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https://www.readbyqxmd.com/read/28605899/generation-and-characterization-of-gas-phase-doubly-charged-biradical-peptide-ions-m2-%C3%A2-%C3%A2
#1
Y L Elaine Wong, Xiangfeng Chen, Ri Wu, Y L Winnie Hung, Hoi Sze Yeung, T-W Dominic Chan
The gas-phase chemistry of peptide radical ions is attracting considerable interest in the fields of biology and mass spectrometry owing to its capability to provide sequence information of peptides and proteins. In this study, we observed that doubly charged peptide ions (M2+) can be produced from the collision-induced dissociation (CID) of Hg(II)-adducted peptide ions. The chemical nature, and thus the dissociation pathways of this hydrogen-deficient biradical M2+ species is intriguing. We investigated the generation and dissociation behavior of this M2+ species under electron-capture dissociation (ECD) and CID conditions...
June 13, 2017: Analytical Chemistry
https://www.readbyqxmd.com/read/28599086/in-silico-design-of-dnp-polarizing-agents-can-current-dinitroxides-be-improved
#2
Frédéric A Perras, Aaron D Sadow, Marek Pruski
Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP-MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. Generally, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near-optimal DNP performance...
June 9, 2017: Chemphyschem: a European Journal of Chemical Physics and Physical Chemistry
https://www.readbyqxmd.com/read/28578583/alkyne-bridged-multi-copper-ii-porphyrin-structures-nuances-of-orbital-symmetry-in-long-range-through-bond-mediated-iso-tropic-spin-exchange-interactions
#3
Ruobing Wang, Alexander Brugh, Jeff Rawson, Michael J Therien, Malcolm D E Forbes
Spin and conformational dynamics in symmetric alkyne-bridged multi[copper(II) porphyrin] structures have been studied in toluene solution at variable temperature using steady-state electron paramagnetic resonance (EPR) spectroscopy. Comparison of the dimer EPR spectra to those of Cu porphyrin monomers shows clear evidence of an isotropic exchange interaction (Javg) in these biradicaloid structures, manifested by a significant line broadening in the dimer spectra. The extent of the line broadening depends on molecular structure and temperature, suggesting that Javg is modulated by conformational dynamics that impact the torsional angle distribution between the porphyrin-porphyrin least-squares planes...
June 3, 2017: Journal of the American Chemical Society
https://www.readbyqxmd.com/read/28574169/dynamic-nuclear-polarization-solid-state-nmr-of-membrane-polypeptides-free-radical-optimization-for-matrix-free-lipid-bilayer-samples
#4
Olivier Ouari, Evgeniy S Salnikov, Sébastien Abel, Ganesan Karthikeyan, Hakim Karoui, Fabien Aussenac, Paul Tordo, Burkhard Bechinger
Dynamic Nuclear Polarization boosts the sensitivity of NMR spectroscopy by orders of magnitude making possible investigations previously out of scope. For MAS solid-state NMR studies the samples are typically mixed with biradicals dissolved in glass forming solvent and investigated at 100K. Here we present new biradical polarizing agents developed for matrix-free samples such as supported lipid bilayers, which are systems widely used for the investigation of membrane proteins of high biomedical importance. A series of 11 biradicals with different structure, geometry and physico-chemical properties was comprehensively tested for DNP performance in lipid bilayers, some of them developed specifically for membranes investigations...
June 2, 2017: Chemphyschem: a European Journal of Chemical Physics and Physical Chemistry
https://www.readbyqxmd.com/read/28560282/clinical-and-biochemical-data-of-endothelial-function-in-women-consuming-combined-contraceptives
#5
Irina I Lobysheva, Sandrine van Eeckhoudt, Flavia Dei Zotti, Ahmad Rifahi, Lucie Pothen, Christophe Beauloye, Jean-Luc Balligand
The data presented in this article are associated with the research article entitled "Heme-Nitrosylated Hemoglobin and Oxidative Stress in Women Consuming Combined Contraceptives. Clinical Application of the EPR Spectroscopy" (Lobysheva et al., 2017 [1]), and describe the characteristics of redox status in blood, as well as biochemical and clinical parameters of young female subjects consuming (or not) contraceptive pills (CP). Erythrocyte concentration of reduced thiols reflecting erythrocyte redox capacity was measured before and after sample deproteinization by electron paramagnetic resonance spectroscopy (EPR) using a nitroxide biradical spin probe specifically interacting with reduced thiols; additional data were obtained by a colorimetric method using Ellman׳s reagents in the same samples...
