bluuebunny/crossref_metadata_2025_split huggingface dataset:
Beyond Oxides: Nitride as a Ligand in a Neutral IrIXNO3 Molecule Bearing a Transition Metal at High Oxidation State
Authors: Wolański Łukasz , Domański Mateusz , Grochala Wojciech , Szarek Paweł 
Published: May 2019

AbstractTheoretical calculations utilizing relativistic ZORA Hamiltonian point to the conceivable existence of an IrNO3 molecule in C3v geometry. This minimum is shown to correspond to genuine nonavalent iridium nitride trioxide, which is a neutral analogue of cationic [IrO4]+ species detected recently. Despite the presence of nitride anion, the molecule is protected by substantial barriers exceeding 200 kJ mol−1 against transformations leading, for example, to global minimum (O=)2Ir−NO, which contains metal at a lower formal oxidation state.
The Use of Workplace Strengths and Proactive and Organizational Citizenship Behaviours: An Examination of the Mediating Role of Well‐Being
Authors: Belleville Karel , Dubreuil Philippe , Courcy François 
Published: May 2019

AbstractPositive psychology suggests relying on workers' strengths to maintain balance between personal fulfillment and organizational goals. This article assesses whether the use of strengths in the workplace are associated with proactive behaviours and organizational citizenship behaviours (OCB) through the mediating role of well‐being. Data were collected from 142 French‐speaking Canadian professionals working in various non‐profit organizations. Results show that the use of strengths can predict some OCBs (notably mutual aid and civic virtue) as well as proactivity. Only the affective dimension of well‐being shows a mediation effect for mutual aid and proactivity. Theoretical contributions, implications for practitioners, limitations, and future research directions are also discussed.
The effect of treatment on patient‐reported distress after breast cancer diagnosis
Authors: Fayanju Oluwadamilola M. , Yenokyan Karine , Ren Yi , Goldstein Benjamin A. , Stashko Ilona , Power Steve , Thornton Madeline J. , Marcom P. Kelly , Hwang E. Shelley 
Published: May 2019

BackgroundThe National Comprehensive Cancer Network (NCCN) Distress Thermometer (DT) uses a 10‐point scale (in which 0 indicates no distress and 10 indicates extreme distress) to measure patient‐reported distress. In the current study, the authors sought to examine the relationship between treatment and NCCN DT scores in patients with breast cancer over time.MethodsThe authors included women aged ≥18 years who were diagnosed with stage 0 to stage IV breast cancer (according to the seventh edition of the American Joint Commission on Cancer staging system) at a 3‐hospital health system from January 2014 to July 2016. Linear mixed effects models adjusted for covariates including stage of disease, race/ethnicity, insurance, and treatment sequence (neoadjuvant vs adjuvant) were used to estimate adjusted mean changes in the DT score (MSCs) per week for patients undergoing lumpectomy, mastectomy only, and mastectomy with reconstruction (MR).ResultsThe authors analyzed 12,569 encounters for 1029 unique patients (median score, 4; median follow‐up, 67 weeks). Patients treated with MR (118 patients) were younger and more likely to be married, white, and privately insured compared with patients undergoing lumpectomy (620 patients) and mastectomy only (291 patients) (all P < .01). After adjusting for covariates, distress scores were found to decline significantly across all 3 surgical cohorts, with patients undergoing MR found to have both the most preoperative distress and the greatest decline in distress prior to surgery (MSC/week: ‐0.073 for MR vs ‐0.031 for lumpectomy vs ‐0.033 for mastectomy only; P = .001). Neoadjuvant therapy was associated with a longitudinal decline in distress for patients treated with lumpectomy (‐1.023) and mastectomy only (‐0.964). Over time, ductal carcinoma in situ (‐0.503) and black race (‐1.198) were found to be associated with declining distress among patients treated with lumpectomy and MR, respectively, whereas divorced patients who were treated with mastectomy only (0.948) and single patients treated with lumpectomy (0.476) experienced increased distress (all P < .05).ConclusionsWhen examined longitudinally in consecutive patients, the NCCN DT can provide patient‐reported data to inform expectations and guide targeted support for patients with breast cancer.
On‐Surface Activation of Trimethylsilyl‐Terminated Alkynes on Coinage Metal Surfaces
Authors: Zhang Liding , Zhang Yi‐Qi , Chen Zhi , Lin Tao , Paszkiewicz Mateusz , Hellwig Raphael , Huang Tianjiao , Ruben Mario , Barth Johannes V. , Klappenberger Florian 
Published: May 2019

