bluuebunny/crossref_metadata_2025 huggingface dataset:
Mo‐Based Ultrasmall Nanoparticles on Hierarchical Carbon Nanosheets for Superior Lithium Ion Storage and Hydrogen Generation Catalysis
Authors: Chen Ling , Jiang Hao , Jiang Haibo , Zhang Haoxuan , Guo Shaojun , Hu Yanjie , Li Chunzhong
Published: May 2017

Constructing 3D hierarchical architecture consisting of 2D hybrid nanosheets is very critical to achieve uppermost and stable electrochemical performance for both lithium‐ion batteries (LIBs) and hydrogen evolution reaction (HER). Herein, a simple synthesis of uniform 3D microspheres assembled from carbon nanosheets with the incorporated MoO2 nanoclusters is demonstrated. The MoO2 nanoclusters can be readily converted into the molybdenum carbide (Mo2C) nanocrystals by using high temperature treatment. Such assembling architecture is highly particular for preventing Mo‐based ultrasmall nanoparticles from coalescing or oxidizing and endowing them with rapid electron transfer. Consequently, the MoO2/C hybrids as LIB anode materials deliver a specific capacity of 625 mA h g−1 at 1600 mA g−1 even after 1000 cycles, which is among the best reported values for MoO2‐based electrode materials. Moreover, the Mo2C/C hybrids also exhibit excellent electrocatalytic activity for HER with small overpotential and robust durability in both acid and alkaline media. The present work highlights the importance of designing 3D structure and controlling ultrasmall Mo‐based nanoparticles for enhancing electrochemical energy conversion and storage applications.
Body fat attenuates muscle mass catabolism among physically active humans in temperate and cold high altitude environments
Authors: Ocobock Cara J.
Published: May 2017

Objective

Typical diet plans are based on an individual's body mass; however, body composition may be important to consider when an individual is in a negative energy balance. This study examines if high initial body fat and dietary macronutrient content reduce muscle mass catabolism during excursions in temperate and cold high altitude environments.

METHODS

Subjects—53 healthy, un‐acclimated volunteers (37 males and 16 females)—took part in 12‐16 week‐long outdoor education courses in moderately high altitude temperate and cold climates in the western United States. Body mass, body fat percentage, fat mass, and muscle mass were measured before and after each excursion. Total energy expenditure and dietary intake were also measured.

RESULTS

In temperate and cold environments, both sexes lost significant amounts of body mass. In temperate climates both sexes lost a significant amount of fat mass, but not muscle mass. In cold climates, there was no significant change in fat mass for either sex; however, females gained muscle mass while males lost muscle mass. In both climates subjects with lower initial body fat percentages lost significantly more muscle mass than subjects with higher initial body fat percentages. There was no significant relationship between macronutrient intake and muscle mass loss for either sex.

CONCLUSION

These results suggests that during a negative energy balance dietary macronutrient content cannot abate the loss of muscle mass, but body fat may have a protective effect. This information should be used to improve individualized diets based on body composition, not body mass.
The ecology of white‐handed and pileated gibbons in a zone of overlap and hybridization in Thailand
Authors: Asensio Norberto , José‐Domínguez Juan Manuel , Kongrit Chalita , Brockelman Warren Y.
Published: May 2017

Objectives

The study of related species in contact zones can elucidate what factors mediate species coexistence and geographical distributions. We investigated niche overlap and group interactions of two gibbon species and their hybrids co‐occurring in a zone of overlap and hybridization.

Methods

The location, composition and behavior of white‐handed, pileated, and mixed‐species gibbon groups were studied by following them during 31 consecutive months in a relatively large part of the contact zone.

Results

Twenty groups of white‐handed gibbon were mapped followed by nine groups of pileated gibbons and five mixed‐species groups. White‐handed, pileated and mixed‐species groups had similar sizes and composition, ate a high proportion of fruits, shared a large number of species in their diets, and presented similar habitat preferences. Group home range sizes did not differ between species and overlapped little with neighboring groups irrespective of species, and intraspecific and interspecific encounter rates were similar.

