bluuebunny/crossref_metadata_2025 huggingface dataset:
In Situ Generation of Poly (Vinylene Carbonate) Based Solid Electrolyte with Interfacial Stability for LiCoO2 Lithium Batteries
Authors: Chai Jingchao , Liu Zhihong , Ma Jun , Wang Jia , Liu Xiaochen , Liu Haisheng , Zhang Jianjun , Cui Guanglei , Chen Liquan
Published: November 2016

Nowadays it is extremely urgent to seek high performance solid polymer electrolyte that possesses both interfacial stability toward lithium/graphitic anodes and high voltage cathodes for high energy density solid state batteries. Inspired by the positive interfacial effect of vinylene carbonate additive on solid electrolyte interface, a novel poly (vinylene carbonate) based solid polymer electrolyte is presented via a facile in situ polymerization process in this paper. It is manifested that poly (vinylene carbonate) based solid polymer electrolyte possess a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 9.82 × 10−5 S cm−1 at 50 °C. Moreover, it is demonstrated that high voltage LiCoO2/Li batteries using this solid polymer electrolyte display stable charge/discharge profiles, considerable rate capability, excellent cycling performance, and decent safety characteristic. It is believed that poly (vinylene carbonate) based electrolyte can be a very promising solid polymer electrolyte candidate for high energy density lithium batteries.
Use of Social Media in Emergency Ultrasound Fellowship Programs
Authors: Amini Richard , Wang Janelle B. , Trueger N. Seth , Hoyer Riley , Adhikari Srikar
Published: November 2016

Objective

Social media has been gaining traction among learners and educators for its ability to stimulate discussion, increase participation, and promote knowledge sharing. Despite the growing research around the benefits of social media in education, there is little evidence on how it is being incorporated into emergency ultrasound (EUS) fellowships. This study aims to determine the preference and use of social media by engaging with program directors across EUS programs in the United States to assess the current landscape of and attitudes toward social media use.

Methods

This was a cross‐sectional study. An online questionnaire was electronically sent to all EUS fellowship directors across the country. The survey consisted of questions regarding current practice patterns, policies, and perceptions regarding the use of social media in EUS fellowship programs.

Results

Ninety‐six ultrasound fellowship programs were identified for inclusion into this study. A total of 64 participants completed the survey, representing a 63% response rate. Thirty‐eight percent (95% confidence interval [CI] = 26% – 50%) of responding fellowship programs have an official social media outlet and 25% have a separate ultrasound handle for their EM residency program. Fifty‐eight percent (95% CI = 46% – 70%) of programs do not provide training to fellows and residents on the social media outlets used by their program. The top two social media outlets currently being used by programs are Twitter and YouTube to disseminate educational content and knowledge sharing. Twenty‐eight percent (95% CI = 17% – 39%) of programs create or post new ultrasound content at least once per month. Regarding barriers in the use of social media in EUS fellowships, 57% (95% CI = 45% – 69%) of program directors sited lack of time as the primary reason for decreased usage and implementation. Eighty‐four percent (95% CI = 75% – 93%) of responders felt that social media has the potential to impact patient care.

Conclusions

The results of this study indicate that there is perceived value in utilizing social media resources in EUS education; however, certain challenges need to be further evaluated.
Evaluation of the R2D2 protocol: A Novel Method for Assessing Emergency Department Disposition for Residents
Authors: Hernandez Jesse , Corker John , Roppolo Lynn , Jones Kyle , Hsu Daniel , Arthur D'Ann Elizabeth , Hynan Linda
Published: November 2016

Background

The emergency department (ED) disposition and discharge process is a critical period in a patient's transition from an acute care setting to self‐care or a bridge to other healthcare providers. The emergency physician plays a pivotal role in this process and is ultimately responsible for ensuring that patients are safely released from their care. We developed a protocol to guide residents through the ED discharge process using the mnemonic “R2D2”: reassess the patient, recheck the workup, discuss the disposition plan with the attending, and finally discuss the discharge plan with the patient.

Objectives

The objective was to assess the effectiveness of the R2D2 discharge protocol, executed by resident physicians, in improving patients' understanding of their diagnosis and treatment plans.

Methods

This is a before‐and‐after study in the ED of a county hospital and included all patients discharged by a resident physician from the ED 1 week before and 1 week after implementation of the R2D2 protocol. All participating resident physicians received a brief 10‐minute orientation to the R2D2 protocol at the end of the first week of the study period. Consecutive patients were identified, consented, and given a brief questionnaire about their discharge by research assistants. Certain exclusion criteria applied such as inability to speak English or Spanish or no phone for follow‐up. One to 2 weeks after ED discharge, patients from both groups were contacted by phone to assess their recall of their discharge instructions. Data analyses were performed using Fisher's exact, chi‐square tests, or two independent‐sample proportions tests as appropriate.

Results

We recruited 164 patients in the control group and 148 patients in the intervention group, totaling 312 patients. A total of 73.8% of the control group patients and 77.0% of the intervention group patients completed the follow‐up. On telephone follow‐up, 88% of the intervention patients knew their discharge diagnosis versus only 74% of control patients (p = 0.0062). Eighty percent of intervention patients knew their discharge treatment plan versus only 67% of control patients (p = 0.0259).

Conclusions

The R2D2 protocol resulted in significant improvement in patients' understanding of their discharge diagnosis and treatment plan.
Making the McMOST out of Milestones and Objectives: Reimagining Standard Setting Using the McMaster Milestones and Objectives Stratification Technique
Authors: Chan Teresa M. , Baw Bandar , McConnell Meghan , Kulasegaram Kulamakan
Published: November 2016

Background

As we enter the era of milestones and competency‐based medical education (CBME), there is an increasing need to examine the procedures for stratifying objectives into levels of achievement. Most techniques used to date (e.g., Delphi surveys) involve some sort of consensus‐based process, essentially crowd‐sourcing wisdom of multiple educators to set anticipated milestones. In most graduate education settings, however, many simply use the judgment of one or two educators when setting educational objectives. Meanwhile, standard‐setting procedures have been historically used in medical education for setting cut‐points to determine levels of acceptable performance and do so in a more robust manner.