AbstractThe controlled attachment of protecting groups combined with the ability to selectively abstract them is central to organic synthesis. The trimethylsilyl (TMS) functional group is a popular protecting group in solution. However, insights on its activation behavior under ultra‐high vacuum (UHV) and surface‐confined conditions are scarce. Here we investigate a series of TMS‐protected alkyne precursors via scanning tunneling microscopy (STM) regarding their compatibility with organic molecular beam epitaxy (OMBE) and their potential deprotection on various coinage metal surfaces. After in‐situ evaporation on the substrates held in UHV at room temperature, we find that all molecules arrived and adsorbed as intact units forming ordered supramolecular aggregates stabilized by non‐covalent interactions. Thus, TMS‐functionalized alkyne precursors with weights up to 1100 atomic mass units are stable against OMBE evaporation in UHV. Furthermore, the TMS activation through thermal annealing is investigated with STM and X‐ray photoelectron spectroscopy (XPS). We observe that deprotection starts to occur between 400 K and 500 K on the copper and gold surfaces, respectively. In contrast, on silver surfaces, the TMS‐alkyne bond remains stable up to temperatures where molecular desorption sets in (≈600 K). Hence, TMS functional groups can be utilized as leaving groups on copper and gold surfaces while they serve as protecting groups on silver surfaces.
Improving the Power‐Conversion Efficiency through Alloying in Common Anion CdZnX (X=S, Se) Nanocrystal Sensitized Solar Cells
Authors: Maiti Sourav , Anand Pranav , Azlan Farazuddin , Dana Jayanta , Ghosh Hirendra N. 
Published: May 2019

AbstractIn this paper, we have investigated the possibility of utilizing CdZnS and CdZnSe alloy nanocrystals (NCs) as sensitizers in quantum‐dot solar cells (QDSCs). The alloy NCs were synthesized by a high‐temperature hot injection method and subsequently characterized through high photoluminescence quantum yield, along with larger size compared to binary NCs. Femtosecond transient absorption measurements revealed long‐lived charge carriers in the alloy structure due to more structural rigidity and less defect states. Finally, the solar‐cell efficiencies of the CdZnS (CdZnSe) NCs were found to be 3.05 % (3.69 %) as compared to 1.23 % (3.12 %) efficiencies for CdS (CdSe) NCs. Thus, common anion ternary NCs have been successfully utilized for solar‐cell assembly and can be helpful for constructing tandem solar cells to harvest the high‐energy portion of solar radiation.
Hydrogen Diffusion Guided Design of Pt‐Based Alloys for Inhibition of Butadiene Over‐Hydrogenation
Authors: Hu Chaoquan , Sun Jiahan , Wang Dongjie , Peng Mi , Shao Mingyuan , Zhu Qingshan , Ma Ding 
Published: May 2019

AbstractAlloying Pt with other metals is an effective strategy to tune its performance towards selective hydrogenation reactions. Herein, we have demonstrated a process to screen Pt‐based alloys for inhibition of butadiene over‐hydrogenation with a model comprising isolated single atoms (ISA) embedded into Pt(111). DFT calculations reveal that the diffusion energy barrier of H co‐adsorbed with 1‐butene is a key parameter for the screening. The output from the ISA model was validated by testing several typical Pt‐based alloys towards butadiene hydrogenation. Furthermore, an unexpected higher selectivity to cis‐2‐butene compared to the trans isomer and 1‐butene over the PtZn alloy was explored employing the ISA model.
Reassessment of the Mechanisms of Thermal C−H Bond Activation of Methane by Cationic Magnesium Oxides: A Critical Evaluation of the Suitability of Different Density Functionals
Authors: Tian Tian , Sun Xiaoli , Weiske Thomas , Cai Yuxi , Geng Caiyun , Li Jilai , Schwarz Helmut 
Published: May 2019

