Far‐Infrared Spectrum and Hindering Potential of Deuterium Peroxide

The hindered‐rotation motion in the deuterium peroxide molecule is investigated through a study of the far‐infrared absorption of the vapor. A 1‐m focal‐length vacuum grating spectrometer was used to scan the region from 20 to 400 cm−1 with an average resolution of 0.4 cm−1. Seven perpendicular‐type hindered‐rotation bands characterized by prominent Q branches and unresolved P‐ and R‐branch structure are observed in the spectrum. The band centers are located at 1.88, 42.3, 123.5, 136.8, 206.7, 250.9, and 302.6 cm−1. From these it is determined that, relative to the ground state, the first five excited hindered‐rotation states are at 1.88, 208.6, 250.9, 387.7, and 511.2 cm−1.A theory of internal rotation, developed for an earlier application to the far‐infrared spectrum of hydrogen peroxide, is applied to the D2O2 spectrum. In this theory the only internal degree of freedom is the dihedral angle x defining the relative position of the two OD groups. The Hamiltonian is put in the form H (asymmetric top) +H (internal rotation), where the inertial coefficients are functions of the internal angle x. A three‐parameter hindering potential is assumed, V(x) = V1cosx+V2cos2x+V3cos3xV(x)=V1cosx+V2cos2x+V3cos3x and the internal‐rotation wave equation is solved numerically by computer to obtain the potential parameters which reproduce the internal‐rotation energy eigenvalues. In the semirigid model adopted, the effective hindering potentials, bond lengths, and bond angles of H2O2 and D2O2 differ slightly. The data do not yield a complete set of effective bond lengths and angles for D2O2, but the product of the OD distance and the sine of the OOD angle is found to be 0.01 Å smaller than its H2O2 counterpart. As a result, the inertial parameter in the internal‐rotation wave equation is 2% larger than is predicted from the H2O2 data. Using this adjusted inertial parameter, the hindering potential V(x) = 994cosx+641cos2x+55cos3xV(x)=994cosx+641cos2x+55cos3x provides a good fit to the D2O2 data. For this potential function the cis and trans potential barrier heights are 2470 and 377 cm−1, respectively, and the potential minima are 110.8° from the cis configuration. These parameter values are similar to the corresponding H2O2 values of 2460 cm−1, 386 cm−1, and 111.5°.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/71155/2/JCPSA6-45-8-3141-1.pd

Internal‐Rotation in Hydrogen Peroxide: The Far‐Infrared Spectrum and the Determination of the Hindering Potential

