Multiplex coherent raman spectroscopy detector and method

A multiplex coherent Raman spectrometer (10) and spectroscopy method rapidly detects and identifies individual components of a chemical mixture separated by a separation technique, such as gas chromatography. The spectrometer (10) and method accurately identify a variety of compounds because they produce the entire gas phase vibrational Raman spectrum of the unknown gas. This is accomplished by tilting a Raman cell (20) to produce a high-intensity, backward-stimulated, coherent Raman beam of 683 nm, which drives a degenerate optical parametric oscillator (28) to produce a broadband beam of 1100-1700 nm covering a range of more than 3000 wavenumber. This broadband beam is combined with a narrowband beam of 532 nm having a bandwidth of 0.003 wavenumbers and focused into a heated windowless cell (38) that receives gases separated by a gas chromatograph (40). The Raman radiation scattered from these gases is filtered and sent to a monochromator (50) with multichannel detection

Robust Chauvenet Outlier Rejection

Sigma clipping is commonly used in astronomy for outlier rejection, but the number of standard deviations beyond which one should clip data from a sample ultimately depends on the size of the sample. Chauvenet rejection is one of the oldest, and simplest, ways to account for this, but, like sigma clipping, depends on the sample's mean and standard deviation, neither of which are robust quantities: Both are easily contaminated by the very outliers they are being used to reject. Many, more robust measures of central tendency, and of sample deviation, exist, but each has a tradeoff with precision. Here, we demonstrate that outlier rejection can be both very robust and very precise if decreasingly robust but increasingly precise techniques are applied in sequence. To this end, we present a variation on Chauvenet rejection that we call "robust" Chauvenet rejection (RCR), which uses three decreasingly robust/increasingly precise measures of central tendency, and four decreasingly robust/increasingly precise measures of sample deviation. We show this sequential approach to be very effective for a wide variety of contaminant types, even when a significant -- even dominant -- fraction of the sample is contaminated, and especially when the contaminants are strong. Furthermore, we have developed a bulk-rejection variant, to significantly decrease computing times, and RCR can be applied both to weighted data, and when fitting parameterized models to data. We present aperture photometry in a contaminated, crowded field as an example. RCR may be used by anyone at https://skynet.unc.edu/rcr, and source code is available there as well.Comment: 62 pages, 48 figures, 7 tables, accepted for publication in ApJ

GSE statistics without spin

Energy levels statistics following the Gaussian Symplectic Ensemble (GSE) of Random Matrix Theory have been predicted theoretically and observed numerically in numerous quantum chaotic systems. However in all these systems there has been one unifying feature: the combination of half-integer spin and time-reversal invariance. Here we provide an alternative mechanism for obtaining GSE statistics that is based on geometric symmetries of a quantum system which alleviates the need for spin. As an example, we construct a quantum graph with a particular discrete symmetry given by the quaternion group Q8. GSE statistics is then observed within one of its subspectra.Comment: 5 pages, 6 figure

Chaotic maps and flows: Exact Riemann-Siegel lookalike for spectral fluctuations

To treat the spectral statistics of quantum maps and flows that are fully chaotic classically, we use the rigorous Riemann-Siegel lookalike available for the spectral determinant of unitary time evolution operators $F$. Concentrating on dynamics without time reversal invariance we get the exact two-point correlator of the spectral density for finite dimension $N$ of the matrix representative of $F$, as phenomenologically given by random matrix theory. In the limit $N\to\infty$ the correlator of the Gaussian unitary ensemble is recovered. Previously conjectured cancellations of contributions of pseudo-orbits with periods beyond half the Heisenberg time are shown to be implied by the Riemann-Siegel lookalike

Semiclassical approach to discrete symmetries in quantum chaos

We use semiclassical methods to evaluate the spectral two-point correlation function of quantum chaotic systems with discrete geometrical symmetries. The energy spectra of these systems can be divided into subspectra that are associated to irreducible representations of the corresponding symmetry group. We show that for (spinless) time reversal invariant systems the statistics inside these subspectra depend on the type of irreducible representation. For real representations the spectral statistics agree with those of the Gaussian Orthogonal Ensemble (GOE) of Random Matrix Theory (RMT), whereas complex representations correspond to the Gaussian Unitary Ensemble (GUE). For systems without time reversal invariance all subspectra show GUE statistics. There are no correlations between non-degenerate subspectra. Our techniques generalize recent developments in the semiclassical approach to quantum chaos allowing one to obtain full agreement with the two-point correlation function predicted by RMT, including oscillatory contributions.Comment: 26 pages, 8 Figure

Pharmacodynamic Assays to Facilitate Preclinical and Clinical Development of Pre-mRNA Splicing Modulatory Drug Candidates

The spliceosome has recently emerged as a new target for cancer chemotherapy and novel antitumor spliceosome targeted agents are under development. Here, we describe two types of novel pharmacodynamic assays that facilitate drug discovery and development of this intriguing class of innovative therapeutics; the first assay is useful for preclinical optimization of small-molecule agents that target the SF3B1 spliceosomal protein in animals, the second assay is an ex vivo validated, gel-based assay for the measurement of drug exposure in human leukocytes. The first assay utilizes a highly specific bioluminescent splicing reporter, based on the skipping of exons 4-11 of a Luc-MDM2 construct, which specifically yields active luciferase when treated with small-molecule spliceosome modulators. We demonstrate that this reporter can be used to monitor alternative splicing in whole cells in vitro. We describe here that cell lines carrying the reporter can be used in vivo for the efficient pharmacodynamic analysis of agents during drug optimization and development. We also demonstrate dose- and time-dependent on-target activity of sudemycin D6 (SD6), which leads to dramatic tumor regression. The second assay relies on the treatment of freshly drawn human blood with SD6 ex vivo treatment. Changes in alternative splicing are determined by RT-PCR using genes previously identified in in vitro experiments. The Luc-MDM2 alternative splicing bioluminescent reporter and the splicing changes observed in human leukocytes should allow for the more facile translation of novel splicing modulators into clinical application

Finite pseudo orbit expansions for spectral quantities of quantum graphs

We investigate spectral quantities of quantum graphs by expanding them as sums over pseudo orbits, sets of periodic orbits. Only a finite collection of pseudo orbits which are irreducible and where the total number of bonds is less than or equal to the number of bonds of the graph appear, analogous to a cut off at half the Heisenberg time. The calculation simplifies previous approaches to pseudo orbit expansions on graphs. We formulate coefficients of the characteristic polynomial and derive a secular equation in terms of the irreducible pseudo orbits. From the secular equation, whose roots provide the graph spectrum, the zeta function is derived using the argument principle. The spectral zeta function enables quantities, such as the spectral determinant and vacuum energy, to be obtained directly as finite expansions over the set of short irreducible pseudo orbits.Comment: 23 pages, 4 figures, typos corrected, references added, vacuum energy calculation expande