AbstractThe mechanisms of the thermal reactions of the two iconic magnesium oxide cations MgO.+ and Mg2O2.+ with methane have been re‐evaluated at the CCSD(T)/CBS//CCSD/def2‐TZVP level of theory. For the reaction of MgO.+ with CH4, only the classical hydrogen‐atom transfer (HAT) was found; in contrast, for the Mg2O2.+/CH4 couple, both HAT and proton‐coupled electron‐transfer (PCET) exist as mechanistic variants. In order to evaluate the suitability of density functional theory (DFT) methods, the reactions were computed by using 27 density functionals. The results obtained demonstrate that the various DFT methods often deliver rather different results for both geometric and energetic features. As to the prediction of the apparent barriers, pure functionals give the largest mean absolute errors. BMK, ωB97XD, and the double‐hybrid functional mPW2PLYP were confirmed to come closest to the results provided by CCSD(T)/CBS. Thus, mechanistic conclusions based on a single DFT method should be viewed with great caution. In summary, this study may assist in the selection of a suitable quantum chemical method to unravel the mechanistic details of C−H bond activation by charged metal oxides.
Computing the Ultrafast and Radiationless Electronic Excited State Decay of Cytosine and 5‐methyl‐cytosine Cations: Uncovering the Role of Dynamic Electron Correlation
Authors: Segarra‐Martí Javier , Tran Thierry , Bearpark Michael J. 
Published: May 2019

AbstractPhotoionisation in DNA, i. e. the process of photoinduced electron removal from the chromophoric species – the nucleobases – leading to their cationic form, has been scarcely studied despite being considered to be responsible for significant damaging instances in our genetic material. In this contribution we theoretically characterise the electronic ground and excited state decay pathways of cationic DNA nucleobase cytosine+ and its epigenetic derivative 5‐methyl‐cytosine+, including the effects of dynamic electron correlation on energies and geometries of minima and conical intersections. We do this by comparing the results of XMS‐CASPT2 calculations with CASSCF estimates and we find some significant differences between the results of these two methods. In particular, including dynamic electron correlation is found to significantly reduce the barrier to access the
conical intersection. We find notable similarities in both cytosine and 5‐methyl‐cytosine cations, and accessible conical intersections in the vicinity of the Franck‐Condon region are found. This points towards an ultrafast depopulation of their electronic excited states. Moreover, the shape of the ground state potential energy surface strongly directs the decaying excited state population towards the cationic ground state minimum on ultrafast timescales, preventing photo‐fragmentation and thus explaining their photostability. To better compare our calculations with the available experimental data we compute the UV (ground and excited state) and IR absorptions.
Unique Calibrators Derived from Fluorescence‐Activated Nanoparticle Sorting for Flow Cytometric Size Estimation of Artificial Vesicles: Possibilities and Limitations
Authors: Simonsen Jens B. , Larsen Jannik B. , Hempel Casper , Eng Niklas , Fossum Anna , Andresen Thomas L. 
Published: May 2019

AbstractThe use of high‐throughput flow cytometry to characterize nanoparticles has received increased interest in recent years. However, to fully realize the potential of flow cytometry for the characterization of nanometer‐sized objects, suitable calibrators for size estimation must be developed and the sensitivity of conventional flow cytometers has to be advanced. Based on the scattered signal, silica and plastic beads have often been used as flow cytometric size calibrators to evaluate the size of extracellular vesicles and artificial vesicles (liposomes). However, several studies have shown that these beads are unable to accurately correlate scatter intensity to vesicle size. In this work, we present a novel method to estimate the size of individual liposomes in flow cytometry based on liposomal size calibrators prepared by fluorescence‐activated cell sorting (FACS), here coined fluorescence‐activated nanoparticle sorting (FANS). These calibration liposomes exhibit sizes, structures, and refractive indexes identical to the particles being studied and thus can serve as unique calibrators. First, a sample of polydisperse fluorophore‐labeled unilamellar liposomes was prepared and analyzed by flow cytometry. Next, different fractions of the polydisperse liposomes were FANS‐sorted according to their fluorescence intensity. Thereafter, we employed nanoparticle tracking analysis (NTA) to evaluate the liposome sizes of the FANS‐sorted liposome fractions. Finally, we correlated the flow cytometric readouts (side scatter and fluorescence intensity) of the FANS‐sorted liposome fractions with their corresponding size obtained by NTA. This procedure enabled us to translate the liposome fluorescence intensity to the liposome size in nanometers for all detected individual liposomes. We validated the size distribution of our polydisperse liposome sample obtained from flow cytometry in combination with our FANS‐calibrators against standard methods for sizing nanoparticles, including NTA and cryo‐transmission electron microscopy. This work also highlights the limitation of using the flow cytometric side scattering readout to determine the size of small (30–300 nm) artificial vesicles. © 2019 International Society for Advancement of Cytometry
Design of a lightweight and anonymous authenticated key agreement protocol for wireless body area networks
Authors: Ostad‐Sharif Arezou , Nikooghadam Morteza , Abbasinezhad‐Mood Dariush 
Published: May 2019