August 2017: Data in Brief
https://www.readbyqxmd.com/read/28544173/frozen-acrylamide-gels-as-dynamic-nuclear-polarization-matrices
#6
Jasmine Viger-Gravel, Pierrick Berruyer, David Gajan, Jean-Marie Basset, Anne Lesage, Paul Tordo, Olivier Ouari, Lyndon Emsley
We show that aqueous acrylamide gels can be used to provide dynamic nuclear polarization (DNP) NMR signal enhancements of around 200 at 9.4 T and 100 K. The enhancements are shown to increase with cross linker concentration and low concentrations of the AMUPol biradical. We show that this DNP matrix can be used in situations where conventional incipient wetness methods fail, such as to obtain DNP surface enhanced NMR spectra from inorganic nanoparticles. In particular, we obtain 113Cd spectra from CdTe-COOH NPs in minutes...
May 23, 2017: Angewandte Chemie
https://www.readbyqxmd.com/read/28537070/para-azaquinodimethane-a-compact-quinodimethane-variant-as-an-ambient-stable-building-block-for-high-performance-low-band-gap-polymers
#7
Xuncheng Liu, Bo He, Christopher L Anderson, Jun Kang, Teresa Chen, Jinxiang Chen, Shizhen Feng, Lianjie Zhang, Matthew A Kolaczkowski, Simon J Teat, Michael A Brady, Chenhui Zhu, Lin-Wang Wang, Junwu Chen, Yi Liu
Quinoidal structures incorporating expanded para-quinodimethane (p-QM) units have garnered great interest as functional organic electronic, optical, and magnetic materials. The direct use of the compact p-QM unit as an electronic building block, however, has been inhibited by the high reactivity conveyed by its biradical character. Herein, we introduce a stable p-QM variant, namely p-azaquinodimethane (p-AQM), that incorporates nitrogen atoms in the central ring and alkoxy substituents on the periphery to increase the stability of the quinoidal structure...
June 21, 2017: Journal of the American Chemical Society
https://www.readbyqxmd.com/read/28507578/lobular-carcinoma-in-situ-of-the-breast-correlation-between-minimally-invasive-biopsy-and-final-pathology
#8
Bartłomiej Szynglarewicz, Piotr Kasprzak, Agnieszka Hałoń, Rafał Matkowski
INTRODUCTION: Lobular carcinoma in situ (LCIS) is regarded as a non-obligate precursor of invasive breast cancer (IBC). Hence, the optimal management of LCIS found on minimally invasive breast biopsy remains a subject of debate. The aim of this study was to evaluate the correlation of biopsy findings with postoperative histology and to identify risk factors for upstaging to IBC. MATERIAL AND METHODS: Twenty-seven patients with pure LCIS diagnosed on image-guided biopsy (vacuum-assisted or core-needle) underwent subsequent surgery...
April 1, 2017: Archives of Medical Science: AMS
https://www.readbyqxmd.com/read/28494278/outcomes-of-ultrasound-guided-axillary-lymph-node-sampling-in-the-absence-of-primary-breast-cancer
#9
Kirema Garcia-Reyes, Heather I Greenwood, Elissa R Price
PURPOSE: To evaluate outcomes of lymph node sampling in patients with suspicious axillary nodes without a diagnosis of breast cancer. MATERIALS AND METHODS: We retrospectively identified all axillary ultrasound-guided sampling performed at our institution from 2003 to 2016 in patients. without malignancy. RESULTS: Seventy-eight lymph nodes met inclusion criteria. Two of the 78 sampled nodes (2.6%) were malignant. CONCLUSION: Sampling of suspicious nodes in patients without a history of breast cancer rarely yields malignancy...
May 5, 2017: Clinical Imaging
https://www.readbyqxmd.com/read/28484972/radical-generation-from-the-gas-phase-activation-of-ionized-lipid-ozonides
#10
Shane R Ellis, Huong T Pham, Marc In Het Panhuis, Adam J Trevitt, Todd W Mitchell, Stephen J Blanksby
Reaction products from the ozonolysis of unsaturated lipids at gas-liquid interfaces have the potential to significantly influence the chemical and physical properties of organic aerosols in the atmosphere. In this study, the gas-phase dissociation behavior of lipid secondary ozonides is investigated using ion-trap mass spectrometry. Secondary ozonides were formed by reaction between a thin film of unsaturated lipids (fatty acid methyl esters or phospholipids) with ozone before being transferred to the gas phase as [M + Na](+) ions by electrospray ionization...
