bluuebunny/crossref_metadata_2025 huggingface dataset:
A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water
Authors: Schöfberger Wolfgang , Faschinger Felix , Chattopadhyay Samir , Bhakta Snehadri , Mondal Biswajit , Elemans Johannes A. A. W. , Müllegger Stefan , Tebi Stefano , Koch Reinhold , Klappenberger Florian , Paszkiewicz Mateusz , Barth Johannes V. , Rauls Eva , Aldahhak Hazem , Schmidt Wolf Gero , Dey Abhishek
Published: January 2016

Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H+/4 e− process, while oxygen can be fully reduced to water by a 4 e−/4 H+ process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2−. We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes.
Tyrosinase versus Catecholoxidase: ein Asparagin macht den Unterschied
Authors: Solem Even , Tuczek Felix , Decker Heinz
Published: January 2016

Tyrosinasen ermöglichen die ortho‐Hydroxylierung und Zwei‐Elektronen‐Oxidation von Monophenolen zu ortho‐Chinonen. Catecholoxidasen katalysieren dagegen nur die Oxidation von Diphenolen. Obwohl diese Prozesse von signifikantem Interesse sind, ist die molekulare Basis des funktionellen Unterschiedes zwischen Tyrosinasen und Catecholoxidasen noch unklar. Vor kurzem wurde postuliert, dass eine Glutaminsäure und ein Asparagin ein konserviertes Wassermolekül binden und aktivieren, um dadurch Monophenole zu deprotonieren. Hier zeigen wir, dass eine Polyphenoloxidase, die nur eine Diphenolase‐Aktivität besitzt, durch die Einführung eines Asparagins mittels Mutagenese in eine Tyrosinase umgewandelt werden kann. Das Asparagin und die konservierte Glutaminsäure sind für eine korrekte Orientierung und Aktivierung des konservierten Wassermoleküls notwendig, damit es die Hydroxygruppe des Monophenols deprotonieren kann.
Stable Boron Peroxides with a Subporphyrinato Ligand
Authors: Tsurumaki Eiji , Sung Jooyoung , Kim Dongho , Osuka Atsuhiro
Published: January 2016

Subporphyrin B‐peroxides have been synthesized in good yields by acid‐catalyzed exchange reactions of subporphyrin B‐methoxide with the corresponding hydroperoxides. Thermal dimerization of the subporphyrin B‐hydroperoxide provided the peroxo‐bridged bis(subporphyrin) quantitatively. These subporphyrin B‐peroxides are fairly stable under ambient conditions, which allowed their isolation and full characterization as the first examples of structurally authenticated boron hydroperoxides, acyclic boron organylperoxides, and neutral peroxo‐bridged diboron species. The subporphyrin B‐peroxides thus prepared were investigated through their crystal structures, IR spectra, and cyclic voltammograms as well as by DFT calculations. The subporphyrin B‐hydroperoxide oxidizes triphenylphosphine quantitatively to triphenylphosphine oxide.
Strategic Choices in Myanmar's Transition and Myanmar's National Security Policies
Authors: Wilson Trevor
Published: January 2016

Since 2011, Myanmar's leaders have concentrated on ensuring the success of their overall political transition, given the expectations created after the ‘Arab Spring’ of 2011–2012. Not surprisingly, designing a new national security policy was less a priority than achieving ‘peace’; national security was viewed as a matter of continuity rather than transition. Moreover, many of the reformist objectives of the political transition were not applied to the evolution of a new national security strategy or to the challenge of adjusting national security policies. Indeed, many historically unacceptable military practices—human rights abuses, targeting of civilian populations in insurgency areas and acting outside the law in confiscating land, labour and resources—continued. While this different approach to national security reflected ingrained sensitivity on the part of Myanmar's leadership, reluctance to expose national security policy to scrutiny and determination to retain political control, they are not necessarily unreceptive to overseas experiences.
Assessing Indonesia's Normative Influence: Wishful Thinking or Hidden Strength
Authors: Davies Mathew , Harris‐Rimmer Susan
Published: January 2016

This article takes a critical stance on Indonesia's normative influence. Whilst normative influence does help explain why Indonesia matters beyond the widespread consensus that it is weak, we also feel that its influence is often overstated. We examine three components of Indonesia's normative influence, modelling, diplomacy and civil society activism. In each component we assess the strengths and weaknesses of Indonesia and identify where wishful thinking predominates over dispassionate analysis. We conclude by arguing that the Jokowi approach to foreign policy destabilises the traditional make‐up of normative influence and, if it is pursued into the future, will lead to a re‐composition of that influence.
Beyond Life Support? Reflections on Solomon Islands after the Regional Assistance Mission
Authors: Allen Matthew , Dinnen Sinclair
Published: January 2016

The Australian‐led Regional Assistance Mission to Solomon Islands was conceived in the ‘state‐building moment’ that informed Western responses to ‘state failure’ over the past two decades. That moment has Now passed with renewed fiscal austerity, growing scepticism with interventionism, and shifts in Australia's regional policy priorities. The decade‐long mission, which has recently begun to drawdown, was successful in restoring security to Solomons but less so in its more ambitious state‐building efforts. Among the key constraints has been the mission's inability to influence a more inclusive political settlement. We highlight inherent tensions between instrumentalised approaches to state building and more organic processes of state formation. Looking forward, we consider how external assistance can contribute to state formation while retaining a focus on the ‘life support’ objectives of state building. We sketch some possibilities for hybrid forms of institutional development that might combine strengths from both local and liberal orders.
How are Foreign Policy Decisions Made in China?
Authors: Jakobson Linda , Manuel Ryan
Published: January 2016