Discussion

Ecological similarities support that competition between the gibbon species exists and takes the form of interspecific territoriality. However, we could not find any clear mechanism of niche partitioning favoring coexistence between species. Our findings suggest that the contact zone is unstable and is maintained by dispersal inward from groups of the parental species. The relatively low numbers of mixed‐species groups and hybrids found suggests a high degree of premating reproductive isolation, perhaps mediated by interspecific miscommunication. The existence of hybrids and backcrosses potentially undetectable from phenotypic characters alone raises the possibility of more widespread introgression than has been evident. Hence, while interspecific territoriality should reduce the rate of gene transfer, it would not necessarily present a barrier to introgression into contiguous populations of the opposite species.
Mapping and comparing bacterial microbiota in the sinonasal cavity of healthy, allergic rhinitis, and chronic rhinosinusitis subjects
Authors: Lal Devyani , Keim Paul , Delisle Josie , Barker Bridget , Rank Matthew A. , Chia Nicholas , Schupp James M. , Gillece John D. , Cope Emily K.
Published: May 2017

Background

The role of microbiota in sinonasal inflammation can be further understood by targeted sampling of healthy and diseased subjects. We compared the microbiota of the middle meatus (MM) and inferior meatus (IM) in healthy, allergic rhinitis (AR), and chronic rhinosinusitis (CRS) subjects to characterize intrasubject, intersubject, and intergroup differences.

Methods

Subjects were recruited in the office, and characterized into healthy, AR, and CRS groups. Endoscopically‐guided swab samples were obtained from the MM and IM bilaterally. Bacterial microbiota were characterized by sequencing the V3‐V4 region of the 16S ribosomal RNA (rRNA) gene.

Results

Intersubject microbiome analyses were conducted in 65 subjects: 8 healthy, 11 AR, and 46 CRS (25 CRS with nasal polyps [CRSwNP]; 21 CRS without nasal polyps [CRSsNP]). Intrasubject analyses were conducted for 48 individuals (4 controls, 11 AR, 8 CRSwNP, and 15 CRSwNP). There was considerable intersubject microbiota variability, but intrasubject profiles were similar (p = 0.001, nonparametric t test). Intrasubject bacterial diversity was significantly reduced in MM of CRSsNP subjects compared to IM samples (p = 0.022, nonparametric t test). CRSsNP MM samples were enriched in Streptococcus, Haemophilus, and Fusobacterium spp. but exhibited loss of diversity compared to healthy, CRSwNP, and AR subject‐samples (p < 0.05; nonparametric t test). CRSwNP patients were enriched in Staphylococcus, Alloiococcus, and Corynebacterium spp.

Conclusion

This study presents the sinonasal microbiome profile in one of the larger populations of non‐CRS and CRS subjects, and is the first office‐based cohort in the literature. In contrast to healthy, AR, and CRSwNP subjects, CRSsNP MM samples exhibited decreased microbiome diversity and anaerobic enrichment. CRSsNP MM samples had reduced diversity compared to same‐subject IM samples, a novel finding.
Stress response and communication in surgeons undergoing training in endoscopic management of major vessel hemorrhage: a mixed methods study
Authors: Jukes Alistair K. , Mascarenhas Annika , Murphy Jae , Stepan Lia , Muñoz Tamara N. , Callejas Claudio A. , Valentine Rowan , Wormald P.J. , Psaltis Alkis J.
Published: May 2017

Background

Major vessel hemorrhage in endoscopic, endonasal skull‐base surgery is a rare but potentially fatal event. Surgical simulation models have been developed to train surgeons in the techniques required to manage this complication. This mixed‐methods study aims to quantify the stress responses the model induces, determine how realistic the experience is, and how it changes the confidence levels of surgeons in their ability to deal with major vascular injury in an endoscopic setting.

Methods

Forty consultant surgeons and surgeons in training underwent training on an endoscopic sheep model of jugular vein and carotid artery injury. Pre‐course and post‐course questionnaires providing demographics, experience level, confidence, and realism scores were taken, based on a 5‐point Likert scale. Objective markers of stress response including blood pressure, heart rate, and salivary alpha‐amylase levels were measured.

Results

Mean “realism” score assessed posttraining showed the model to be perceived as highly realistic by the participants (score 4.02). Difference in participant self‐rated pre‐course and post‐course confidence levels was significant (p < 0.0001): mean pre‐course confidence level 1.66 (95% confidence interval [CI], 1.43 to 1.90); mean post‐course confidence level 3.42 (95% CI, 3.19 to 3.65). Differences in subjects’ heart rates (HRs) and mean arterial blood pressures (MAPs) were significant between injury models (p = 0.0008, p = 0.0387, respectively). No statistically significant difference in salivary alpha‐amylase levels pretraining and posttraining was observed.