Objectives

Inspired by these standard‐setting procedures, the authors sought to develop a new way to stratify objectives into three relative levels of achievement (junior [ACGME level 1], intermediate [ACGME level 2–3], senior [ACGME level 4]).

Methods

The authors describe a novel, stepwise method that is composed of four steps. There are four steps to the McMOST procedure: 1) sorting objectives with a group of experienced teachers, 2) factor analysis to group preferences, 3) labeling components and reorganizing groupings, and 4) confirmation and final review by educational and content experts.

Results

Using McMOST method resulted in a change of placement for 15 of 34 (44%) of the milestones and improved agreement in two of three levels (intermediate from intraclass correlation of 0.56 to 0.80; senior from 0.69 to 0.79).

Conclusions

The authors describe a novel protocol for stratifying objectives that may be useful to stratify and sort competencies into various levels of achievement (e.g., milestones) in this era of CBME.
Management of maternal anaphylaxis in pregnancy: a case report
Authors: Tsuzuki Yasunobu , Narita Mitsuo , Nawa Masayuki , Nakagawa Urara , Wakai Toshiaki
Published: November 2016

Case

A 26‐year‐old woman (gravida 2, para 1) at 25 weeks’ gestation was brought to the emergency department because of anaphylactic symptoms. She reported eating Japanese soba and developed symptoms of dyspnea, generalized itchy rash, abdominal pain, and severe uterine contractions within 15–30 min of eating. She was immediately treated by normal saline infusion, two injections of epinephrine (intramuscularly), and a nebulized short‐acting β2‐receptor agonist, followed by H1‐antihistamine and methylprednisolone. Obstetrical management was undertaken by an obstetrician.

Outcome

The patient recovered rapidly without a biphasic reaction of anaphylaxis. After 11 weeks, a healthy, neurologically intact baby was born.

Conclusion

Management of anaphylaxis in pregnant patients is basically the same of that in non‐pregnant ones. Treatment should commence immediately to prevent further development of the anaphylaxis reaction and fetal neurological deficiency.
Non‐traumatic bladder rupture showing less than 10 Hounsfield units of ascites
Authors: Mizumura Naoto , Okumura Satoshi , Toyoda Sho , Imagawa Atsuo , Ogawa Masao , Kawasaki Masayasu
Published: November 2016

Aim

Bladder ruptures are commonly misdiagnosed as gastrointestinal perforations or intestinal ischemia. If a diagnosis is made preoperatively, conservative treatment is a safe and effective option. We evaluated the validity of using the attenuation value of ascites, measured by non‐contrast computed tomography (CT), to identify patients with bladder ruptures.

Methods

A retrospective search of our hospital database identified 7 patients with confirmed bladder ruptures between 2007 and 2013. We also enrolled 18 patients with gastrointestinal perforations and 10 patients with intestinal ischemia with detectable ascites on abdominal CT that had undergone emergency exploratory laparotomy between 2007 and 2013. Between‐group comparisons of attenuation values of ascites as obtained by non‐contrast CT were evaluated.

Results

All attenuation values were less than 10 Hounsfield units (HU) in bladder rupture patients. Moreover, the attenuation value of ascites in cases of bladder rupture (median, 5.7; range, 3.1–6.1) was significantly lower than in cases of gastrointestinal perforation (median, 14.7; range, 4.7–25.4) and intestinal ischemia (median, 13.3; range, 6.0–18.1) (P = 0.004 for both comparisons).

Conclusion

Bladder rupture mimics gastrointestinal perforation and intestinal ischemia with acute kidney injury. Therefore, the diagnosis of bladder rupture using the attenuation value of ascites on non‐contrast CT is both useful and highly significant. We suggest that bladder rupture be considered in the differential diagnosis of patients presenting with acute abdominal pain and attenuation values of ascites of less than 10 Hounsfield units.
Diagnostic accuracy of radiographs for detecting supraglottitis: a systematic review and meta‐analysis
Authors: Fujiwara Takashi , Miyata Toyohisa , Tokumasu Hironobu , Gemba Hiroko , Fukuoka Toshio
Published: November 2016

Aim

To assess the diagnostic performance of lateral radiograph of the neck for supraglottitis in adults and children.

Methods

Electronic database searches (including PubMed, EMBASE, CINAHL, Web of Science, and WHO International Clinical Trials Registry Platform) were carried out through July 2014. Citations of included studies and recent narrative reviews were searched. Studies that compared lateral radiograph of the neck with a reference standard of direct/indirect laryngoscopy were included. Two reviewers independently assessed the methodological quality of included studies by Quality Assessment of Diagnostic Accuracy Studies 2 (QUADAS‐2).

Results

Of 2,088 potentially relevant citations, two single‐gate (cohort) studies and six two‐gate (case–control) studies were identified. These included studies of design are at the moderate or high risk of bias in QUADAS‐2. The pooled sensitivity from bivariate random‐effects regression was 92.9% (95% confidence interval [CI], 88.5–95.9%) and the pooled specificity was 89.2% (95% CI, 85.9–91.9%), but the diagnostic value would be overestimated because of selection bias in the six two‐gate studies. The sensitivity and specificity of the single‐gate studies were 100.0% (95% CI, 92.2–100.0%) and 30.6% (95% CI, 15.5–35.6%) in children and 81.0% (95% CI, 78.2–93.2%) and 85.7% specificity (95% CI, 78.2–93.2%) in adults.