The growing number of actors involved in China's international activities has led to fractured authority in foreign policy decision‐making. Actors vie for the attention of senior officials to promote their interests on any specific issue. As a result, decision making is often a slow process; there are multiple channels of information, and actors appeal to public opinion to support their claims. Since 2012, Xi Jinping has taken charge of all foreign policy related decision‐making bodies in what appears to be an attempt to improve coordination of interest groups. A slight shift to a more personified foreign policy than during the Hu or Jiang eras has also taken place. In this paper, we describe how foreign policy decisions should be made in China according to formal rules; next, we take into account the reality of how the Chinese political system deals with China's evolving international role. We conclude by assessing the risks of fragmentation, on the one hand, and Xi's efforts to recentralise foreign policy, on the other hand.
Indonesia's ‘Great Power’ Aspirations: A Critical View
Authors: Fealy Greg , White Hugh
Published: January 2016

Indonesia is readying itself for a return to a diplomatic assertiveness not seen since the early 1960s. Partly, this reflects the approach of 0050 resident Joko Widodo and his government, but it also reflects growing aspirations among the wider circles of Indonesia's elites for their country to act as, and be acknowledged as a ‘big country’ – negara besar. This constitutes a significant shift from the traditions of low‐key diplomacy of the New Order and Reformasi eras. Several factors are pushing this shift. Indonesia's growing economic weight will, over time, provide more of the foundations of national power than it has had hitherto. The changing regional strategic and political order will make it harder for Indonesia to take its place in Asia for granted and to assume that its intentional interests can be protected primarily through ASEAN. And domestically the trend to rising nationalism will provide political incentives to greater assertiveness. On the other hand, Indonesia still has big hurdles to overcome before it can act as an effective major power in Asia. Its economic trajectory remains uncertain, its military is weak, its diplomatic capacities are underdeveloped, and it lacks a clearly articulated set of policy objectives to pursue. So, it remains to be seen whether Indonesia's aspirations to major power status will be realised.
Benzimidazole‐Based Quinazolines: In Vitro Evaluation, Quantitative Structure–Activity Relationship, and Molecular Modeling as Aurora Kinase Inhibitors
Authors: Sharma Alka , Luxami Vijay , Saxena Sanjai , Paul Kamaldeep
Published: January 2016

A series of benzimidazole‐based quinazoline derivatives with different substitutions of primary and secondary amines at the C2 position (1–12) were evaluated for their Aurora kinase inhibitory activities. All compounds except for 3 and 6 showed good activity against Aurora kinase inhibitors, with IC50 values in the range of 0.035–0.532 μM. The ligand efficiency (LE) of the compounds with Aurora A kinase was also determined. The structure–activity relationship and the quantitative structure–activity relationship revealed that the Aurora inhibitory activities of these derivatives primarily depend on the different substitutions of the amine present at the C2 position of the quinazoline core. Molecular docking studies in the active binding site also provided theoretical support for the experimental biological data acquired. The current study identifies a novel class of Aurora kinase inhibitors, which can further be used for the treatment of cancer.
Supramolecular Porphyrin‐Based Metal–Organic Frameworks with Fullerenes: Crystal Structures and Preferential Intercalation of C70
Authors: Ohmura Tetsushi , Usuki Arimitsu , Mukae Yusuke , Motegi Hirofumi , Kajiya Shuji , Yamamoto Masami , Senda Shunsuke , Matsumoto Tsuyoshi , Tatsumi Kazuyuki
Published: January 2016

The syntheses and characterization of two new porphyrin‐based metal–organic frameworks (P‐MOFs), through the complexation of 5,10,15,20‐tetra‐4‐pyridyl‐21 H,23 H‐porphine (H2TPyP) and copper(II) acetate (CuAcO) in the presence of the fullerenes C60 or C70 are reported. Complex 1 was synthesized in conjunction with C60, and this reaction produced a two‐dimensional (2D) porous structure with the composition CuAcO‐CuTPyP⊃m‐dichlorobenzene (m‐DCB), in which C60 molecules were not intercalated. Complex 2 was synthesized in the presence of C70, generating a three‐dimensional (3D) porous structure, in which C70 was intercalated, with the composition CuAcO‐CuTPyP⋅C70⊃m‐DCB⋅CHCl3. The structures of these materials were determined by X‐ray diffraction to identify the supramolecular interactions that lead to 2D and 3D crystal packing motifs. When a combination of C60 and C70 was employed, C70 was found to be preferentially intercalated between the porphyrins.
Chitosan‐Assisted Crystallization and Film Forming of Perovskite Crystals through Biomineralization
Authors: Yang Yang , Sun Chen , Yip Hin‐Lap , Sun Runcang , Wang Xiaohui
Published: January 2016

Biomimetic mineralization is a powerful approach for the synthesis of advanced composite materials with hierarchical organization and controlled structure. Herein, chitosan was introduced into a perovskite precursor solution as a biopolymer additive to control the crystallization and to improve the morphology and film‐forming properties of a perovskite film by way of biomineralization. The biopolymer additive was able to control the size and morphology of the perovskite crystals and helped to form smooth films. The mechanism of chitosan‐mediated nucleation and growth of the perovskite crystals was explored. As a possible application, the chitosan–perovskite composite film was introduced into a planar heterojunction solar cell and increased power conversion efficiency relative to that observed for the pristine perovskite film was achieved. The biomimetic mineralization method proposed in this study provides an alternative way of preparing perovskite crystals with well‐controlled morphology and properties and extends the applications of perovskite crystals in photoelectronic fields, including planar‐heterojunction solar cells.
Racemization of undesired enantiomers: Immobilization of mandelate racemase and application in a fixed bed reactor
Authors: Wrzosek Katarzyna , García Rivera Mariel A. , Bettenbrock Katja , Seidel‐Morgenstern Andreas
Published: January 2016

