68 research outputs found
Raman Scattering in the Inorganic Spin-Peierls System alpha'-Na_{1-delta}V_2O_5
We have studied the spin-Peierls (SP) transition in alpha'-Na_{1-delta}V_2O_5
(delta = 0, 0.01 and 0.1) by means of Raman scattering. At room temperature, we
observe six A_1 and three A_2 phonon modes and a broad Raman band. Below
T_{SP}several new peaks and a new broad band appear. The new peak at 62 cm^{-1}
originates from the SP-gap excitation. The new peak at 128 cm^{-1} and the new
broad band between 130 and 400 cm^{-1} come from two magnetic excitations. The
new peaks at 102, 646 and 944 cm^{-1} are assigned to the folded phonon modes
and their Na^+-ion deficiency dependence shows that the defect of Na^+ ion
suppresses the SPtransition. The polarized Raman spectra below T_{SP} suggest
that the possible crystal symmetry is C_s^2(Pn) or C_1^1(P1). The asymmetric
lineshape of the 531-cm^{-1} peak superimposed on the electronic Raman band
from the d-d transition around 600 cm^{-1} is interpreted in terms of the Fano
resonance between the electronic continuous band and the phonon with a finite
lifetime. The defects of the Na^+ ions reduce the Fano effect because the life
time of the phonon and the phonon-continuum interaction are decreased.Comment: 24 pages, 10 Postscript figures,uses jpsj.sty and epsf.sty. in press
in J. Phys. Soc. Jp
Lattice vibrations of alpha'-NaV2O5
We have measured far infrared reflectance and transmittance spectra as well
as Raman scattering spectra of \alpha'-NaV2O5 single crystals for all the
principal polarizations. The temperature range above the phase transition
temperature T_c=35 K was investigated, mainly. On the basis of this
experimental study and of the lattice dynamics calculations we conclude that
the symmetry of NaV2O5 in the high temperature phase is described by the
centrosymmetric D_{2h}^{13} space group. The assignment of the observed phonons
is given. Values of dielectric constants are obtained from the infrared data.
Asymmetric shapes of several infrared lines as well as higher order infrared
vibrational spectra are discussed. The crystal field energy levels of the 3d
electron localized at the V^{4+} site have been calculated in the framework of
the exchange charge model using the values of effective charges obtained from
the lattice dynamics calculations. According to the results of these
calculations, the earlier observed broad optical bands in the region of 1 eV
can be interpreted as phonon assisted d-d transitions.Comment: 12 pages, 8 figures, 5 tables; submitted to PR
Inflammation-Associated Nitrotyrosination Affects TCR Recognition through Reduced Stability and Alteration of the Molecular Surface of the MHC Complex
Nitrotyrosination of proteins, a hallmark of inflammation, may result in the production of MHC-restricted neoantigens that can be recognized by T cells and bypass the constraints of immunological self-tolerance. Here we biochemically and structurally assessed how nitrotyrosination of the lymphocytic choriomeningitis virus (LCMV)-associated immunodominant MHC class I-restricted epitopes gp33 and gp34 alters T cell recognition in the context of both H-2Db and H-2Kb. Comparative analysis of the crystal structures of H-2Kb/gp34 and H-2Kb/NY-gp34 demonstrated that nitrotyrosination of p3Y in gp34 abrogates a hydrogen bond interaction formed with the H-2Kb residue E152. As a consequence the conformation of the TCR-interacting E152 was profoundly altered in H-2Kb/NY-gp34 when compared to H-2Kb/gp34, thereby modifying the surface of the nitrotyrosinated MHC complex. Furthermore, nitrotyrosination of gp34 resulted in structural over-packing, straining the overall conformation and considerably reducing the stability of the H-2Kb/NY-gp34 MHC complex when compared to H-2Kb/gp34. Our structural analysis also indicates that nitrotyrosination of the main TCR-interacting residue p4Y in gp33 abrogates recognition of H-2Db/gp33-NY complexes by H-2Db/gp33-specific T cells through sterical hindrance. In conclusion, this study provides the first structural and biochemical evidence for how MHC class I-restricted nitrotyrosinated neoantigens may enable viral escape and break immune tolerance
The Prosensory Function of Sox2 in the Chicken Inner Ear Relies on the Direct Regulation of Atoh1
The proneural gene Atoh1 is crucial for the development of inner ear hair cells and it requires the function of the transcription factor Sox2 through yet unknown mechanisms. In the present work, we used the chicken embryo and HEK293T cells to explore the regulation of Atoh1 by Sox2. The results show that hair cells derive from Sox2-positive otic progenitors and that Sox2 directly activates Atoh1 through a transcriptional activator function that requires the integrity of Sox2 DNA binding domain. Atoh1 activation depends on Sox transcription factor binding sites (SoxTFBS) present in the Atoh1 3′ enhancer where Sox2 directly binds, as shown by site directed mutagenesis and chromatin immunoprecipitation (ChIP). In the inner ear, Atoh1 enhancer activity is detected in the neurosensory domain and it depends on Sox2. Dominant negative competition (Sox2HMG-Engrailed) and mutation of the SoxTFBS abolish the reporter activity in vivo. Moreover, ChIP assay in isolated otic vesicles shows that Sox2 is bound to the Atoh1 enhancer in vivo. However, besides activating Atoh1, Sox2 also promotes the expression of Atoh1 negative regulators and the temporal profile of Atoh1 activation by Sox2 is transient suggesting that Sox2 triggers an incoherent feed-forward loop. These results provide a mechanism for the prosensory function of Sox2 in the inner ear. We suggest that sensory competence is established early in otic development through the activation of Atoh1 by Sox2, however, hair cell differentiation is prevented until later stages by the parallel activation of negative regulators of Atoh1 function