Conclusion

Results from this study indicate that this highly realistic simulation model provides surgeons with an increased level of confidence in their ability to deal with the rare but potentially catastrophic event of major vessel injury in endoscopic skull‐base surgery.
Pyrimethamine significantly lowers cerebrospinal fluid Cu/Zn superoxide dismutase in amyotrophic lateral sclerosis patients with SOD1 mutations
Authors: Lange Dale J. , Shahbazi Mona , Silani Vincenzo , Ludolph Albert C. , Weishaupt Jochen H. , Ajroud‐Driss Senda , Fields Kara G. , Remanan Rahul , Appel Stanley H. , Morelli Claudia , Doretti Alberto , Maderna Luca , Messina Stefano , Weiland Ulrike , Marklund Stefan L. , Andersen Peter M.
Published: May 2017

Objective

Cu/Zn superoxide dismutase (SOD1) reduction prolongs survival in SOD1‐transgenic animal models. Pyrimethamine produces dose‐dependent SOD1 reduction in cell culture systems. A previous phase 1 trial showed pyrimethamine lowers SOD1 levels in leukocytes in patients with SOD1 mutations. This study investigated whether pyrimethamine lowered SOD1 levels in the cerebrospinal fluid (CSF) in patients carrying SOD1 mutations linked to familial amyotrophic lateral sclerosis (fALS/SOD1).

Methods

A multicenter (5 sites), open‐label, 9‐month‐duration, dose‐ranging study was undertaken to determine the safety and efficacy of pyrimethamine to lower SOD1 levels in the CSF in fALS/SOD1. All participants underwent 3 lumbar punctures, blood draw, clinical assessment of strength, motor function, quality of life, and adverse effect assessments. SOD1 levels were measured in erythrocytes and CSF. Pyrimethamine was measured in plasma and CSF. Appel ALS score, ALS Functional Rating Scale–Revised, and McGill Quality of Life Single‐Item Scale were measured at screening, visit 6, and visit 9.

Results

We enrolled 32 patients; 24 completed 6 visits (18 weeks), and 21 completed all study visits. A linear mixed effects model showed a significant reduction in CSF SOD1 at visit 6 (p < 0.001) with a mean reduction of 13.5% (95% confidence interval [CI] = 8.4–18.5) and at visit 9 (p < 0.001) with a mean reduction of 10.5% (95% CI = 5.2–15.8).

Interpretation

Pyrimethamine is safe and well tolerated in ALS. Pyrimethamine is capable of producing a significant reduction in total CSF SOD1 protein content in patients with ALS caused by different SOD1 mutations. Further long‐term studies are warranted to assess clinical efficacy. Ann Neurol 2017;81:837–848
A Rhodium(II)‐Catalyzed Formal [4+1]‐Cycloaddition toward Spirooxindole Pyrrolone Construction Employing Vinyl Isocyanates as 1,4‐Dipoles
Authors: Meloche Jennifer L. , Ashfeld Brandon L.
Published: May 2017

A RhII‐catalyzed, formal [4+1]‐cycloaddition between diazooxindoles as electrophilic C1 synthons and 1,3‐heterodienes for the construction of spirooxindole pyrrolones is described. Employing vinyl isocyanates as 1,4‐dipoles, the cycloannulation occurs under relatively mild conditions and provides the corresponding pyrrolones in good to excellent yields.
Multi‐shelled Dendritic Mesoporous Organosilica Hollow Spheres: Roles of Composition and Architecture in Cancer Immunotherapy
Authors: Yang Yannan , Lu Yao , Abbaraju Prasanna Lakshmi , Zhang Jun , Zhang Min , Xiang Guangya , Yu Chengzhong
Published: May 2017

Developing potent adjuvants for the stimulation of robust immune response is central for effective cancer immunotherapy. Double‐shelled dendritic mesoporous organosilica hollow spheres are an excellent adjuvant and provide superior immunity in cancer immunotherapy, and better than their counterparts either with a pure silica composition or a single‐walled architecture. This study provides new insights in the rational design of effective nanostructured adjuvants for vaccine developments.
Construction of Chiral Tetrahydro‐β‐Carbolines: Asymmetric Pictet–Spengler Reaction of Indolyl Dihydropyridines
Authors: Wang Shou‐Guo , Xia Zi‐Lei , Xu Ren‐Qi , Liu Xi‐Jia , Zheng Chao , You Shu‐Li
Published: May 2017