SummaryWireless body area networks (WBANs) are a network designed to gather critical information about the physical conditions of patients and to exchange this information. WBANs are prone to attacks, more than other networks, because of their mobility and the public channel they use. Therefore, mutual authentication and privacy protection are critical for WBANs to prevent attackers from accessing confidential information of patients and executing undetectable physical attacks. In addition, in the authentication and key agreement process, messages should be transferred anonymously such that they are not linkable. In this paper, we first indicate that one of the most recently introduced authentication protocol is vulnerable to the wrong session key agreement attack and desynchronization attack. Second, we propose a lightweight authentication and key agreement protocol, which can withstand the well‐known attacks and provide the anonymity feature. Eventually, we analyze the security of our proposed protocol using both Automated Validation of Internet Security Protocols and Applications (AVISPA) and random oracle model and compare its performance with the related works. The results demonstrate the superiority of our proposed protocol in comparison with the other protocols.
Case study on vibration health risk and comfort levels in loading crane trucks
Authors: Picoral Filho José Gilberto , Fedatto Neto Mário , Quintas Juan Pablo Raggio , Gomes Herbert Martins 
Published: May 2019

SummaryAccording to a survey published by the Brazilian National Transportation Confederation, recently, the Brazilian truck fleet has been increasing about 84.3%, accounting to, in 2016, a total value of 2 684 227 vehicles. Despite this growth, the quality of the road network did not increase proportionally to the necessary infrastructure for agricultural production flow. This work aims to infer, by the analysis of occupational exposure, the vibration levels acting on truck drivers, analyzing the vibrational degree for health risk and comfort levels. The whole‐body vibration (WBV) in trucks of different models and capacities, at some speeds and pavement types, are evaluated using a portable vibration analyzer with triaxial accelerometers. The daily exposure to vibration A(8) is evaluated and compared with the occupational exposure limits defined by a National Regulation Standard, with measurement procedures defined by an Occupational Hygiene Standard, and level requirements defined by an International ISO Standard. It is concluded that the degree of comfort is higher for heavier vehicles with large wheelbase. Relative to the health risk conditions, the study arrives at the same conclusion; the degree of risk increases as the vehicle' speed and pavement's longitudinal irregularity increase. Regarding human exposure to vibration, the vehicles in their actual working situations presented a vibration scenario where the exposure limits are exceeded, resulting in unhealthy working conditions.
Quality improvement of health systems in an epidemic context: A framework based on lessons from the Ebola virus disease outbreak in West Africa
Authors: Brugnara Lucia , Pervilhac Cyril , Kohler François , Dramé Mohamed Lamine , Sax Sylvia , Marx Michael 
Published: May 2019

SummaryQuality improvement (QI) in health generally focuses on the provision of health services with the aim of improving service delivery. Yet QI can be applied not only to health services but also to health systems overall. This is of growing relevance considering that due to deficiencies in health systems, the main countries affected by Ebola virus disease (EVD) outbreak in West Africa (2014–2016) were insufficiently prepared for the epidemic, and according to the WHO, epidemics are increasingly becoming a threat to global health. Our objective is to analyze QI constraints in health systems during that EVD epidemic and to propose a practical framework for QI in health systems for epidemics in developing countries. We applied a framework analysis using experiences shared at the “Second International Quality Forum” organized by the University of Heidelberg and partners in July 2015 and information gathered from a systematic literature review. Empirical results revealed multiple deficiencies in the health systems. We systemized these shortfalls as well as the QI measures taken as a response during the epidemic. On the basis of these findings, we identified six specific “priority intervention areas,” which ultimately resulted in the synthesis of a practical QI framework. We deem that this framework that integrates the priority intervention areas with the WHO building blocks is suitable to improve, monitor, and evaluate health system performance in epidemic contexts in developing countries.
RasGRP1 is a target for VEGF to induce angiogenesis and involved in the endothelial‐protective effects of metformin under high glucose in HUVECs
Authors: Xu Jing , Liu Miao , Yu Muqiao , Shen Jiayi , Zhou Jiecan , Hu Jinglei , Zhou Yong , Zhang Wei 
Published: May 2019