Production of optically pure products can be based on simple unselective synthesis of racemic mixtures combined with a subsequent separation of the enantiomers; however, this approach suffers from a 50% yield limitation which can be overcome by racemization of the undesired enantiomer and recycling. Application of biocatalyst for the racemization steps offers an attractive option for high‐yield manufacturing of commercially valuable compounds. Our work focuses on exploiting the potential of racemization with immobilized mandelate racemase. Immobilization of crude mandelate racemase via covalent attachment was optimized for two supports: Eupergit® CM and CNBr‐activated Sepharose 4 Fast Flow. To allow coupling of enzymatic reaction with enantioselective chromatography, a mobile phase composition compatible with both processes was used in enzymatic reactor. Kinetic parameters obtained analyzing experiments carried out in a batch reactor could be successfully used to predict fixed‐bed reactor performance. The applicability of the immobilized enzyme and the determined kinetic parameters were validated in transient experiments recording responses to pulse injections of R‐mandelic acid. The approach investigated can be used for futher design and optimization of high yield combined resolution processes. The characterized fixed‐bed enzymatic reactor can be integrated e.g. with chromatographic single‐ or multicolumn steps in various configurations.
Peptidoglycan microarray as a novel tool to explore protein–ligand recognition
Authors: Wang Ning , Hirata Akiyoshi , Nokihara Kiyoshi , Fukase Koichi , Fujimoto Yukari
Published: January 2016

Peptidoglycan is a giant bag‐shaped molecule essential for bacterial cell shape and resistance to osmotic stresses. The activity of a large number of bacterial surface proteins involved in cell growth and division requires binding to this macromolecule. Recognition of peptidoglycan by immune effectors is also crucial for the establishment of the immune response against pathogens. The availability of pure and chemically defined peptidoglycan fragments is a major technical bottleneck that has precluded systematic studies of the mechanisms underpinning protein‐mediated peptidoglycan recognition. Here, we report a microarray strategy suitable to carry out comprehensive studies to characterize proteins–peptidoglycan interactions. We describe a method to introduce a functional group on peptidoglycan fragments allowing their stable immobilization on amorphous carbon chip plates to minimize nonspecific binding. Such peptidoglycan microarrays were used with a model peptidoglycan binding protein—the human peptidoglycan recognition protein‐S (hPGRP‐S). We propose that this strategy could be implemented to carry out high‐throughput analyses to study peptidoglycan binding proteins. © 2016 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 422–429, 2016.
Vascular interventions in the elderly
Authors: Hinchliffe R J , Earnshaw J J
Published: January 2016

Overused?
Molecular and biological hallmarks of ageing
Authors: Aunan J R , Watson M M , Hagland H R , Søreide K
Published: January 2016

Background

Ageing is the inevitable time-dependent decline in physiological organ function that eventually leads to death. Age is a major risk factor for many of the most common medical conditions, such as cardiovascular disease, cancer, diabetes and Alzheimer's disease. This study reviews currently known hallmarks of ageing and their clinical implications.

Methods

A literature search of PubMed/MEDLINE was conducted covering the last decade.

Results

Average life expectancy has increased dramatically over the past century and is estimated to increase even further. Maximum longevity, however, appears unchanged, suggesting a universal limitation to the human organism. Understanding the underlying molecular processes of ageing and health decline may suggest interventions that, if used at an early age, can prevent, delay, alleviate or even reverse age-related diseases. Hallmarks of ageing can be grouped into three main categories. The primary hallmarks cause damage to cellular functions: genomic instability, telomere attrition, epigenetic alterations and loss of proteostasis. These are followed by antagonistic responses to such damage: deregulated nutrient sensing, altered mitochondrial function and cellular senescence. Finally, integrative hallmarks are possible culprits of the clinical phenotype (stem cell exhaustion and altered intercellular communication), which ultimately contribute to the clinical effects of ageing as seen in physiological loss of reserve, organ decline and reduced function.

Conclusion

The sum of these molecular hallmarks produces the clinical picture of the elderly surgical patient: frailty, sarcopenia, anaemia, poor nutrition and a blunted immune response system. Improved understanding of the ageing processes may give rise to new biomarkers of risk or prognosis, novel treatment targets and translational approaches across disciplines that may improve outcomes.
Surgery for an ageing population
Authors: Søreide K , Wijnhoven B P L
Published: January 2016

The greatest surgical challenge
The impact of phospholipids and phospholipid removal on bioanalytical method performance
Authors: Carmical Jennifer , Brown Stacy
Published: January 2016

Phospholipids (PLs) are a component of cell membranes, biological fluids and tissues. These compounds are problematic for the bioanalytical chemist, especially when PLs are not the analytes of interest. PL interference with bioanalysis highly impacts reverse‐phase chromatographic methods coupled with mass spectrometric detection. Phospholipids are strongly retained on hydrophobic columns, and can cause significant ionization suppression in the mass spectrometer, as they out‐compete analyte molecules for ionization. Strategies for improving analyte detection in the presence of PLs are reviewed, including in‐analysis modifications and sample preparation strategies. Removal of interfering PLs prior to analysis seems to be most effective at moderating the matrix effects from these endogenous cellular components, and has the potential to simplify chromatography and improve column lifetime. Products targeted at PL removal for sample pre‐treatment, as well as products that combine multiple modes of sample preparation (i.e. Hybrid SPE), show significant promise in mediating the effect on PL interference in bioanalysis. Copyright © 2016 John Wiley & Sons, Ltd.
Hematologic malignancies in South Africa 2000–2006: analysis of data reported to the National Cancer Registry
Authors: Schonfeld Sara J. , Erdmann Friederike , Wiggill Tracey , Singh Elvira , Kellett Patricia , Babb Chantal , Schüz Joachim
Published: January 2016