Oxidative protein labeling in mass-spectrometry-based proteomics
Oxidation of proteins and peptides is a common phenomenon, and can be employed as a labeling technique for mass-spectrometry-based proteomics. Nonspecific oxidative labeling methods can modify almost any amino acid residue in a protein or only surface-exposed regions. Specific agents may label reactive functional groups in amino acids, primarily cysteine, methionine, tyrosine, and tryptophan. Nonspecific radical intermediates (reactive oxygen, nitrogen, or halogen species) can be produced by chemical, photochemical, electrochemical, or enzymatic methods. More targeted oxidation can be achieved by chemical reagents but also by direct electrochemical oxidation, which opens the way to instrumental labeling methods. Oxidative labeling of amino acids in the context of liquid chromatography(LC)–mass spectrometry (MS) based proteomics allows for differential LC separation, improved MS ionization, and label-specific fragmentation and detection. Oxidation of proteins can create new reactive groups which are useful for secondary, more conventional derivatization reactions with, e.g., fluorescent labels. This review summarizes reactions of oxidizing agents with peptides and proteins, the corresponding methodologies and instrumentation, and the major, innovative applications of oxidative protein labeling described in selected literature from the last decade
Analyzing and Modeling Real-World Phenomena with Complex Networks: A Survey of Applications
The success of new scientific areas can be assessed by their potential for
contributing to new theoretical approaches and in applications to real-world
problems. Complex networks have fared extremely well in both of these aspects,
with their sound theoretical basis developed over the years and with a variety
of applications. In this survey, we analyze the applications of complex
networks to real-world problems and data, with emphasis in representation,
analysis and modeling, after an introduction to the main concepts and models. A
diversity of phenomena are surveyed, which may be classified into no less than
22 areas, providing a clear indication of the impact of the field of complex
networks.Comment: 103 pages, 3 figures and 7 tables. A working manuscript, suggestions
are welcome
Effects of hospital facilities on patient outcomes after cancer surgery: an international, prospective, observational study
Background Early death after cancer surgery is higher in low-income and middle-income countries (LMICs) compared with in high-income countries, yet the impact of facility characteristics on early postoperative outcomes is unknown. The aim of this study was to examine the association between hospital infrastructure, resource availability, and processes on early outcomes after cancer surgery worldwide.Methods A multimethods analysis was performed as part of the GlobalSurg 3 study-a multicentre, international, prospective cohort study of patients who had surgery for breast, colorectal, or gastric cancer. The primary outcomes were 30-day mortality and 30-day major complication rates. Potentially beneficial hospital facilities were identified by variable selection to select those associated with 30-day mortality. Adjusted outcomes were determined using generalised estimating equations to account for patient characteristics and country-income group, with population stratification by hospital.Findings Between April 1, 2018, and April 23, 2019, facility-level data were collected for 9685 patients across 238 hospitals in 66 countries (91 hospitals in 20 high-income countries; 57 hospitals in 19 upper-middle-income countries; and 90 hospitals in 27 low-income to lower-middle-income countries). The availability of five hospital facilities was inversely associated with mortality: ultrasound, CT scanner, critical care unit, opioid analgesia, and oncologist. After adjustment for case-mix and country income group, hospitals with three or fewer of these facilities (62 hospitals, 1294 patients) had higher mortality compared with those with four or five (adjusted odds ratio [OR] 3.85 [95% CI 2.58-5.75]; p<0.0001), with excess mortality predominantly explained by a limited capacity to rescue following the development of major complications (63.0% vs 82.7%; OR 0.35 [0.23-0.53]; p<0.0001). Across LMICs, improvements in hospital facilities would prevent one to three deaths for every 100 patients undergoing surgery for cancer.Interpretation Hospitals with higher levels of infrastructure and resources have better outcomes after cancer surgery, independent of country income. Without urgent strengthening of hospital infrastructure and resources, the reductions in cancer-associated mortality associated with improved access will not be realised
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