A highly efficient synthesis of the enantioenriched tetrahydro‐β‐carbolines was developed by using a chiral phosphoric acid catalyzed Pictet–Spengler reaction of indolyl dihydropyridines. The reaction proceeds under mild reaction conditions to afford the desired chiral tetrahydro‐β‐carbolines in good to excellent yields (up to 96 %) and high enantioselectivities (up to 99 % ee). With this method, a formal synthesis of tangutorine and a total synthesis of deplancheine were achieved in a highly efficient manner.
Nickel‐Catalyzed α‐Allylation of Aldehydes and Tandem Aldol Condensation/Allylation Reaction with Allylic Alcohols
Authors: Bernhard Yann , Thomson Brodie , Ferey Vincent , Sauthier Mathieu
Published: May 2017

An additive‐free nickel‐catalyzed α‐allylation of aldehydes with allyl alcohol is reported. The reaction is promoted by 1 mol % of in situ formed nickel complex in methanol, and water is the sole by‐product of the reaction. The experimental conditions allow the conversion of various α‐branched aldehydes and α,β‐unsaturated aldehydes as nucleophiles. The same catalyst and reaction conditions enabled a tandem aldol condensation of aldehyde/α‐allylation reaction.
Phase‐Selective Syntheses of Cobalt Telluride Nanofleeces for Efficient Oxygen Evolution Catalysts
Authors: Gao Qiang , Huang Chuan‐Qi , Ju Yi‐Ming , Gao Min‐Rui , Liu Jian‐Wei , An Duo , Cui Chun‐Hua , Zheng Ya‐Rong , Li Wei‐Xue , Yu Shu‐Hong
Published: May 2017

Cobalt‐based nanomaterials have been intensively explored as promising noble‐metal‐free oxygen evolution reaction (OER) electrocatalysts. Herein, we report phase‐selective syntheses of novel hierarchical CoTe2 and CoTe nanofleeces for efficient OER catalysts. The CoTe2 nanofleeces exhibited excellent electrocatalytic activity and stablity for OER in alkaline media. The CoTe2 catalyst exhibited superior OER activity compared to the CoTe catalyst, which is comparable to the state‐of‐the‐art RuO2 catalyst. Density functional theory calculations showed that the binding strength and lateral interaction of the reaction intermediates on CoTe2 and CoTe are essential for determining the overpotential required under different conditions. This study provides valuable insights for the rational design of noble‐metal‐free OER catalysts with high performance and low cost by use of Co‐based chalcogenides.
Full Protection of Intensely Luminescent Gold(I)–Silver(I) Cluster by Phosphine Ligands and Inorganic Anions
Authors: Lei Zhen , Pei Xiao‐Li , Guan Zong‐Jie , Wang Quan‐Ming
Published: May 2017

An intensely luminescent gold(I)–silver(I) cluster [(C)(AuPPhpy2)6Ag6(CF3CO2)3](BF4)5 (PPhpy2=bis(2‐pyridyl)phenylphosphine) (3) is synthesized by the reaction of [(C)(AuPPhpy2)6Ag4](BF4)6 with AgCF3CO2. All eight faces of the octahedral C@Au6 core in 3 are capped, that is, six faces are capped by silver ions and two by tetrafluoroborates. Cluster 3 is intensely luminescent in solution with a quantum yield of 92 %. Ligation of CF3CO2− ions is vital for the construction and emission properties of 3, as confirmed by DFT calculations. BF4− ions are involved in the protecting sphere of the metal core, as evidenced by 19F NMR data. The participation of phosphines, CF3CO2−, and BF4− ions in the protection of the emissive core and the enhancement of the rigidity of the cluster result in the high emission efficiency. This is the first example of organic ligands and inorganic anions forming a rigid protecting sphere for luminescent coinage‐metal clusters.
Palladium‐Catalyzed Enantioselective Redox‐Relay Heck Alkynylation of Alkenols To Access Propargylic Stereocenters
Authors: Chen Zhi‐Min , Nervig Christine S. , DeLuca Ryan J. , Sigman Matthew S.
Published: May 2017