Conclusion

This study determines that there are insufficient studies of lateral neck radiograph for detecting supraglottitis. Lateral radiograph of the neck seems to have moderate accuracy for detecting supraglottitis. Further approximately unbiased studies are needed to obtain more valid and reliable estimates of test accuracy.
Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels
Authors: Yoon Youngmin , Hall Anthony Shoji , Surendranath Yogesh
Published: November 2016

An electrode's performance for catalytic CO2 conversion to fuels is a complex convolution of surface structure and transport effects. Using well‐defined mesostructured silver inverse opal (Ag‐IO) electrodes, it is demonstrated that mesostructure‐induced transport limitations alone serve to increase the turnover frequency for CO2 activation per unit area, while simultaneously improving reaction selectivity. The specific activity for catalyzed CO evolution systematically rises by three‐fold and the specific activity for catalyzed H2 evolution systematically declines by ten‐fold with increasing mesostructural roughness of Ag‐IOs. By exploiting the compounding influence of both of these effects, we demonstrate that mesostructure, rather than surface structure, can be used to tune CO evolution selectivity from less than 5 % to more than 80 %. These results establish electrode mesostructuring as a powerful complementary tool for tuning both catalyst selectivity and efficiency for CO2 conversion into fuels.
Evaporite Borate‐Containing Mineral Ensembles Make Phosphate Available and Regiospecifically Phosphorylate Ribonucleosides: Borate as a Multifaceted Problem Solver in Prebiotic Chemistry
Authors: Kim Hyo‐Joong , Furukawa Yoshihiro , Kakegawa Takeshi , Bita Andrei , Scorei Romulus , Benner Steven A.
Published: November 2016

RNA is currently thought to have been the first biopolymer to support Darwinian natural selection on Earth. However, the phosphate esters in RNA and its precursors, and the many sites at which phosphorylation might occur in ribonucleosides under conditions that make it possible, challenge prebiotic chemists. Moreover, free inorganic phosphate may have been scarce on early Earth owing to its sequestration by calcium in the unreactive mineral hydroxyapatite. Herein, it is shown that these problems can be mitigated by a particular geological environment that contains borate, magnesium, sulfate, calcium, and phosphate in evaporite deposits. Actual geological environments, reproduced here, show that Mg2+ and borate sequester phosphate from calcium to form the mineral lüneburgite. Ribonucleosides stabilized by borate mobilize borate and phosphate from lüneburgite, and are then regiospecifically phosphorylated by the mineral. Thus, in addition to guiding carbohydrate pre‐metabolism, borate minerals in evaporite geoorganic contexts offer a solution to the phosphate problem in the “RNA first” model for the origins of life.
Kryo‐Elektronenmikroskopie als Methode für die strukturbasierte Wirkstoffentwicklung
Authors: Merino Felipe , Raunser Stefan
Published: November 2016

Über Jahrzehnte hinweg waren die Röntgenkristallographie und NMR‐Spektroskopie die wichtigsten Techniken, um atomare Strukturen von Makromolekülen zu erforschen. Aufgrund ihrer Größe, Instabilität, niedrigen Ausbeuten und anderen Faktoren sind jedoch viele Makromoleküle schwer zu kristallisieren oder nicht geeignet für NMR‐Studien. Die Kryo‐Elektronenmikroskopie (Kryo‐EM) benötigt keine Kristalle und ist deshalb oft die Methode der Wahl für makromolekulare Komplexe, die nicht kristallisiert werden können. Die Methode litt aber bisher unter der Einschränkung, dass selten atomare Auflösung erreicht wurde. Eine neue Generation von Detektoren, die in der Lage sind, einfallende Elektronen direkt zu messen, hat aber das Gebiet in den vergangenen drei Jahren revolutioniert. Mit dieser Technik gelingt es nun routinemäßig, die Strukturen von Makromolekülen mit nahezu atomarer Auflösung zu bestimmen. In diesem Aufsatz stellen wir einige der jüngsten Beispiele für hochaufgelöste Kryo‐EM‐Strukturen vor. Wir legen den Schwerpunkt auf Proteine mit pharmakologischer Relevanz, deren Strukturen mittels klassischer Kristallographie bisher nicht lösbar waren. Des Weiteren diskutieren wir Beispiele, in denen die Wechselwirkungen von Proteinen mit kleinen Molekülen bei atomarer Auflösung charakterisiert wurden. Abschließend erörtern wir die derzeitigen Grenzen der Kryo‐EM sowie wichtige Aspekte bezüglich ihrer Anwendung als Routine‐Methode für die Wirkstoffentwicklung.
Ketenimines from Isocyanides and Allyl Carbonates: Palladium‐Catalyzed Synthesis of β,γ‐Unsaturated Amides and Tetrazoles
Authors: Qiu Guanyinsheng , Mamboury Mathias , Wang Qian , Zhu Jieping
Published: November 2016

The reaction of allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc)2 provided ketenimines through β‐hydride elimination of the allyl imidoylpalladium intermediates. The insertion of the isocyanide into the π‐allyl Pd complex proceeded via an unusual η1‐allyl Pd species. The resulting ketenimines were hydrolyzed to β,γ‐unsaturated carboxamides during purification by flash column chromatography on silica gel or converted in situ into 1,5‐disubstituted tetrazoles by [3+2] cycloaddition with hydrazoic acid or trimethylsilyl azide.
Pentafluorethylkieselsäuren
Authors: Schwarze Nico , Steinhauer Simon , Neumann Beate , Stammler Hans‐Georg , Hoge Berthold
Published: November 2016