May 8, 2017: Journal of the American Society for Mass Spectrometry
https://www.readbyqxmd.com/read/28480663/correlations-between-tumor-to-background-ratio-on-breast-specific-gamma-imaging-and-prognostic-factors-in-breast-cancer
#11
Soo Jin Lee, Yun Young Choi, Chanwoo Kim, Min Sung Chung
The purpose of this study was to investigate the correlations between tumor-to-background ratio (TBR) obtained from breast-specific gamma imaging (BSGI) and the prognostic factors of breast cancer. Sixty-seven patients with invasive ductal carcinoma who underwent preoperative BSGI were enrolled. The BSGI images were visually scored from 1 to 5 according to a breast imaging reporting and data system (BIRADS). The TBR results obtained from positive BSGI images were compared according to the following prognostic factors: tumor size; axillary lymph node metastasis; nuclear grade (NG); histologic grade (HG); subtype; Ki-67; and the expression profile of estrogen receptor (ER), progesterone receptor (PR), and human epidermal growth factor receptor 2 (HER2)...
June 2017: Journal of Korean Medical Science
https://www.readbyqxmd.com/read/28471621/automated-breast-volumetric-sonography-compared-with-magnetic-resonance-imaging-in-jewish-brca-1-2-mutation-carriers
#12
Osnat Halshtok Neiman, Zippy Erlich, Eitan Friedman, Arie Rundstein, Anat Shalmon, Yael Servadio, Miri Sklair Levy
BACKGROUND: Automated breast volumetric sonography (ABVS) is a new technology with various possible applications. OBJECTIVES: To compare ABVS and breast magnetic resonance imaging (MRI) in the surveillance of women with BRCA1/2 gene mutation carriers. METHODS: We conducted a prospective study in Jewish female BRCA1/2 mutation carriers who underwent breast MRI and ABVS. The results of both exams performed 6 months apart or less, and relevant clinical data, were reviewed...
October 2016: Israel Medical Association Journal: IMAJ
https://www.readbyqxmd.com/read/28456883/gas-phase-reactivity-of-meta-benzyne-analogs-toward-small-oligonucleotides-of-differing-lengths
#13
Fanny Widjaja, Joann P Max, Zhicheng Jin, John J Nash, Hilkka I Kenttämaa
The gas-phase reactivity of two aromatic carbon-centered σ,σ-biradicals (meta-benzyne analogs) and a related monoradical towards small oligonucleotides of differing lengths was investigated in a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer coupled with laser-induced acoustic desorption (LIAD). The mono- and biradicals were positively charged to allow for manipulation in the mass spectrometer. The oligonucleotides were evaporated into the gas phase as intact neutral molecules by using LIAD...
April 29, 2017: Journal of the American Society for Mass Spectrometry
https://www.readbyqxmd.com/read/28446334/improving-sensitivity-of-solid-state-nmr-spectroscopy-by-rational-design-of-polarizing-agents-for-dynamic-nuclear-polarization
#14
Dominik J Kubicki, Lyndon Emsley
We review our recent efforts to optimize the efficiency of polarizing agents for Dynamic Nuclear Polarization (DNP) in solid-state MAS NMR spectroscopy. We elucidate the links between DNP performance, molecular structure and electronic relaxation properties of dinitroxide biradicals. We show that deuteration and increased bulkiness lead to slower electronic relaxation and in turn to higher DNP enhancements. We also show that the incorporation of solid dielectric particles into the sample is a general method of amplifying DNP enhancements by about a factor of two...
April 26, 2017: Chimia
https://www.readbyqxmd.com/read/28441477/local-electron-correlation-treatment-in-extended-multireference-calculations-effect-of-acceptor-donor-substituents-on-the-biradical-character-of-the-polycyclic-aromatic-hydrocarbon-heptazethrene
#15
Anita Das, Thomas Müller, Felix Plasser, David B Krisiloff, Emily A Carter, Hans Lischka
The implementation of a local correlation (LC) treatment of multireference (MR) configuration interaction approaches within the COLUMBUS program system is reported. The LC treatment is based on the weak pairs approximation of Sæbø and Pulay (Ann. Rev. Phys. Chem. 1993, 44, 213) and a geometrical analysis of Walter et al. (Chem. Phys. Lett. 2001, 346, 177). The removal of simultaneous single excitations out of the weak pairs is based on the reference doubly occupied space only, leading to a straightforward program implementation and a conceptual simplicity in terms of well-defined localized orbitals...
