver Clingo. This enables the application of expressive logic-based reasoning to large streams and opens the door to a wider range of stream reasoning use cases.Comment: 19 pages, 5 figures. Extended version of accepted paper at ISWC 201