Far Infrared and Raman Spectroscopic Investigations of the Lattice:Modes of Crystalline Thiophene

Vibrational spectroscopic measurements combined with the lattice statics and lattice mod es calculations have been applied in order to derive the most probable structure of the low temperature (stable) phase V of thiophene (below 112 K). The far infrared spectrum has been recorded from 135 to 30 cm? of this phase of thiophene at 20 K. The low frequency Raman spectrum from 150 to 10 cm" has also been record ed for the phase V at 35 K. From the fact that there is coincidence between lattice mode frequencies observed in the infrared and Raman spectra, one can exclude centrosymmetric space groups. The observations of 20 lattice modes in the Raman spectrum and 14 modes in the FIR spectrum eliminate the possibility of tetragonal symmetry, but the data are consistent with orthorhombic symmetry with the unit cell containing 4 molecules on Cl sites. In spite of the glassy-like transition observed for this phase at 42 K, both spectra bear striking resemblance to the typical low frequency spectra of molecular crystals. Therefore, it is assumed, for the purposes of the static and dynamic studies, that the thiophene in phase V can be considered as an ideally ordered crystal. Calculations of the lattice energy and lattice mode frequencies, based on the atom-atom potential, appear to be most consistent with space group Pca2l (C2v5) which is in agreement with most of the earlier predictions made for the structure of the thiophene phase V. The Raman spectrum of the metastable phase II2 is also given

Far Infrared and Raman Spectroscopic Investigations of the Lattice:Modes of Crystalline Thiophene

Vibrational spectroscopic measurements combined with the lattice statics and lattice mod es calculations have been applied in order to derive the most probable structure of the low temperature (stable) phase V of thiophene (below 112 K). The far infrared spectrum has been recorded from 135 to 30 cm? of this phase of thiophene at 20 K. The low frequency Raman spectrum from 150 to 10 cm" has also been record ed for the phase V at 35 K. From the fact that there is coincidence between lattice mode frequencies observed in the infrared and Raman spectra, one can exclude centrosymmetric space groups. The observations of 20 lattice modes in the Raman spectrum and 14 modes in the FIR spectrum eliminate the possibility of tetragonal symmetry, but the data are consistent with orthorhombic symmetry with the unit cell containing 4 molecules on Cl sites. In spite of the glassy-like transition observed for this phase at 42 K, both spectra bear striking resemblance to the typical low frequency spectra of molecular crystals. Therefore, it is assumed, for the purposes of the static and dynamic studies, that the thiophene in phase V can be considered as an ideally ordered crystal. Calculations of the lattice energy and lattice mode frequencies, based on the atom-atom potential, appear to be most consistent with space group Pca2l (C2v5) which is in agreement with most of the earlier predictions made for the structure of the thiophene phase V. The Raman spectrum of the metastable phase II2 is also given

Combined BIMA and OVRO observations of comet C/1999 S4 (LINEAR)

We present results from an observing campaign of the molecular content of the coma of comet C/1999 S4 (LINEAR) carried out jointly with the millimeter-arrays of the Berkeley-Illinois-Maryland Association (BIMA) and the Owens Valley Radio Observatory (OVRO). Using the BIMA array in autocorrelation (`single-dish') mode, we detected weak HCN J=1-0 emission from comet C/1999 S4 (LINEAR) at 14 +- 4 mK km/s averaged over the 143" beam. The three days over which emission was detected, 2000 July 21.9-24.2, immediately precede the reported full breakup of the nucleus of this comet. During this same period, we find an upper limit for HCN 1-0 of 144 mJy/beam km/s (203 mK km/s) in the 9"x12" synthesized beam of combined observations of BIMA and OVRO in cross-correlation (`imaging') mode. Together with reported values of HCN 1-0 emission in the 28" IRAM 30-meter beam, our data probe the spatial distribution of the HCN emission from radii of 1300 to 19,000 km. Using literature results of HCN excitation in cometary comae, we find that the relative line fluxes in the 12"x9", 28" and 143" beams are consistent with expectations for a nuclear source of HCN and expansion of the volatile gases and evaporating icy grains following a Haser model.Comment: 18 pages, 3 figures. Uses aastex. AJ in pres

Polarimetry and the Long Awaited Superoutburst of BZ UMa

BZ UMa is a cataclysmic variable star whose specific classification has eluded researchers since its discovery in 1968. It has outburst and spectral properties consistent with both U Gem class dwarf novae and intermediate polars. We present new photometric and polarimetric measurements of recent outbursts, including the first detected superoutburst of the system. Statistical analysis of these and archival data from outbursts over the past 40 years present a case for BZ UMa as a non-magnetic, U Gem class, SU-UMa subclass dwarf novae.Comment: Accepted by PASP for the November, 2009 issu