Reine, wasserfreie Hexafluorkieselsäure, H2[SiF6], ist immer noch schwer fassbar, obwohl ihre Existenz in wässriger Lösung ausführlich dokumentiert wurde. Beim Einengen entsprechender Lösungen tritt unausweichlich Zersetzung unter Bildung von Tetrafluorsilan und Fluorwasserstoff ein. Auch Oxoniumhexafluorosilicat ist bei Raumtemperatur nicht stabil. Partielle Substitution von Fluoratomen im [SiF6]2−‐Ion durch stark elektronenziehende Perfluoralkylgruppen führt zu einer erheblichen Stabilisierung der entsprechenden Fluorkieselsäure‐Derivate. So wurden mono‐ und bis(pentafluorethyl)substituierte Fluorkieselsäuren durch Umsetzung der zugehörigen Halogensilane (Si(C2F5)nX4−n, mit X=Cl, Br) mit Flusssäure (wässrige HF) synthetisiert und in Form ihrer Oxonium‐Salze als farblose Feststoffe isoliert. Die Präparate sind bei Raumtemperatur mehrere Monate ohne Zersetzung beständig und repräsentieren die ersten stabilen Hydrate von Fluorkieselsäuren.
Phosphor(V)‐nitrid macht pyrotechnische Tarnnebel sicherer
Authors: Koch Ernst‐Christian , Cudziło Stanisław
Published: November 2016

Der mögliche Ersatz von rotem Phosphor, PR, durch Phosphor(V)‐nitrid, P3N5, wurde theoretisch und experimentell untersucht. P3N5 kann gefahrlos mit KNO3 und sogar KClO3 sowie KClO4 gemischt werden. Die entsprechenden Formulierungen sind erstaunlicherweise reibunempfindlich und wenig schlagempfindlich. P3N5/KNO3‐Sätze mit ξ=20–80 Gew.‐% P3N5 erzeugen ein dichtes Aerosol und brennen etwa 200‐mal schneller ab als entsprechende Sätze mit PR. Daher haben P3N5/KNO3‐Tarnnebelsätze eine Leistungskennzahl, die diejenige herkömmlicher Tarnnebel auf der Grundlage von PR deutlich übersteigt. Auch ist P3N5 an feuchter Luft stabil und liefert nicht wie PR verschiedene Phosphorsäuren und Phosphan, PH3. P3N5 ist daher ein sicherer, stabiler und leistungsstarker Ersatz für PR zur Verwendung in unempfindlicher Munition.
Rhodium(I)‐Catalyzed C−C Bond Activation of Siloxyvinylcyclopropanes with Diazoesters
Authors: Feng Sheng , Mo Fanyang , Xia Ying , Liu Zhenxing , Liu Zhen , Zhang Yan , Wang Jianbo
Published: November 2016

The rhodium(I)‐catalyzed C−C bond activation reaction of siloxyvinylcyclopropanes with diazoesters demonstrates a novel mode of C−C bond cleavage of siloxyvinvylcyclopanes. The alkene products were obtained as single E‐configured isomers in good yields. A σ,η3‐allyl rhodium complex, which has been previously proposed as the key intermediate in rhodium(I)‐catalyzed cycloaddition of vinylcyclopropanes, has been isolated and characterized by X‐ray crystallography.
Direct Observation of Oxygen Dissociation on Non‐Stoichiometric Metal Oxide Catalysts
Authors: Huang Yi‐Lin , Pellegrinelli Chistopher , Wachsman Eric D.
Published: November 2016

Oxygen dissociation on metal oxides is a key reaction step, limiting the efficiency of numerous technologies. The complexity of the multi‐step oxygen reduction reaction (ORR) makes it difficult to investigate the oxygen dissociation step independently. Direct observation of the oxygen dissociation process is described, quantitatively, on perovskites La0.6Sr0.4Co0.2Fe0.8O3‐δ and (La0.8Sr0.2)0.95MnO3±δ, using gas‐phase isotope‐exchange with a 1:1 16O2:18O2 ratio. Oxygen transport mechanisms between gas–surface reactions and surface–bulk exchange are deconvoluted. Our findings show that regardless of participation of lattice oxygen, La0.6Sr0.4Co0.2Fe0.8O3‐δ is better at oxygen dissociation than (La0.8Sr0.2)0.95MnO3±δ. Heteroexchange, involving lattice oxygen, dominates on La0.6Sr0.4Co0.2Fe0.8O3‐δ. In contrast, (La0.8Sr0.2)0.95MnO3±δ shows both homoexchange and heteroexchange, with the latter only happening above 600 °C. Using a 1:1 isotope mixture, a simple method is presented for separation of the oxygen dissociation step from the overall ORR.
Chemically Delaminated Free‐Standing Ultrathin Covalent Organic Nanosheets
Authors: Khayum M. Abdul , Kandambeth Sharath , Mitra Shouvik , Nair Sanoop B. , Das Anuja , Nagane Samadhan S. , Mukherjee Rabibrata , Banerjee Rahul
Published: November 2016

Covalent organic nanosheets (CONs) are a new class of porous thin two‐dimensional (2D) nanostructures that can be easily designed and functionalized and could be useful for separation applications. Poor dispersion, layer restacking, and difficult postsynthetic modifications are the major hurdles that need to be overcome to fabricate scalable CON thin films. Herein, we present a unique approach for the chemical exfoliation of an anthracene‐based covalent organic framework (COF) to N‐hexylmaleimide‐functionalized CONs, to yield centimeter‐sized free‐standing thin films through layer‐by‐layer CON assembly at the air–water interface. The thin‐layer fabrication technique presented here is simple, scalable, and does not require any surfactants or stabilizing agents.
Identification of Two Distinct Sites for Antagonist and Biased Agonist Binding to the Human Chemokine Receptor CXCR3
Authors: Milanos Lampros , Saleh Noureldin , Kling Ralf C. , Kaindl Jonas , Tschammer Nuska , Clark Timothy
Published: November 2016