The torsional oscillation between the two OH groups of the hydrogen peroxide molecule is investigated through a study of the far‐infrared absorption spectrum of the molecule. A 1‐m‐focal‐length vacuum grating monochromator was used to scan the region from 15 to 700 cm−1 with an average resolution of 0.3 cm−1. The observed spectrum contains seven perpendicular‐type bands of which only the Q branches are resolved. The centers of the seven bands are at 11.43, 116.51, 198.57, 242.76, 370.70, 521.68, and 557.84 cm−1. These bands result from transitions between different states of the internal rotation and their identification makes it possible to construct the internal‐rotation energy level scheme through the first five excited states. Relative to the torsional ground state, these levels occur at 11.43, 254.2, 370.7, 569.3, and 775.9 cm−1.A theory of internal rotation in the hydrogen peroxide molecule is developed for use in the analysis of the far‐infrared spectra. In this theory, the Hamiltonian is constructed assuming all structural distances and angles fixed except the dihedral angle x defining the relative position of the two OH bars. By the use of a contact transformation the Hamiltonian is put in the form H (asymmetric top)+H(internal rotation) where the interaction between the internal and over‐all rotations arises through the x dependence of the inertial parameters of H(asymmetric top). It is assumed that the relative position of the two OH bars is governed by a potential‐energy function of the form V(x) = V1cosx+V2cos2x+V3cos3xV(x)=V1cosx+V2cos2x+V3cos3x. The internal‐rotation wave equation [αpx2+V(x)]M(x) = EM(x)[αpx2+V(x)]M(x)=EM(x) is solved numerically by an electronic‐computer and the potential function parameters V1=993 cm−1, V2=636 cm−1, and V3=44 cm−1 are chosen to fit the internal‐rotation energy‐level scheme. The trans and cis potential barrier heights are 386 and 2460 cm−1, respectively, and the potential‐function minima are located 111.5° from the cis configuration. Diagonalization of the matrix of the complete Hamiltonian to second order by the use of perturbation theory is sufficient to account for the observed Q‐branch shapes in the far infrared region.Two microwave frequencies observed by Massey and Bianco at 22 054.5 and 27 639.6 Mc/sec are identified from their Stark effects as the first excited‐state transitions J, K, n, τ=8, 6, 1, 1→7, 5, 1, 3 and J, K, n, τ=8, 5, 1, 3→9, 6, 1, 1, respectively, where the internal‐rotation quantum number n=1 denotes the first excited torsional state and where τ denotes trans symmetric (τ=1 and 2) or antisymmetric (τ=3 and 4) states. The form of the dipole moment operator is assumed to be μ0 cos(x/2) and μ0 is found to be 3.15 D in agreement with the value obtained from the torsional ground‐state transitions.Two J=0 microwave series observed by Massey, Beard, and Jen in a mixed sample of the deuterated species D2O2 and HOOD give confirmation of the potential function determined from the H2O2 analysis. The K=4→5 series is identified as the D2O2 first excited torsional state transition n=1→1, τ=4→2. The K=0→1 series is identified as the HOOD torsional ground‐state transition n=0→0, τ=4→2. Only very small changes in the trans barrier height are necessary to fit the constant terms of these series exactly. These changes, which are expected to arise from vibration‐internal rotation interactions, show a reasonable progression from H2O2 to D2O2: V (trans, HOOH) = 386 cm−1, V (trans, HOOD) = 381 cm−1 and V (trans, DOOD) = 378 cm−1.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/71115/2/JCPSA6-42-6-1931-1.pd

A high-resolution study of the OH-stretch fundamental of methanol

The OH-stretch fundamental of CH3OH has been observed with 0.025 cm-1 resolution between 3430 and 3940 cm-1 and the resulting spectrum deconvoluted using the procedure of P. A. Jansson. Approximately 600 lines have been assigned to a total of 67 P- or R-branch series and some 30 excited state levels have been determined. Of these, 14 belong to the lowest torsional state with n = 0, 13 to N = 1 and 3 to N = 2. A nonlinear least-squares fit to these levels varying the major parameters used by Y. Y. Kwan and D. M. Dennison in their analysis of the normal state produces an rms deviation between observed and calculated levels of 0.51 cm-1. Variation of all the parameters including those of the smaller Kirtman perturbation terms produces only a slight improvement in the fit. Both analyses yield a barrier height of 411 cm-1 in the excited vibrational state as compared to the normal state value of 373 cm-1. A number of unexplained anomalies appear in the spectra including large and irregular changes in the coefficient of J2 + J for different torsion-rotation states.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/22170/1/0000601.pd

Marek\u27s Disease Virus (MDV) Encodes an Interleukin-8 Homolog (vIL-8): Characterization of the vIL-8 Protein and a vIL-8 Deletion Mutant MDV