Little is known about the incidence patterns of hematologic malignancies in Sub‐Saharan Africa, including South Africa. We estimated incidence rates of pathology‐confirmed adult cases of leukemia, myeloma and related diseases (myeloma), Hodgkin lymphoma (HL), and non‐Hodgkin lymphoma (NHL) reported to the National Cancer Registry of South Africa (NCR) between 2000 and2006, by age, gender, and population group (Black, White, Coloured, Asian/Indian). Gender‐specific age‐standardized rates were calculated overall and by population group and incidence rate ratios (IRRs) were estimated using Poisson regression models. Between 2000 and 2006, there were 14662 cases of leukemia, myeloma, HL, and NHL reported to the registry. Incidence rates of reported hematologic malignancies were generally 20–50% higher among males than females. Our analyses suggested marked differences in the rates of reported hematologic malignancies by population group which were most pronounced when comparing the White versus Black population groups (IRRs ranging from 1.6 for myeloma to 3.8 for HL for males and females combined). Challenges related to diagnosis and reporting of cancers may play a role in the patterns observed by population group while the set‐up of the NCR (pathology‐based) could lead to some degree of under‐ascertainment in all groups. This is the first country‐wide report of the incidence of hematologic malignancies in South Africa. Despite challenges, it is important to analyze and report available national cancer incidence data to raise awareness of the cancer burden and to characterize patterns by demographic characteristics so as ultimately to improve the provision of cancer‐related health care.
Adjunctive Chinese Herbal Medicine therapy improves survival of patients with chronic myeloid leukemia: a nationwide population‐based cohort study
Authors: Fleischer Tom , Chang Tung‐Ti , Chiang Jen‐Huai , Chang Ching‐Mao , Hsieh Ching‐Yun , Yen Hung‐Rong
Published: January 2016

Despite good clinical results of current drugs, a good reason still exists to search for additional therapies for the management of Chronic Myeloid Leukemia (CML). Chinese Herbal Medicine (CHM) has thus far been overlooked by researchers and no data exists on the subject. We studied the impact of adjunctive CHM on the disease course of CML, using mortality as the major outcome measurement. We used the Taiwanese National Health Insurance Research Database to perform a nationwide population‐based cohort study. Our study included CML patients diagnosed between 2000 and 2010. We matched groups according to age, sex, Charlson Comorbidity Index (CCI) score and use of imatinib, and compared the Hazard Ratios (HR) of CHM group and non‐CHM users, as well as characterized trends of prescriptions used for treating CML. 1371 patients were diagnosed with CML in the years examined, of which 466 were included in to this study. We found that the HR of CHM group was significantly lower compared to non‐CHM groups (0.32, 95% CI 0.22–0.48, P < 0.0001). We also established that this association between reduced HR was dose‐dependent, and the longer CHM users received prescriptions, the lower the HR (P < 0.01). We also analyzed the most commonly used herbal products as well as the HR associated to their use, thus providing future research candidates. Our results supply a strong reason to assume that when administered by properly trained physicians, CHM may have a substantial positive impact on the management of CML.
The effect of comorbidity on the use of adjuvant chemotherapy and type of regimen for curatively resected stage III colon cancer patients
Authors: Hsieh Mei‐Chin , Thompson Trevor , Wu Xiao‐Cheng , Styles Timothy , O'Flarity Mary B. , Morris Cyllene R. , Chen Vivien W.
Published: January 2016

Postsurgical chemotherapy is guideline‐recommended therapy for stage III colon cancer patients. Factors associated with patients not receiving adjuvant chemotherapy were identified in numerous studies; comorbidity was recognized as an important factor besides patient's age. We assessed the association between comorbidity and the use of adjuvant chemotherapy and type of chemotherapy regimen. Stage III colon cancer patients who underwent surgical resection were obtained from ten Centers for Disease Control and Prevention (CDC)‐NPCR Specialized Registries which participated in the Comparative Effectiveness Research (CER) project. Comorbidity was classified into no comorbidity recorded, Charlson, non‐Charlson comorbidities, number, and severity of Charlson comorbidity. Pearson chi‐square test and multivariable logistic regression were employed. Of 3180 resected stage III colon cancer patients, 64% received adjuvant chemotherapy. After adjusting for patient's demographic and tumor characteristics, there were no significant differences in receipt of chemotherapy between Charlson and non‐Charlson comorbidity. However, patients who had two or more Charlson comorbidities or had moderate to severe disease were significantly less likely to have chemotherapy (ORs 0.69 [95% CI, 0.51–0.92] and 0.62 [95% CI, 0.42–0.91], respectively) when compared with those with non‐Charlson comorbidity. In addition, those with moderate or severe comorbidities were more likely to receive single chemotherapy agent (P < 0.0001). Capecitabine and FOLFOX were the most common single‐ and multi‐agent regimens regardless of type of comorbidity grouping. Both the number and severity of comorbidity were significantly associated with receipt of guideline‐recommended chemotherapy and type of agent in stage III resected colon cancer patients. Better personalized care based on individual patient's condition ought to be recognized.
Imaging Cancer Cells Expressing the Folate Receptor with Carbon Dots Produced from Folic Acid
Authors: Bhunia Susanta Kumar , Maity Amit Ranjan , Nandi Sukhendu , Stepensky David , Jelinek Raz
Published: January 2016