The chemokine receptor CXCR3 is a G protein‐coupled receptor that conveys extracellular signals into cells by changing its conformation upon ligand binding. We previously hypothesized that small‐molecule allosteric CXCR3‐agonists do not bind to the same allosteric binding pocket as 8‐azaquinazolinone‐based negative allosteric modulators. We have now performed molecular‐dynamics (MD) simulations with metadynamics enhanced sampling on the CXCR3 system to refine structures and binding modes and to predict the CXCR3‐binding affinities of the biased allosteric agonist FAUC1036 and the negative allosteric modulator RAMX3. We have identified two distinct binding sites; a “shallow” and a second “deeper” pocket to which the biased allosteric agonist FAUC1036 and negative allosteric modulator RAMX3 bind, respectively.
Structure and Reactivity of an Asymmetric Synthetic Mimic of Nitrogenase Cofactor
Authors: Tanifuji Kazuki , Sickerman Nathaniel , Lee Chi Chung , Nagasawa Takayuki , Miyazaki Kosuke , Ohki Yasuhiro , Tatsumi Kazuyuki , Hu Yilin , Ribbe Markus W.
Published: November 2016

The Mo nitrogenase catalyzes the ambient reduction of N2 to NH3 at its M‐cluster site. A complex metallocofactor with a core composition of [MoFe7S9C], the M‐cluster, can be extracted from the protein scaffold and used to facilitate the catalytic reduction of CN−, CO, and CO2 into hydrocarbons in the isolated state. Herein, we report the synthesis, structure, and reactivity of an asymmetric M‐cluster analogue with a core composition of [MoFe5S9]. This analogue, referred to as the Mo‐cluster, is the first synthetic example of an M‐cluster mimic with Fe and Mo positioned at opposite ends of the cluster. Moreover, the ability of the Mo‐cluster to reduce C1 substrates to hydrocarbons suggests the feasibility of developing nitrogenase‐based biomimetic approaches to recycle C1 waste into fuel products.
Enhanced Hydrogen Evolution under Simulated Sunlight from Neutral Electrolytes on (ZnSe)0.85(CuIn0.7Ga0.3Se2)0.15 Photocathodes Prepared by a Bilayer Method
Authors: Kaneko Hiroyuki , Minegishi Tsutomu , Nakabayashi Mamiko , Shibata Naoya , Domen Kazunari
Published: November 2016

A (ZnSe)0.85(CuIn0.7Ga0.3Se2)0.15 photocathode with a bilayer structure was fabricated and found to exhibit a photocurrent almost twice that of a photocathode with a monolayer structure during hydrogen evolution from water. The cathodic photocurrent reached maximum values of 12 and 4.9 mA cm−2 at 0 and 0.6 VRHE in a neutral phosphate buffer under simulated sunlight, while the half‐cell solar‐to‐hydrogen conversion efficiency was 3.0 % at 0.6 VRHE, with a maximum value of 3.6 % at 0.45 VRHE. Cross‐sectional mapping of the electron‐beam‐induced current established that the increased photocurrent can be attributed to improved uniformity at the solid–liquid junction in the bilayer sample, which results in enhanced carrier collection.
Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide
Authors: Fabini Douglas H. , Stoumpos Constantinos C. , Laurita Geneva , Kaltzoglou Andreas , Kontos Athanassios G. , Falaras Polycarpos , Kanatzidis Mercouri G. , Seshadri Ram
Published: November 2016

The structure of the hybrid perovskite HC(NH2)2PbI3 (formamidinium lead iodide) reflects competing interactions associated with molecular motion, hydrogen bonding tendencies, thermally activated soft octahedral rotations, and the propensity for the Pb2+ lone pair to express its stereochemistry. High‐resolution synchrotron X‐ray powder diffraction reveals a continuous transition from the cubic α‐phase (Pm
m, #221) to a tetragonal β‐phase (P4/mbm, #127) at around 285 K, followed by a first‐order transition to a tetragonal γ‐phase (retaining P4/mbm, #127) at 140 K. An unusual reentrant pseudosymmetry in the β‐to‐γ phase transition is seen that is also reflected in the photoluminescence. Around room temperature, the coefficient of volumetric thermal expansion is among the largest for any extended crystalline solid.
Magnetically separable CoFe2O4/CoxFey/activated carbon composites for Cd(II) removal from wastewater
Authors: Xu Jingcai , Hong Bo , Jin Hongxiao , Jin Dingfeng , Peng Xiaoling , Wang Xinqing
Published: November 2016

CoFe2O4 and CoxFey were anchored into activated carbon (AC) to synthesize CoFe2O4/CoxFey/AC composites using the sol–gel method for Cd(II) adsorption from wastewater. The results indicated that CoFe2O4 and CoxFey nanoparticles existed in the pores of AC. The magnetic properties of CoFe2O4/CoxFey/AC indicated it could be separated and retrieved easily using an external magnet after Cd(II) adsorption. The effects of solution pH, temperature and initial Cd(II) concentration on the Cd(II) adsorption of AC and CoFe2O4/CoxFey/AC were investigated. The standard free energy, enthalpy change and entropy change were evaluated. The kinetic parameters of Langmuir and Freundlich isothermal equation were analyzed, and the Freundlich kinetic model was feasible for describing the Cd(II) adsorption process of CoFe2O4/CoxFey/AC composites.
A route to magnetically separable nanocatalysts: Combined experimental and theoretical investigation of alkyl substituent role in ligand backbone towards epoxidation ability
Authors: Chattopadhyay Tanmay , Chakraborty Aratrika , Dasgupta Sanchari , Dutta Arnab , Menéndez M. Isabel , Zangrando Ennio
Published: November 2016