Chemokines induce chemotaxis, cell migration, and inflammatory responses. We report the identification of an interleukin-8 (IL-8) homolog, termed vIL-8, encoded within the genome of Marek\u27s disease virus (MDV). The 134-amino-acid vIL-8 shares closest homology to mammalian and avian IL-8, molecules representing the prototype CXC chemokine. The gene for vIL-8 consists of three exons which map to the BamHI-L fragment within the repeats flanking the unique long region of the MDV genome. A 0.7-kb transcript encoding vIL-8 was detected in an n-butyrate-treated, MDV-transformed T-lymphoblastoid cell line, MSB-1. This induction is essentially abolished by cycloheximide and herpesvirus DNA polymerase inhibitor phosphonoacetate, indicating that vIL-8 is expressed with true late (gamma2) kinetics. Baculovirus-expressed vIL-8 was found to be secreted into the medium and shown to be functional as a chemoattractant for chicken peripheral blood mononuclear cells but not for heterophils. To characterize the function of vIL-8 with respect to MDV infection in vivo, a recombinant MDV was constructed with a deletion of all three exons and a soluble-modified green fluorescent protein (smGFP) expression cassette inserted at the site of deletion. In two in vivo experiments, the vIL-8 deletion mutant (RB1BvIL-8DeltasmGFP) showed a decreased level of lytic infection in comparison to its parent virus, an equal-passage-level parent virus, and to another recombinant MDV containing the insertion of a GFP expression cassette at the nonessential US2 gene. RB1BvIL-8DeltasmGFP retained oncogenicity, albeit at a greatly reduced level. Nonetheless, we have been able to establish a lymphoblastoid cell line from an RB1BvIL-8DeltasmGFP-induced ovarian lymphoma (MDCC-UA20) and verify the presence of a latent MDV genome lacking vIL-8. Taken together, these data describe the identification and characterization of a chemokine homolog encoded within the MDV genome that is dispensable for transformation but may affect the level of MDV in vivo lytic infection

Hemiretinal vein occlusion 12-month outcomes are unique with vascular endothelial growth factor inhibitors: data from the Fight Retinal Blindness! Registry

BACKGROUND/AIMS To describe baseline characteristics and 12-month outcomes with vascular endothelial growth factor (VEGF) inhibitors of treatment-naïve hemiretinal vein occlusion (HRVO) compared with branch (BRVO) and central (CRVO) variants in routine clinical care. METHODS A database observational study recruited 79 HRVO eyes, 590 BRVO eyes and 344 CRVO eyes that initiated therapy over 10 years. The primary outcome was mean change in visual acuity (VA-letters read on a logarithm of minimal angle of resolution chart) at 12 months. Secondary outcomes included mean change in central subfield thickness (CST), injections and visits. RESULTS At baseline, mean VA in HRVO (53.8) was similar to CRVO (51.9; p=0.40) but lower than BRVO (59.4; p=0.009). HRVO eyes improved to match BRVO eyes from soon after treatment started through 12 months. Mean change in VA was greater in HRVO (+16.4) than both BRVO (+11.4; p=0.006) and CRVO (+8.5; p<0.001). Mean change in CST in HRVO (-231 µm) was similar to CRVO (-259 µm; p=0.33) but greater than BRVO eyes (-151 µm; p=0.003). The groups had similar median burdens of eight injections and nine visits. CONCLUSIONS HRVO generally experienced the greatest mean change in VA of the three types of RVO when treated with VEGF inhibitors, ending with similar 12-month VA and CST to BRVO despite starting closer to CRVO. Inclusion of HRVO in BRVO or CRVO cohorts of clinical trials would be expected to proportionally inflate and skew the visual and anatomic outcomes

The Vehicle, Spring 1981

Vol. 22, No. 2 Table of Contents Old Farmers at the Arcade CafeJohn Stockmanpage 4 ConfettiCathy Georgepage 6 Ode to a Corned Beef SandwichJeff Bennettpage 6 The Ice on Kirschner\u27s CreekScott Fishelpage 7 Love Poem to LindaJohn Stockmanpage 7 Grandfather\u27s PortraitJames Marshpage 8 The MassageKathleen Alakspage 9 A Driving ForceSandy Youngpage 10 King DandelionNancy Siebenpage 12 One Afternoon - Contemplating HouseworkKelli Sanderpage 13 Tent WallsAndy Sudkamppage 14 The SentinelElise Hempelpage 16 Daddy\u27s AftershaveJeff Bennettpage 16 The WeddingChris Goerlichpage 17 UntitledCarol Hansenpage 17 Treasures in the YardScott Fishelpage 18 Hitchhiker\u27s BootsAndy Sudkamppage 20 The RaffleLaura Henrypage 21 A Walk at NightJudi Jinespage 24 Morning in the DumpJeff Bennettpage 24 In Praise of Chocolate Ice CreamJohn Stockmanpage 25 Summer on the Isle of PalmsElisabeth Cristpage 26 The WaveHerbert S. Demminpage 27 RememberingJohn Kleinsteiberpage 27 PotatoJohn Stockmanpage 28 Late ShowChris Goerlichpage 30 Love in Him - JoeDebbie Klinnertpage 31 ShoeScott Fishelpage 35 The DrinkerBob Huntpage 36 The WidowGeorge Ndu Igbudupage 37 ElectricityScott Fishelpage 37 Hatchet JackB.L. Davidsonpage 39 Walking Home LateJohn Stockmanpage 41 NovemberCindy Hubbarttpage 41 On the BusLaura Henrypage 42 HaikuJames Marshpage 43 SpillwayGloria Rhoadspage 43 Art Cover design by Linda Fraembs PhotographRobin Scholzpage 3 PhotographRobin Scholzpage 5 PhotographMichelle Glassmeyerpage 15 PhotographRobert Schinaglpage 19 PhotographTom Robertspage 38 PhotographRobert Schinaglpage 44https://thekeep.eiu.edu/vehicle/1039/thumbnail.jp