Development of new imaging tools for cancer cells in vitro and in vitro is important for advancing cancer research, elucidating drug effects upon cancer cells, and studying cellular processes. We showed that fluorescent carbon dots (C‐dots) synthesized from folic acid can serve as an effective vehicle for imaging cancer cells expressing the folate receptor on their surface. The C‐dots, synthesized through a simple one‐step process from folic acid as the carbon source, exhibited selectivity towards cancer cells displaying the folate receptor, making such cells easily distinguishable in fluorescence microscopy imaging. Biophysical measurements and competition experiments both confirmed the specific targeting and enhanced uptake of C‐dots by the folate receptor‐expressing cells. The folic acid‐derived C‐dots were not cytotoxic, and their use in bioimaging applications could aid biological studies of cancer cells, identification of agonists/antagonists, and cancer diagnostics.
The assessment of thrombotic markers utilizing ionic versus non‐ionic contrast during coronary angiography and intervention trial
Authors: Shah Binita , Berger Jeffrey S. , Allen Nicole , Guo Yu , Sedlis Steven P. , Xu Jinfeng , Perez Adriana , Attubato Michael , Slater James , Feit Frederick
Published: January 2016

Objective

To determine how two different types of iodinated contrast media (CM), low‐osmolar ionic dimer ioxaglate (Hexabrix) and iso‐osmolar non‐ionic dimer iodixanol (Visipaque), affect multiple indices of hemostasis.

Background

In vitro models demonstrate differential effects of ionic and non‐ionic CM on markers of hemostasis.

Methods

This blinded endpoint trial randomized 100 patients to ioxaglate or iodixanol. The primary endpoint was change in endogenous thrombin potential (ETP) following diagnostic angiography. Secondary endpoints included change in markers of fibrinolysis [tissue plasminogen activator (tPA) and plasminogen activator inhibitor 1 (PAI‐1)] and platelet aggregation following diagnostic angiography and percutaneous coronary intervention (PCI) with bivalirudin. Data are presented as median [interquartile range].

Results

ETP significantly decreased after diagnostic angiography in both ioxaglate (baseline 1810 nM*minute [1540‐2089] to post‐angiography 649 nM*minute [314‐1347], p < 0.001) and iodixanol groups (baseline 1682 nM*minute [1534‐2147] to post‐angiography 681 nM*minute [229‐1237], p < 0.001), but the decrease was not different between CM (p = 0.70). There was a significant increase in ETP during PCI (n = 45), despite the use of bivalirudin, suggesting a prothrombotic effect of PCI (post‐angiography 764 nM*minute [286‐1283] to post‐PCI 1081 nM*minute [668‐1552], p = 0.02). There were no significant differential effects on tPA, PAI‐1, and markers of platelet activity.

Conclusion

There were no significant differential effects between ioxaglate and iodixanol. Both CM led to significant reductions in thrombin generation and no significant effects on fibrinolytic activity or platelet activity, thereby contributing to a favorable antithrombotic milieu. © 2016 Wiley Periodicals, Inc.
Two‐year results and subgroup analyses of the PEPCAD China in‐stent restenosis trial: A prospective, multicenter, randomized trial for the treatment of drug‐eluting stent in‐stent restenosis
Authors: Xu Bo , Qian Jie , Ge Junbo , Wang Jian'an , Chen Fang , Chen Jiyan , Wei Meng , Chen Yundai , Yang Yuejin , Gao Runlin ,   on behalf of PEPCAD China ISR investigators
Published: January 2016

Background

The PEPCAD China ISR trial investigated the safety and efficacy of paclitaxel‐coated balloon (PCB) angioplasty in an Asian patient population with coronary drug‐eluting stent in‐stent restenosis (DES‐ISR). Methods: A total of 220 patients with coronary DES‐ISR were treated with PCB angioplasty or with paclitaxel‐eluting stents (PES). This randomized (1:1), single‐blind prospective multicenter trial in a Chinese population used 9‐month in‐segment late lumen loss (LLL) as the primary endpoint. Secondary endpoints included the 24‐month clinical event rates. Results: Both treatment groups were similar in terms of patient, lesion, or procedural characteristics. After the 12‐month follow‐up evaluation, additional clinical events only occurred in the PES study group. The combined rate of all‐cause mortality and myocardial infarction (MI) in the PCB group was significantly lower than that in the PES group (3.7% vs. 11.8%, P = 0.03). Additional subgroup analyses of 9‐month in‐segment LLL and 2‐year target lesion failure in patients with diabetes, small vessels, diffuse ISR, and stent margin restenosis did not show more favorable results for one specific treatment group. Conclusions: The 2‐year follow‐up demonstrated sustained long‐term clinical efficacy for both devices. PCB angioplasty was associated with significantly lower overall and cardiovascular mortality/MI rates in patients with DES‐ISR lesions while avoiding the use of additional metal layers for drug release (ClinicalTrials.gov identifier: NCT 01622075). © 2016 Wiley Periodicals, Inc.
Planned versus provisional rotational atherectomy for severe calcified coronary lesions: Insights From the ROTATE multi‐center registry
Authors: Kawamoto Hiroyoshi , Latib Azeem , Ruparelia Neil , Boccuzzi Giacomo G. , Pennacchi Mauro , Sardella Gennaro , Garbo Roberto , Meliga Emanuele , D'Ascenzo Fabrizio , Moretti Claudio , Rossi Marco Luciano , Presbitero Patrizia , Ielasi Alfonso , Magri Caroline , Nakamura Sunao , Colombo Antonio
Published: January 2016

Objectives

We aimed to investigate procedural feasibility and outcomes associated with planned rotational atherectomy (RA) for severely calcified coronary lesions. Background: Limited data are available addressing the benefits of planned RA compared to provisional RA.