AbstractImpaired angiogenesis in endothelial cells is a hallmark of diabetes vascular complications. Ras guanine‐releasing protein 1 (RasGRP1) is a guanine nucleotide exchange factor for Ras, and its role in endothelial angiogenesis has not been investigated. Given the importance of Ras in vascular endothelial growth factor (VEGF)‐induced angiogenesis, we hypothesized that RasGRP1 may be a critical pathway downstream of VEGF and involved in endothelial angiogenesis. Furthermore, we investigate whether RasGRP1‐dependent VEGF signaling was downregulated under high glucose conditions mimicking diabetes and required for the endothelial protective action of metformin in human umbilical vein endothelial cells (HUVECs). HUVECs were transfected with either RasGRP1 small interfering RNA (siRNA) or pEnter‐RasGRP1 plasmid to down‐ and upregulate RasGRP1 expression before different treatments, such as added VEGF or not, exposed to high glucose (35 mM) or normal glucose (5 mM) in the presence or absence of metformin. Expression of VEGF, RasGRP1, and their signaling targets were analyzed by Western blot; migration and tube formation were detected by transwell chamber assay and Matrigel angiogenesis assay, respectively. Knockdown of RasGRP1 significantly attenuated VEGF‐induced migration and tube formation activities of HUVECs and activation of AKT pathway. The expression of VEGF, RasGRP1, and AKT phosphorylation was downregulated in HUVECs exposed to high glucose compared with normal glucose, whereas metformin upregulated the RasGRP1‐dependent VEGF signaling and ameliorates the impaired angiogenesis caused by high glucose. RasGRP1 is involved in the VEGF‐induced angiogenesis and the pro‐angiogenesis effects of metformin under hyperglycemia. © 2019 IUBMB Life, 71(9):1391–1400, 2019
Age-Related Changes in the Mechanical Regulation of Bone Healing Are Explained by Altered Cellular Mechanoresponse
Authors: Borgiani Edoardo , Figge Christine , Kruck Bettina , Willie Bettina M , Duda Georg N , Checa Sara 
Published: May 2019

ABSTRACT
Increasing age is associated with a reduced bone regeneration potential and increased risk of morbidities and mortality. A reduced bone formation response to mechanical loading has been shown with aging, and it remains unknown if the interplay between aging and mechanical stimuli during regeneration is similar to adaptation. We used a combined in vivo/in silico approach to investigate age-related alterations in the mechanical regulation of bone healing and identified the relative impact of altered cellular function on tissue patterns during the regenerative cascade. To modulate the mechanical environment, femoral osteotomies in adult and elderly mice were stabilized using either a rigid or a semirigid external fixator, and the course of healing was evaluated using histomorphometric and micro-CT analyses at 7, 14, and 21 days post-surgery. Computer models were developed to investigate the influence of the local mechanical environment within the callus on tissue formation patterns. The models aimed to identify the key processes at the cellular level that alter the mechanical regulation of healing with aging. Fifteen age-related biological alterations were investigated on two levels (adult and elderly) with a design of experiments setup. We show a reduced response to changes in fixation stability with age, which could be explained by reduced cellular mechanoresponse, simulated as alteration of the ranges of mechanical stimuli driving mesenchymal stem cell differentiation. Cellular mechanoresponse has been so far widely ignored as a therapeutic target in aged patients. Our data hint to mechanotherapeutics as a potential treatment to enhance bone healing in the elderly. © 2019 American Society for Bone and Mineral Research.
Transcranial color‐coded sonography may indirectly reveal an intracranial meningioma
Authors: Bartolini Emanuele , Filippi Andria , Cafforio Gianfranco 
Published: May 2019

AbstractMeningiomas are extra‐axial tumors with a long‐standing indolent clinical course. Sphenoid wing meningiomas may slowly grow, spreading toward the orbitofrontal and temporal regions as well as encasing the middle cerebral artery (MCA). Herein, we report the incidental finding of a sphenoid wing meningioma compressing the MCA in a patient who undergone a transcranial sonography study for recurrent speech disorders. We illustrate the associated sonographic “red flags” which should prompt to suspect an underlying compressive space‐occupying lesion.