We have prepared two chiral Schiff base ligands, H2L1 and H2L2, and one achiral Schiff base ligand, H2L3, by treating 2,6‐diformyl‐4‐methylphenol separately with (R)‐1,2‐diaminopropane, (R)‐1,2‐diaminocyclohexane and 1,1′‐dimethylethylenediamine, in ethanolic medium, respectively. The complexes MnL1ClO4 (1), MnL2ClO4 (2), MnL3ClO4 (3), FeL1ClO4 (4), FeL2ClO4 (5) and FeL3ClO4 (6) have been obtained by reacting the ligands H2L1, H2L2 and H2L3 with manganese(III) perchlorate or iron(III) perchlorate in methanol. Circular dichroism studies suggest that ligands H2L1 and H2L2 and their corresponding complexes have asymmetric character. Complexes 1–6 have been used as homogeneous catalysts for epoxidation of alkenes. Manganese systems have been found to be much better than iron counterparts for alkene epoxidation, with 3 as the best catalyst among manganese systems and 6 as the best among iron systems. The order of their experimental catalytic efficiency has also been rationalized by theoretical calculations. We have observed higher enantiomeric excess product with catalysts 1 and 4, so they were attached to surface‐modified magnetic nanoparticles to obtain two new magnetically separable nanocatalysts, Fe3O4@dopa@MnL1 and Fe3O4@dopa@FeL4. They have been characterized and their alkene epoxidation ability has been investigated. These catalysts can be easily recovered by magnetic separation and recycled several times without significant loss of catalytic activity. Hence our study focuses on the synthesis of a magnetically recoverable asymmetric nanocatalyst that finds applications in epoxidation of alkenes and at the same time can be recycled and reused.
Novel dinuclear and trinuclear ruthenium clusters derived from 2‐aryl‐substituted indenylphosphines via C─H bond cleavage
Authors: Meng Tong , Yuan Jia , Han Zhi‐Jun , Luo Xue , Wu Qing‐Guo , Liu Sheng‐Hua , Chen Jian , Yu Guang‐Ao
Published: November 2016

Treatment of Ru3(CO)12 with an equivalent of (2‐phenyl‐1H‐inden‐3‐yl)dicyclohexylphosphine (1) and (2‐pyridyl‐1H‐inden‐1‐yl)dicyclohexylphosphine (4) in refluxing heptane gave the novel trinuclear ruthenium clusters (μ3‐η1:η2:η5–2‐phenyl‐3‐Cy2PC9H4)Ru3(CO)8 (1c) and [μ2‐η1–2‐(pyridin‐2‐yl)‐3‐Cy2PC9H6]Ru3(CO)9 (4a), respectively, via C─H bond cleavage. (2‐Mesityl‐1H‐inden‐3‐yl)dicyclohexylphosphine (2) reacted with Ru3(CO)12 in refluxing heptane to give the trinuclear ruthenium cluster [μ‐2‐mesityl‐(3‐Cy2PC9H5)](μ2‐CO)Ru3(CO)9 (2c) via C─H bond cleavage and carbonyl insertion. 2‐(Anthracen‐9‐yl)‐1H–inden‐3‐yldicyclohexylphosphine (3) reacted with Ru3(CO)12 in refluxing heptane to give the dinuclear ruthenium cluster [μ2‐η3:η3–2‐(anthracen‐9‐yl)‐3‐Cy2PC9H6]Ru2(CO)5 (3a). The structures of 1c, 2c, 3a and 4a were fully characterized using IR and NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. These results suggest that the 2‐aryl substituent on the indenyl ring has a pronounced effect on the reaction and coordination modes of Ru3(CO)12.
Quiescent crystallization of poly(lactic acid) studied by optical microscopy and light‐scattering techniques
Authors: Lohmeijer P. J. A. , Goossens J. G. P. , Peters G. W. M.
Published: November 2016

The crystallization behavior of poly(lactic acid) (PLA) has been studied extensively, and this has resulted in different reported values for the nucleation densities (Ns) and crystal growth rates (Gs) for similar grades. These inconsistencies may be magnified when they are used in subsequent modeling studies. Therefore, the quiescent crystallization behaviors of three PLA grades were studied with polarized optical microscopy and small‐angle light‐scattering experiments. The Gs and Ns were determined at several isothermal crystallization temperatures with a device that provided near‐instantaneous cooling to the isothermal crystallization temperature. Two growth rate regimes, which were attributed to α and α′ crystallization with a transition around 120 °C, were observed. Avrami analysis revealed that the poly(l‐lactic acid) homopolymer crystal growth was three‐dimensional and was unaffected by the presence of stereocomplex PLA. The PLA copolymer crystals had a transition from an initial sheaflike conformation to three‐dimensional growth. Furthermore, the lamellar twisting of the homopolymer was observed at the isothermal crystallization temperature around 144 °C. These findings can be used for future modeling studies to predict material behavior in various industrial processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44566.
Removal of nitrogen containing reducing agents from water coolant systems using ion exchange resin and membranes
Authors: Padmakumari T. V. , Jacob Kaleekkal Noel , Mohan D. , Velmurugan S.
Published: November 2016

Oxidizing environment prevailing in water coolant systems aggravates the corrosion of structural materials. Reducing agents are added to the reactor coolant systems to control the oxidants and mitigate material corrosion. Maintenance of required concentration of the reducing agents in the system and their removal after completing the processes can be done using ion exchange resins as well as ion exchange membranes. In this article, a comparative study on the efficacy in removing the reducing agents from aqueous solutions by the cation exchange resin and membranes such as sulfonated polysulfone and nafion is evaluated. Some of the membranes were synthesized in the laboratory and characterized by SEM, FTIR and pure water flux studies. Nitrogen containing reducing agents such as hydrazine, hydroxylamine, and ammonium hydroxide have been chosen for the study. Results indicate that strong acid cation exchange (SAC) resin taken in a column and sulfonated polysulfone (SPSf) membrane as a stack are found to be equally efficient in purification of coolant system from the added reducing agents. Uptake of metal ions was observed to be higher on SAC resin column in presence of reducing agent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44588.
Thermomechanical and cyclic behavior of biocomposites based on renewable thermoplastics from dimer fatty acids
Authors: Reulier M. , Matadi Boumbimba R. , Walsh Korb Z. , Vaudemont R. , Avérous L.
Published: November 2016