Methods

Between 2002 and 2013, all patients with calcified lesions treated by RA were enrolled. Of these, patients treated with planned RA (358 patients) were compared to those treated with provisional RA (309 patients).

Results

In‐hospital major adverse cardiovascular events (MACE) were tended to be better in the planned RA group (unadjusted OR: 0.76; 95% CI: 0.44–1.31, P = 0.32, and adjusted OR: 0.59; 95% CI: 0.33–1.05, P = 0.07). The number of pre‐dilation balloon catheters was significantly lower in the planned RA group (1.17 ± 0.60 vs. 1.47 ± 0.76, P < 0.001). Procedure time, fluoroscopy time, and contrast volume used were all significantly reduced in the planned RA group compared to the provisional RA group (procedure time; 65.2 ± 36.8min vs. 84.4 ± 43.1min, P < 0.001, fluoroscopy time; 33.1 ± 22.9min vs. 51.2 ± 29.6min, P < 0.001, and contrast volume; 232.9 ± 141.6ml vs. 302.9 ± 150.3ml, P < 0.001). The incidence of MACE at 1‐year was significantly higher amongst the unadjusted population, whereas the difference was less marked between groups after propensity‐score adjustment (unadjusted HR: 1.78; 95% CI: 1.16–2.74, P = 0.01, and adjusted HR: 1.44; 95% CI: 0.92–2.26, P = 0.11).

Conclusions

Planned RA appears to be safe and was associated with a reduction in procedural and fluoroscopy times, contrast volume, and the number of pre‐dilation balloon catheters used. If there is a strong likelihood of requiring RA for the treatment of severely calcified lesions, operators should have a low threshold for adopting a planned RA strategy. © 2016 Wiley Periodicals, Inc.
Severity assessment of intracranial large artery stenosis by pressure gradient measurements: A feasibility study
Authors: Han Yun‐Fei , Liu Wen‐Hua , Chen Xiang‐Liang , Xiong Yun‐Yun , Yin Qin‐ , Xu Ge‐Lin , Zhu Wu‐Sheng , Zhang Ren‐Liang , Ma Min‐Min , Li Min‐ , Dai Qi‐Liang , Sun Wen‐ , Liu De‐Zhi , Duan Li‐Hui , Liu Xin‐Feng
Published: January 2016

Background

Fractional flow reserve (FFR)‐guided revascularization strategy is popular in coronary intervention. However, the feasibility of assessing stenotic severity in intracranial large arteries using pressure gradient measurements still remains unclear.

Methods

Between March 2013 and May 2014, 12 consecutive patients with intracranial large artery stenosis (including intracranial internal carotid artery, middle cerebral M1 segment, intracranial vertebral artery, and basilar artery) were enrolled in this study. The trans‐stenotic pressure gradient was measured before and/or after percutaneous transluminal angioplasty and stenting (PTAS), and was then compared with percent diameter stenosis. A Pd/Pa cut‐off of ≤0.70 was used to guide stenting of hemodynamically significant stenoses. The device‐related and procedure‐related serious adverse events and recurrent cerebral ischemic events were recorded.

Results

The target vessel could be reached in all cases. No technical complications occurred due to the specific study protocol. Excellent pressure signals were obtained in all patients. For seven patients who performed PTAS, the mean pre‐procedural pressure gradient decreased from 59.0 ± 17.2 to 13.3 ± 13.6 mm Hg after the procedure (P < 0.01). Only one patient who refused stenting experienced a TIA event in the ipsilateral MCA territory. No recurrent ischemic event was observed in other patients.

Conclusion

Mean trans‐stenotic pressure gradients can be safely and easily measured with a 0.014‐inch fluid‐filled guide wire in intracranial large arteries. © 2016 Wiley Periodicals, Inc.
Mechanism of the Accelerated Reduction of an Oxidized Metal Catalyst under Electric Discharge
Authors: Kim Taegyu , Lee Dae Hoon , Jo Sungkwon , Pyun Sung Hyun , Kim Kwan‐Tae , Song Young‐Hoon
Published: January 2016

The mechanism of accelerated reduction of oxidized metal catalysts by plasma was herein explored. Hydrogen radicals produced by discharge are important for generating energetic hydroxyl radicals by an Eley–Rideal‐type reaction, and these radicals in turn undergo desorption without further reaction. The desorbed hydroxyl radicals react with hydrogen radicals to produce gas‐phase water. The results obtained herein discuss the advantages of employing plasma catalysis for surface reactions.
Enhancement of Catalytic Activity in Epoxide Hydration by Increasing the Concentration of Cobalt(III)/Salen in Porous Polymer Catalysts
Authors: Dai Zhifeng , Sun Qi , Chen Fang , Pan Shuxiang , Wang Liang , Meng Xiangju , Li Jixue , Xiao Feng‐Shou
Published: January 2016