Effects of antiplatelet therapy on stroke risk by brain imaging features of intracerebral haemorrhage and cerebral small vessel diseases: subgroup analyses of the RESTART randomised, open-label trial

Background Findings from the RESTART trial suggest that starting antiplatelet therapy might reduce the risk of recurrent symptomatic intracerebral haemorrhage compared with avoiding antiplatelet therapy. Brain imaging features of intracerebral haemorrhage and cerebral small vessel diseases (such as cerebral microbleeds) are associated with greater risks of recurrent intracerebral haemorrhage. We did subgroup analyses of the RESTART trial to explore whether these brain imaging features modify the effects of antiplatelet therapy

Social Class

Discussion of class structure in fifth-century Athens, historical constitution of theater audiences, and the changes in the comic representation of class antagonism from Aristophanes to Menander

Mutational Correlates of Virological Failure in Individuals Receiving a WHO-Recommended Tenofovir-Containing First-Line Regimen: An International Collaboration.

Tenofovir disoproxil fumarate (TDF) genotypic resistance defined by K65R/N and/or K70E/Q/G occurs in 20% to 60% of individuals with virological failure (VF) on a WHO-recommended TDF-containing first-line regimen. However, the full spectrum of reverse transcriptase (RT) mutations selected in individuals with VF on such a regimen is not known. To identify TDF regimen-associated mutations (TRAMs), we compared the proportion of each RT mutation in 2873 individuals with VF on a WHO-recommended first-line TDF-containing regimen to its proportion in a cohort of 50,803 antiretroviral-naïve individuals. To identify TRAMs specifically associated with TDF-selection pressure, we compared the proportion of each TRAM to its proportion in a cohort of 5805 individuals with VF on a first-line thymidine analog-containing regimen. We identified 83 TRAMs including 33 NRTI-associated, 40 NNRTI-associated, and 10 uncommon mutations of uncertain provenance. Of the 33 NRTI-associated TRAMs, 12 - A62V, K65R/N, S68G/N/D, K70E/Q/T, L74I, V75L, and Y115F - were more common among individuals receiving a first-line TDF-containing compared to a first-line thymidine analog-containing regimen. These 12 TDF-selected TRAMs will be important for monitoring TDF-associated transmitted drug-resistance and for determining the extent of reduced TDF susceptibility in individuals with VF on a TDF-containing regimen

Voices from the field: How did you come to engage in students-as-partners work?

The language of students as partners was cemented into higher education (HE) practice and scholarship 10 years ago. While it had been circulating in higher education policy, practices, and publications before that, two key 2014 publications on engaging students as partners, or SaP, inspired a myriad of practices and publications brought together by the relational, values-based ethos of partnership (Cook-Sather et al., 2014; Healey et al., 2014). A seductively simple idea— that students can collaborate with staff as partners on matters of teaching and learning—landed at the right time. The higher education sector was increasingly fixated on student involvement and engagement, particularly on how university changes students (Klemenčič, 2024). SaP offered a related but direction-shifting proposition: what if students could shape higher education