Microbiocomposites based on renewable thermoplastic matrices such as thermoplastic polyurethane (TPU) and polyamide (DAPA), synthesized from dimer fatty acids, and high aspect ratio talc were prepared. TPU/DAPA blends and their corresponding biocomposites exhibited mechanical behavior, which is linked to those of the matrices and their relative contents, i.e., going from a typical semicrystalline behavior (DAPA) to an elastomeric one (TPU). The understanding of the thermomechanical and cyclic behavior of these advanced materials, particularly for TPU/DAPA with high TPU content, is detailed. Addition of particles of high aspect ratio natural talc (HAR) improved the storage modulus over the whole temperature range (almost five times with 5 wt % HAR). Under cyclic manipulation, the biocomposites displayed a stress softening related to the Mullins' effect. An increase of the hysteresis and the residual deformation with the HAR content has been shown. The hyperelastic models of Mooney–Rivlin and Ogden–Dorfmann, used to predict the loading and unloading behavior, fitted with experimental data. The present work also reports the experimental characterization of the deformation mechanisms of these renewable biocomposites through different microscopic techniques at different scales, such as atomic force, scanning electron and transmission electron microscopies. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44610.
Progressive Decline of Lung Function in Rheumatoid Arthritis–Associated Interstitial Lung Disease
Authors: Zamora‐Legoff Jorge A. , Krause Megan L. , Crowson Cynthia S. , Ryu Jay H. , Matteson Eric L.
Published: November 2016

Objective

Interstitial lung disease (ILD) is associated with substantial morbidity in rheumatoid arthritis (RA), but very little is known about its long‐term progression. This study was undertaken to investigate the progression of pulmonary disease using a large single‐center cohort of patients with RA‐associated ILD.

Methods

Records of all patients with RA‐associated ILD seen at Mayo Clinic between 1998 and 2014, with at least 4 weeks follow‐up and at least 1 pulmonary function test, were identified and manually screened for study inclusion. Progression was defined as a diffusing capacity for carbon monoxide (DLco) <40% predicted (or patients whose illness was too advanced to undergo screening) or a forced vital capacity (FVC) <50% predicted. Time to progression was analyzed using the Kaplan‐Meier method.

Results

Of the 167 patients included in the study, 81 (49%) were female, with a mean ± SD age of 67 ± 10 years at diagnosis of ILD. Median follow‐up time from diagnosis of ILD was 3.3 years (range 0.01–14.8). One‐third of the patients required supplemental oxygen, 40% developed DLco <40% predicted, and 22% developed FVC <50% predicted within 5 years after ILD diagnosis. Usual interstitial pneumonia (UIP) versus nonspecific interstitial pneumonia (NSIP) was a risk factor for DLco progression (hazard ratio 3.29 [95% confidence interval 1.28–8.41]). Lower DLco and FVC at baseline increased the risk for progression to DLco <40% predicted and FVC <50% predicted, and higher rates of change in the first 6 months also increased the risk of progression.

Conclusion

Progressive loss of pulmonary function is common in RA‐associated ILD and is worse in patients with UIP than in those with NSIP. Predictors of progression in patients with RA‐associated ILD may aid clinicians in identifying patients at highest risk for progression of ILD.
A rapid and high‐throughput method for the determination of serum uric acid based on microarray technology and nanomaterial
Authors: Li Xiaohua , Bai Yunfeng , Feng Feng , Zhang Zhujun
Published: November 2016

Serum uric acid (SUA) is a new therapeutic target for non‐alcoholic fatty liver disease (NAFLD). In this study, we introduced a chemiluminescence (CL) method combined with microarray technology and a simple fabrication procedure to obtain a highly sensitive SUA probe based on a mesoporous metal oxide nanomaterial. The high‐throughput method was based on the generation of H2O2 from SUA by immobilized uricase and its measurement by a CL reaction catalyzed by mesoporous metal oxide nanomaterials. The CL probe was designed for SUA The linear range of the uric acid concentration was 0.6–9 μM and the detection limit was 0.1 μM. In comparison with the other SUA detection techniques, this method has the advantages of a low detection limit, high sensitivity and simplicity. A new sensitive high‐throughput approach was obtained for the determination of SUA.
Evaluation of eco‐friendly zwitterionic detergents for enveloped virus inactivation
Authors: Conley Lynn , Tao Yinying , Henry Alexis , Koepf Edward , Cecchini Douglas , Pieracci John , Ghose Sanchayita
Published: November 2016

Inclusion of a detergent in protein biotherapeutic purification processes is a simple and very robust method for inactivating enveloped viruses. The detergent Triton X‐100 has been used for many years and is part of the production process of several commercial therapeutic proteins. However, recent ecological studies have suggested that Triton X‐100 and its break‐down products can potentially behave as endocrine disrupters in aquatic organisms, raising concerns from an environmental impact perspective. As such, discharge of Triton X‐100 into the waste water treatment plants is regulated in some jurisdictions, and alternative detergents for viral inactivation are required. In this work, we report on the identification and evaluation of more eco‐friendly detergents as viable replacements for Triton X‐100. Five detergent candidates with low to moderate environmental impact were initially identified and evaluated with respect to protein stability, followed by proof‐of‐concept virus inactivation studies using a model enveloped virus. From the set of candidates lauryldimethylamine N‐oxide (LDAO) was identified as the most promising detergent due to its low ecotoxicity, robust anti‐viral activity (LRV >4 at validation set‐point conditions with X‐MuLX), and absence of any negative impact on protein function. This detergent exhibited effective and robust virus inactivation in a broad range of protein concentrations, solution conductivities, pHs, and in several different cell culture fluid matrices. The only process parameter which correlated with reduced virus inactivation potency was LDAO concentration, and then only when the concentration was reduced to below the detergent's critical micelle concentration (CMC). Additionally, this work also demonstrated that LDAO was cleared to below detectable levels after Protein A affinity chromatography, making it suitable for use in a platform process that utilizes this chromatographic mode for protein capture. All these findings suggest that LDAO may be a practical alternative to Triton X‐100 for use in protein therapeutic production processes for inactivating enveloped viruses. Biotechnol. Bioeng. 2017;114: 813–820. © 2016 Wiley Periodicals, Inc.
Clinical signs of fibrosis in small intestinal neuroendocrine tumours
Authors: Daskalakis K , Karakatsanis A , Stålberg P , Norlén O , Hellman P
Published: November 2016