The rational design of catalytic materials from the reaction characteristics is expected to be a useful strategy to create highly efficient catalysts. Herein, according to a well‐established reaction pathway of epoxide hydration catalyzed a dual‐molecular system of Co3+/salen in which a high concentration of active sites is favorable to enhance the activity, we provide an alternative way to prepare a highly efficient heterogeneous catalyst with a high concentration of Co3+/salen from the polymerization of vinyl‐functionalized salen monomers followed by the loading of Co3+ species (Co3+/POL‐salen). Co3+/POL‐salen has a hierarchical porosity and an extraordinary hydrothermal stability. Importantly, catalytic tests in epoxide hydration demonstrate that Co3+/POL‐salen affords excellent high activities, which are even better than those of the homogeneous version. This phenomenon is related to the very high concentration of Co3+/salen in the catalyst. In addition, this catalyst can be recycled readily because of its excellent hydrothermal stability.
Mercury Removal by Adsorption on Pectin Extracted from Sugar Beet Pulp: Optimization by Response Surface Methodology
Authors: Ma Xinfang , Li Deqiang , Wu Zhansheng , Zhang Haiyan , Chen Xiaoxuan , Liu Zhiyong
Published: January 2016

Considering the rich sugar beet resource in Xinjiang, China, the possibilities for Hg(II) removal by pectin extracted from sugar beet pulp and optimization of the extraction process using response surface methodology (RSM) were studied. The experiments were proposed by Box‐Behnken design (BBD) and a second‐order regression model was developed for regression analysis and analysis of variance. Optimized conditions in terms of temperature, concentration, and solid‐liquid ratio were determined. The effects of different parameters like pH, time, temperature, and initial Hg(II) concentration on adsorption capacity were investigated. The isotherm adsorption experiments were fitted with the Langmuir model which indicated monolayer adsorption.
How Many Water Molecules Does it Take to Dissociate HCl?
Authors: Vargas‐Caamal Alba , Cabellos Jose Luis , Ortiz‐Chi Filiberto , Rzepa Henry S. , Restrepo Albeiro , Merino Gabriel
Published: January 2016

The potential energy surfaces of the HCl(H2O)n (n is the number of water molecules) clusters are systematically explored using density functional theory and high‐level ab initio computations. On the basis of electronic energies, the number of water molecules needed for HCl dissociation is four as reported by some experimental groups. However, this number is five owing to the inclusion of entropic factors. Wiberg bond indices are calculated and analyzed, and the results provide a quadratic correlation and classification of clusters according to the nondissociated, partially dissociated, and fully dissociated character of the H−Cl bond. Our computations show that if temperature is not controlled during the experiment, the values obtained for the dipole moment (or for any measurable property) are susceptible to change, providing a different picture of the number of water molecules needed for HCl dissociation in a nanoscopic droplet.
Advances on the Determination of the Astatine Pourbaix Diagram: Predomination of AtO(OH)2− over At− in Basic Conditions
Authors: Sergentu Dumitru‐Claudiu , Teze David , Sabatié‐Gogova Andréa , Alliot Cyrille , Guo Ning , Bassal Fadel , Silva Isidro Da , Deniaud David , Maurice Rémi , Champion Julie , Galland Nicolas , Montavon Gilles
Published: January 2016

It is generally assumed that astatide (At−) is the predominant astatine species in basic aqueous media. This assumption is questioned in non‐complexing and non‐reductive aqueous solutions by means of high‐pressure anion‐exchange chromatography. Contrary to what is usually believed, astatide is found to be a minor species at pH=11. A different species, which also bears a single negative charge, becomes predominant when the pH is increased beyond 7. Using competition experiments, an equilibrium constant value of 10−6.9 has been determined for the formation of this species from AtO(OH) with the exchange of one proton. The identification of this species, AtO(OH)2−, is achieved through relativistic quantum mechanical calculations, which rule out the significant formation of the AtO2− species, while leading to a hydrolysis constant of AtO(OH) in excellent agreement with experiment when the AtO(OH)2− species is considered. Beyond the completion of the Pourbaix diagram of astatine, this new information is of interest for the development of 211At radiolabeling protocols.
Real‐Time Chemical Analysis of E‐Cigarette Aerosols By Means Of Secondary Electrospray Ionization Mass Spectrometry
Authors: García‐Gómez Diego , Gaisl Thomas , Barrios‐Collado César , Vidal‐de‐Miguel Guillermo , Kohler Malcolm , Zenobi Renato
Published: January 2016

Chemical analysis of aerosols collected from electronic cigarettes (ECs) has shown that these devices produce vapors that contain harmful and potentially harmful compounds. Conventional analytical methods used for the analysis of electronic cigarettes do not reflect the actual composition of the aerosols generated because they usually neglect the changes in the chemical composition that occur during the aerosol generation process and after collection. The aim of this work was to develop and apply a method for the real‐time analysis of electronic cigarette aerosols, based on the secondary electrospray ionization technique coupled to high‐resolution mass spectrometry, by mimicking the “vaping” process. Electronic cigarette aerosols were successfully analyzed and quantitative differences were found between the liquids and aerosols. Thanks to the high sensitivity shown by this method, more than 250 chemical substances were detected in the aerosols, some of them showing a high correlation with the operating power of the electronic cigarettes. The method also allows proper quantification of several chemical components such as alkaloids and flavor compounds.
Observation of Main‐Group Tricarbonyls [B(CO)3] and [C(CO)3]+ Featuring a Tilted One‐Electron Donor Carbonyl Ligand
Authors: Jian Jiwen , Jin Jiaye , Qu Hui , Lin Hailu , Chen Mohua , Wang Guanjun , Zhou Mingfei , Andrada Diego M. , Hermann Markus , Frenking Gernot
Published: January 2016