Atomic Tunneling from a STM/AFM tip: Dissipative Quantum Effects from Phonons

We study the effects of phonons on the tunneling of an atom between two surfaces. In contrast to an atom tunneling in the bulk, the phonons couple very strongly, and qualitatively change the tunneling behavior. This is the first example of {\it ohmic} coupling from phonons for a two-state system. We propose an experiment in which an atom tunnels from the tip of an STM, and show how its behavior would be similar to the Macroscopic Quantum Coherence behavior predicted for SQUIDS. The ability to tune and calculate many parameters would lead to detailed tests of the standard theories. (For a general intro to this work on the on the World-Wide-Web: http://www.lassp.cornell.edu. Click on ``Entertaining Science Done Here'' and ``Quantum Tunneling of Atoms'')Comment: 12 pages, ReVTex3.0, two figures (postscript). This is a (substantially) revised version of cond-mat/9406043. More info (+ postscript text) at : http://www.lassp.cornell.edu/ardlouis/publications.htm

Microwave, infrared and Raman spectra, r0 structural parameters, ab initio calculations and vibrational assignment of 1-fluoro-1-silacyclopentanea)

The microwave spectrum (6500–18 500 MHz) of 1-fluoro-1-silacyclopentane, c-C4H8SiHF has been recorded and 87 transitions for the 28Si, 29Si, 30Si, and 13C isotopomers have been assigned for a single conformer. Infrared spectra (3050-350 cm−1) of the gas and solid and Raman spectrum (3100-40 cm−1) of the liquid have also been recorded. The vibrational data indicate the presence of a single conformer with no symmetry which is consistent with the twist form. Ab initio calculations with a variety of basis sets up to MP2(full)/aug-cc-pVTZ predict the envelope-axial and envelope-equatorial conformers to be saddle points with nearly the same energies but much lower energy than the planar conformer. By utilizing the microwaverotational constants for seven isotopomers (28Si, 29Si, 30Si, and four 13C) combined with the structural parameters predicted from the MP2(full)/6–311+G(d,p) calculations, adjusted r0 structural parameters have been obtained for the twist conformer. The heavy atom distances in Å are: r0(SiC2) = 1.875(3); r0(SiC3) = 1.872(3); r0(C2C4) = 1.549(3); r0(C3C5) = 1.547(3); r0(C4C5) = 1.542(3); r0(SiF) = 1.598(3) and the angles in degrees are: ∠CSiC = 96.7(5); ∠SiC2C4 = 103.6(5); ∠SiC3C5 = 102.9(5); ∠C2C4C5 = 108.4(5); ∠C3C5C4 = 108.1(5); ∠F6Si1C2 = 110.7(5); ∠F6Si1C3 = 111.6(5). The heavy atom ring parameters are compared to the corresponding rs parameters. Normal coordinate calculations with scaled force constants from MP2(full)/6–31G(d) calculations were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values, and infrared band contours. These experimental and theoretical results are compared to the corresponding quantities of some other five-membered rings

Taxonomy of GRB optical light-curves: identification of a salient class of early afterglows

The temporal behaviour of the early optical emission from Gamma-Ray Burst afterglows can be divided in four classes: fast-rising with an early peak, slow-rising with a late peak, flat plateaus, and rapid decays since first measurement. The fast-rising optical afterglows display correlations among peak flux, peak epoch, and post-peak power-law decay index that can be explained with a structured outflow seen off-axis, but the shock origin (reverse or forward) of the optical emission cannot be determined. The afterglows with plateaus and slow-rises may be accommodated by the same model, if observer location offsets are larger than for the fast-rising afterglows, or could be due to a long-lived injection of energy and/or ejecta in the blast-wave. If better calibrated with more afterglows, the peak flux-peak epoch relation exhibited by the fast and slow-rising optical light-curves could provide a way to use this type of afterglows as standard candles.Comment: 8 pages, submitted to MNRA