Background

In patients with small intestinal neuroendocrine tumours (SI-NETs), serotonin and other cytokines released from tumour cells may induce fibrosis, leading to carcinoid heart disease and abdominal fibrotic reactions. The aim of this study was to assess the prevalence, clinical complications and management of this reaction in the abdomen.

Methods

This was a retrospective cohort study of patients with SI-NETs diagnosed between 1985 and 2015. Clinical data, outcomes, radiological findings, and surgical and radiological interventions were reviewed.

Results

A total of 824 patients were diagnosed with SI-NETs in the study interval. Clinically significant abdominal signs and symptoms of fibrosis occurred in 36 patients. Of these, 20 had critically symptomatic central mesenteric fibrosis causing obstruction of mesenteric vessels, and 16 had retroperitoneal fibrosis causing obstructive uropathy with hydronephrosis. Extensive fibrosis causing mesenteric vessel obstruction and/or obstructive uropathy was more often associated with symptomatic and advanced disease encompassing lymph node metastases in the mesenteric root, para-aortic lymph node metastases, as well as liver metastases and peritoneal carcinomatosis. Palliative intervention in terms of superior mesenteric vein stenting or resection of central mesenteric metastases and/or percutaneous nephrostomy and J stent treatment was beneficial in the majority of the patients.

Conclusion

Extensive abdominal fibrosis associated with clinically significant symptoms of intestinal ischaemia and/or obstructive uropathy was linked to advanced disease in patients with SI-NETs. Prompt recognition and minimally invasive intervention was effective in disease palliation.
Long non‐coding RNA MALAT1 functions as a mediator in cardioprotective effects of fentanyl in myocardial ischemia‐reperfusion injury
Authors: Zhao Zhi‐hui , Hao Wei , Meng Qing‐tao , Du Xiao‐bing , Lei Shao‐qing , Xia Zhong‐yuan
Published: November 2016

Long non‐coding (lncRNA) MALAT1 can be increased by hypoxia or ischemic limbs. Also, downregulation of MALAT1 contributes to reduction of cardiomyocyte apoptosis. However, the functional involvement of MALAT1 in myocardial ischemia‐reperfusion (I/R) injury has not been defined. This study investigated the functional involvement of lncRNA‐MALAT1 in cardioprotective effects of fentanyl. HL‐1, a cardiac muscle cell line from the AT‐1 mouse atrial cardiomyocyte tumor lineage was pre‐treated with fentanyl and generated cell model of hypoxia‐reoxygenation (H/R). Relative expression of MALAT1, miR‐145, and Bnip3 mRNA in cells was determined by quantitative real‐time PCR. Cardiomyocyte H/R injury was indicated by lactate dehydrogenase (LDH) release and cell apoptosis. The results showed that fentanyl abrogates expression of responsive gene for H/R and induces downregulation of MALAT1 and Bnip3 and upregulation of miR‐145. We found that miR‐145/Bnip3 pathway was negatively regulated by MALAT1 in H/R‐HL‐1 cell with or without fentanyl treatment. Moreover, both MALAT1 overexpression and miR‐145 knockdown reverse cardioprotective effects of fentanyl, as indicated by increase in LDH release and cell apoptosis. The reversal effect of MALAT1 for fentanyl is confirmed in cardiac ischemia/reperfusion (I/R) mice. In summary, lncRNA‐MALAT1 is sensitive to H/R injury and abrogates cardioprotective effects of Fentanyl by negatively regulating miR‐145/Bnip3 pathway.
Nuclear subcompartments: an overview
Authors: Nunes Vinícius Santana , Moretti Nilmar Silvio
Published: November 2016

The advance in biochemical and microscopy techniques has revealed the complexity and intricate nucleoplasm structure. Several subcompartments were identified in nucleus and the importance of these subcompartments in processes crucial for normal nuclear activity has been demonstrated. In this mini‐review, we will give an overview about the composition, function, and importance of the major nuclear subcompartments. Also, we will show the impact that perturbing these structures can cause in normal nuclear activity, and how these can contribute to the development of some human diseases.
Mechanistic Studies of Ullmann‐Type C–N Coupling Reactions: Carbonate‐Ligated Copper(III) Intermediates
Authors: Gurjar Kamlesh K. , Sharma Rajendra K.
Published: November 2016

In Ullmann‐type C−N coupling reactions, the involvement of CuIII species has been proposed many times on the basis of the oxidative addition–reductive elimination (OA‐RE) path for these reactions, but actual species could not be traced in experimental studies. In the C−N coupling reactions, carbonate and phosphate were considered widely as bases. In the present study, Cu‐mediated C−N coupling reactions of aryl halides and NuNH (amide and imide) were investigated extensively, and we provide direct spectroscopic evidence of actual CuIII species. For the first time, we reveal that carbonate and phosphate ions act as bidentate ligands as well as a base in the catalytic cycle, and thus the actual intermediate species is a carbonate‐ or phosphate‐ligated, distorted octahedral CuIII complex. Our experimental and computational studies have strengthened the hypothesis that these reactions follow an OA‐RE path.