May 2, 2017: Journal of Chemical Theory and Computation
https://www.readbyqxmd.com/read/28440644/direct-observation-of-the-ultrafast-evolution-of-open-shell-biradical-in-photochromic-radical-dimer
#16
Yoichi Kobayashi, Hajime Okajima, Hikaru Sotome, Takeshi Yanai, Katsuya Mutoh, Yusuke Yoneda, Yasuteru Shigeta, Akira Sakamoto, Hiroshi Miyasaka, Jiro Abe
Delocalized biradicals have been extensively studied because of fundamental interests to singlet biradicals and several potential applications such as to two-photon absorption materials. However, many of the biradical studies only focus on the static properties of the rigid molecular structures. It is expected that the biradical properties of the delocalized biradicals are sensitive to the subtle changes of the molecular structures and their local environments. Therefore, the studies of the dynamic properties of the system will give further insight into stable radical chemistry...
April 28, 2017: Journal of the American Chemical Society
https://www.readbyqxmd.com/read/28431205/cyclization-of-ynamide-tethered-1-3-8-triynes
#17
Venkata R Sabbasani, Hyunjin Lee, Peipei Xie, Yuanzhi Xia, Daesung Lee
A facile thermal cyclization of ynamide-tethered 1,3,8-triynes to form a 3,5,6,7-tetrahydro-1H-pyrano[3,4-c]pyridine skeleton is described. Although the mechanism of this unusual reaction has yet to be defined, the formation of either a strained keteniminium or a biradical intermediate followed by a 1,5-hydride or -hydrogen shift is tentatively proposed as the key elementary steps in the reaction sequence. Appropriate electronic activation at the carbon center donating a hydride or hydrogen is crucial for successful cyclization...
April 21, 2017: Chemistry: a European Journal
https://www.readbyqxmd.com/read/28428140/automated-annotation-and-classification-of-bi-rads-assessment-from-radiology-reports
#18
Sergio M Castro, Eugene Tseytlin, Olga Medvedeva, Kevin Mitchell, Shyam Visweswaran, Tanja Bekhuis, Rebecca S Jacobson
The Breast Imaging Reporting and Data System (BI-RADS) was developed to reduce variation in the descriptions of findings. Manual analysis of breast radiology report data is challenging but is necessary for clinical and healthcare quality assurance activities. The objective of this study is to develop a natural language processing (NLP) system for automated BI-RADS categories extraction from breast radiology reports. We evaluated an existing rule-based NLP algorithm, and then we developed and evaluated our own method using a supervised machine learning approach...
May 2017: Journal of Biomedical Informatics
https://www.readbyqxmd.com/read/28425509/a-macrocyclic-co-0-complex-the-relevance-of-ligand-non-innocence-to-reactivity
#19
Manuel Kaspar, Philipp J Altmann, Alexander Pöthig, Stephen Sproules, Corinna R Hess
We present a formally zero-valent compound, [Co(Mabiq)Na(OEt2)]2 (1). The complex was characterized by crystallographic, spectroscopic and DFT computational methods. The electronic structure is described as a Co(II)-(ligand-biradical). Compound 1 is reactive toward proton sources; Co(I) or Co(II) products result, depending on the source of protons used. The redox non-innocence of the Mabiq ligand, which accepts both protons and electrons, has important ramifications for reactivity.
April 20, 2017: Chemical Communications: Chem Comm
https://www.readbyqxmd.com/read/28351284/impact-of-breast-cancer-awareness-month-on-detection-of-breast-cancer-in-a-private-hospital
#20
Onder Karabay, Mustafa Hasbahceci, Huseyin Kadioglu
Objective Breast cancer awareness month increases public awareness in association with increased rates of screening and new diagnoses. This study aimed to evaluate the effect of breast cancer awareness month on primary diagnosis of breast cancer. Methods Asymptomatic women with the intention of breast cancer screening were included. The non-BCAM (Breast cancer awareness month) group were screened from February to September 2016 and the BCAM group during October 2016. Ultrasound and mammography were performed in all women and in those aged ≥ 40 years, respectively...
January 1, 2017: Journal of International Medical Research
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