CCSD(T) Study of CD3-O-CD3 and CH3-O-CD3 Far-Infrared Spectra

From a vibrationally corrected 3D potential energy surface determined with highly correlated ab initio calculations (CCSD(T)), the lowest vibrational energies of two dimethyl-ether isotopologues, 12CH3–16O–12CD3 (DME-d3) and 12CD3–16O–12CD3 (DME-d6), are computed variationally. The levels that can be populated at very low temperatures correspond to the COC-bending and the two methyl torsional modes. Molecular symmetry groups are used for the classification of levels and torsional splittings. DME-d6 belongs to the G36 group, as the most abundant isotopologue 12CH3–16O–12CH3 (DME-h6), while DME-d3 is a G18 species. Previous assignments of experimental Raman and far-infrared spectra are discussed from an effective Hamiltonian obtained after refining the ab initio parameters. Because a good agreement between calculated and experimental transition frequencies is reached, new assignments are proposed for various combination bands corresponding to the two deuterated isotopologues and for the 020 → 030 transition of DME-d6. Vibrationally corrected potential energy barriers, structural parameters, and anharmonic spectroscopic parameters are provided. For the 3N – 9 neglected vibrational modes, harmonic and anharmonic fundamental frequencies are obtained using second-order perturbation theory by means of CCSD and MP2 force fields. Fermi resonances between the COC-bending and the torsional modes modify DME-d3 intensities and the band positions of the torsional overtones

Second Revision of the International Staging System (R2-ISS) for Overall Survival in Multiple Myeloma: A European Myeloma Network (EMN) Report Within the HARMONY Project

PURPOSEPatients with newly diagnosed multiple myeloma (NDMM) show heterogeneous outcomes, and approximately 60% of them are at intermediate-risk according to the Revised International Staging system (R-ISS), the standard-of-care risk stratification model. Moreover, chromosome 1q gain/amplification (1q+) recently proved to be a poor prognostic factor. In this study, we revised the R-ISS by analyzing the additive value of each single risk feature, including 1q+.PATIENTS AND METHODSThe European Myeloma Network, within the HARMONY project, collected individual data from 10,843 patients with NDMM enrolled in 16 clinical trials. An additive scoring system on the basis of top features predicting progression-free survival (PFS) and overall survival (OS) was developed and validated.RESULTSIn the training set (N = 7,072), at a median follow-up of 75 months, ISS, del(17p), lactate dehydrogenase, t(4;14), and 1q+ had the highest impact on PFS and OS. These variables were all simultaneously present in 2,226 patients. A value was assigned to each risk feature according to their OS impact (ISS-III 1.5, ISS-II 1, del(17p) 1, high lactate dehydrogenase 1, and 1q+ 0.5 points). Patients were stratified into four risk groups according to the total additive score: low (Second Revision of the International Staging System [R2-ISS]-I, 19.2%, 0 points), low-intermediate (II, 30.8%, 0.5-1 points), intermediate-high (III, 41.2%, 1.5-2.5 points), high (IV, 8.8%, 3-5 points). Median OS was not reached versus 109.2 versus 68.5 versus 37.9 months, and median PFS was 68 versus 45.5 versus 30.2 versus 19.9 months, respectively. The score was validated in an independent validation set (N = 3,771, of whom 1,214 were with complete data to calculate R2-ISS) maintaining its prognostic value.CONCLUSIONThe R2-ISS is a simple prognostic staging system allowing a better stratification of patients with intermediate-risk NDMM. The additive nature of this score fosters its future implementation with new prognostic variables

Broad targeting of resistance to apoptosis in cancer

Apoptosis or programmed cell death is natural way of removing aged cells from the body. Most of the anti-cancer therapies trigger apoptosis induction and related cell death networks to eliminate malignant cells. However, in cancer, de-regulated apoptotic signaling, particularly the activation of an anti-apoptotic systems, allows cancer cells to escape this program leading to uncontrolled proliferation resulting in tumor survival, therapeutic resistance and recurrence of cancer. This resistance is a complicated phenomenon that emanates from the interactions of various molecules and signaling pathways. In this comprehensive review we discuss the various factors contributing to apoptosis resistance in cancers. The key resistance targets that are discussed include (1) Bcl-2 and Mcl-1 proteins; (2) autophagy processes; (3) necrosis and necroptosis; (4) heat shock protein signaling; (5) the proteasome pathway; (6) epigenetic mechanisms; and (7) aberrant nuclear export signaling. The shortcomings of current therapeutic modalities are highlighted and a broad spectrum strategy using approaches including (a) gossypol; (b) epigallocatechin-3-gallate; (c) UMI-77 (d) triptolide and (e) selinexor that can be used to overcome cell death resistance is presented. This review provides a roadmap for the design of successful anti-cancer strategies that overcome resistance to apoptosis for better therapeutic outcome in patients with cancer