A combined experimental and theoretical study on the main‐group tricarbonyls [B(CO)3] in solid noble‐gas matrices and [C(CO)3]+ in the gas phase is presented. The molecules are identified by comparing the experimental and theoretical IR spectra and the vibrational shifts of nuclear isotopes. Quantum chemical ab initio studies suggest that the two isoelectronic species possess a tilted η1(μ1‐CO)‐bonded carbonyl ligand, which serves as an unprecedented one‐electron donor ligand. Thus, the central atoms in both complexes still retain an 8‐electron configuration. A thorough analysis of the bonding situation gives quantitative information about the donor and acceptor properties of the different carbonyl ligands. The linearly bonded CO ligands are classical two‐electron donors that display classical σ‐donation and π‐back‐donation following the Dewar–Chatt–Duncanson model. The tilted CO ligand is a formal one‐electron donor that is bonded by σ‐donation and π‐back‐donation that involves the singly occupied orbital of the radical fragments [B(CO)2] and [C(CO)2]+.
Enantiomeric Separations of Pyriproxyfen and its Six Chiral Metabolites by High‐Performance Liquid Chromatography
Authors: Zhang Chuntao , Liu Hui , Liu Donghui , Wang Liying , Gao Jing , Zhou Zhiqiang , Wang Peng
Published: January 2016

Pyriproxyfen is a chiral insecticide, and over 10 metabolites have been identified in the environment. In this work the separations of the enantiomers of pyriproxyfen and its six chiral metabolites were studied by high‐performance liquid chromatography (HPLC). Both normal phase and reverse phase were applied using the chiral columns Chiralpak IA, Chiralpak IB, Chiralpak IC, Chiralcel OD, Chiralcel OD‐RH, Chiralpak AY‐H, Chiralpak AD‐H, Chiracel OJ‐H, (R,R)‐Whelk‐O 1, and Lux Cellulose‐3. The effects of the chromatographic parameters such as mobile phase composition and temperature on the separations were investigated and the enantiomers were identified with an optical rotation detector. The enantiomers of these targets could obtain complete separations (resolution factor Rs > 1.5) on Chiralpak IA, Chiralpak IB, Chiralcel OD, Chiralpak AY‐H, or Chiracel OJ‐H under normal conditions. Chiralcel OJ‐H showed the best chiral separation results with n‐hexane as mobile phase and isopropanol (IPA) as modifier. The simultaneous enantiomeric separation of pyriproxyfen and four chiral metabolites was achieved on Chiralcel OJ‐H under optimized condition: n‐hexane/isopropanol = 80/20, 15°C, flow rate of 0.8 ml/min, and UV detection at 230 nm. The enantiomers of pyriproxyfen and the metabolites A, C, and D obtained complete separations on Chiralpak IA, Chiralpak IC, and Lux Cellulose‐3 under reverse phase using acetonitrile/water as the mobile phase. The retention factors (k) and selectivity factors (α) decreased with increasing temperature, and the separations were better under low temperature in most cases. The work is of significance for the investigation of the environmental behaviors of pyriproxyfen on an enantiomeric level. Chirality 28:245–252, 2016. © 2016 Wiley Periodicals, Inc.
Chemical looping syngas from CO2 and H2O over manganese oxide minerals
Authors: Perreault Patrice , Patience Gregory S.
Published: January 2016

Rather than sequestering carbon dioxide from the exhaust of chemical looping combustion reactors, together with the water, it could be used as a source of syngas. For the first time, we split water to hydrogen and carbon dioxide to carbon monoxide with a manganese ore. Specific CO production is 10–100 times higher than Sr, Ce, and Fe doped perovskites and perovskites. At a contact time of 0.01 s and at temperatures ranging from 810–960 °C the maximum specific CO production was 5.5 . A combined kinetic‐axial dispersion hydrodynamic model accounts for 97 % of the variance in the data assuming the reaction rate is first‐order in and surface reduced sites and in equilibrium with the reverse reaction—a first‐order reaction in CO with surface oxidized sites. A second reaction accounts for the diffusion of surface oxygen to the bulk lattice. Hydrogen productivity peaked at 4.8 at 947 °C, which is twice as high as reported in previous studies on and in the hercynite cycle.
Micro‐syngas technology options for GtL
Authors: Trevisanut Cristian , Jazayeri Seyed M. , Bonkane Said , Neagoe Cristian , Mohamadalizadeh Ali , Boffito Daria C. , Bianchi Claudia L. , Pirola Carlo , Visconti Carlo Giorgio , Lietti Luca , Abatzoglou Nicolas , Frost Lyman , Lerou Jan , Green William , Patience Gregory S.
Published: January 2016

Natural gas emissions contribute to climate change, and equally importantly, affect the health of populations near gas fields.[1] At night, the flares from the Bakken fields in North Dakota burn as bright as the lights in cities as large as Minneapolis. Rather than flaring (or worse, venting), this associated natural gas represents a multi‐billion dollar opportunity.[2] Pipelines and liquefying natural gas are cost prohibitive in many cases. Converting methane to fuels is an attractive alternative.

We examined three options to convert natural gas to syngas ( and CO), which is the first step to producing fuels: Steam Methane Reforming (SMR), Auto‐Thermal Reforming (ATR), and Catalytic Partial Oxidation (CPOX). Based on a multi‐objective optimization analysis, C hydrocarbon yields are highest with CPOX as the first step followed by Fischer‐Tropsch synthesis (FT). A micro‐refinery with the CPOX‐FT process treating (100 ) natural gas, produces 1300 (8.2 ) of C hydrocarbons. Maximum yields for the SMR‐FT and ATR‐FT processes are 938 and 1100 (5.9 , 7.0 ) of C, respectively. Large‐scale POX and ATR processes produce 1600 L per 2800 kL (10 bbl per 100 MCF) of natural gas.