An enantioselective redox‐relay Heck alkynylation of di‐ and trisubstituted alkenols to construct propargylic stereocenters is disclosed using a new pyridine oxazoline ligand. This strategy allows direct access to chiral β‐alkynyl carbonyl compounds employing allylic alcohol substrates in contrast to more traditional conjugate addition methods.
Thiourea dioxide‐grafted γ‐Fe2O3/HAp magnetic nanoparticles: Efficient, green and reusable nanocatalyst for synthesis of pyranopyridine derivatives
Authors: Azarifar Davood , Ghaemi Masoumeh
Published: May 2017

A novel thiourea dioxide‐functionalized hydroxyapatite‐encapsulated hybrid core‐shell γ‐Fe2O3@HAp‐TUD nanoparticles (MNPs) were prepared and characterized by FT‐IR, EDX, SEM, XRD, TGA and VSM analytical methods. The catalytic activity of these MNPs was evaluated through one‐pot three‐component reactions between various substituted aldehydes, malononitrile and 3‐cyano‐6‐hydroxy‐4‐methyl‐pyridin‐2(1H)‐one to afford the corresponding pyrano[2,3‐b]pyridines in high yields under mild and solvent‐free conditions. The catalyst can be easily recycled in a magnetic field and reused in five consecutive runs without significant decrease of its catalytic activity.
Orientational behaviors of silk fibroin hydrogels
Authors: Chen Daqi , Yin Zhuping , Wu Feng , Fu Hua , Kundu Subhas C. , Lu Shenzhou
Published: May 2017

In this study, a novel shear‐induced silk fibroin (SF) hydrogel with three‐dimensional (3D) anisotropic and oriented gel skeleton/network morphology is presented. Amphipathic anionic and nontoxic sodium surfactin is blended with the SF to decrease its gelation time during the mechanical shearing process. The fibroin/surfactin blended solutions undergo a facial shearing process to accomplish a sol–gel transition within 1 hour. The dynamic sol–gel transition kinetic analysis, gel skeleton/network morphology, and mechanical property measurements are determined in order to visualize the fibroin/surfactin sol–gel transition during the shearing process and its resulting hydrogel. The results demonstrate that there is significant β‐sheet assembly from random coil conformations in the fibroin/surfactin blended system during the facile shearing process. The SF β‐sheets further transform into a fibrous large‐scale aggregation with orientational and parallel arrangements to the shearing direction. The shear‐induced fibroin/surfactin hydrogel exhibits notable anisotropic and oriented 3D skeleton/network morphology and a significant mechanical compressive strength in proportion to the shearing stress, compared with the control fibroin/surfactin hydrogel undergoing no shearing process. Due to its oriented gel skeleton/network structure and significantly enhanced mechanical properties, the shear‐induced fibroin/surfactin gel may be suitable as a biomaterial in 3D oriented tissue regeneration, including for nerves, the cultivation of bone cells, and the repair of defects in muscle and ligament tissues. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45050.
Preparation and properties of cotton stalk bark fibers using combined steam explosion and laccase treatment
Authors: Hou Xiuliang , Zhang Li , Wizi Jakpa , Liao Xiangru , Ma Bomou , Yang Yiqi
Published: May 2017

Cotton stalk bark fibers (CSBF) were prepared using combined steam explosion and laccase treatment (explosion–laccase). CSBF have been applied to reinforce thermoplastic composites, but were difficult to be spun into yarns due to their inferior fineness and high stiffness. In order to improve the fineness and flexibility with a green method, explosion–laccase treatment was used to separate bark of cotton stalks. The results indicated that steam explosion at 1.7 MPa for 3 min effectively facilitated laccase penetration into the lignocellulose complex to enhance delignification without negative effects on activity of laccase. Compared with CSBF after explosion, CSBF after explosion–laccase had better fineness (31 dtex), higher aspect ratio (1110), higher tensile strength (2.81 cN/dtex), higher flexibility (321 twist/(m·dtex)), and better thermal stability, which meets the requirement of textile fibers. CSBF had higher water retention (127%) and moisture regain (10.3%) than cotton. Explosion–laccase is an effective and eco‐friendly method of preparing CSBF for textiles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45058.
Ensemble analysis of topical journal ranking in bioinformatics
Authors: Song Min , Kim SuYeon , Lee Keeheon
Published: May 2017

Journal rankings, frequently determined by the journal impact factor or similar indices, are quantitative measures for evaluating a journal's performance in its discipline, which is presently a major research thrust in the bibliometrics field. Recently, text mining was adopted to augment journal ranking‐based evaluation with the content analysis of a discipline taking a time‐variant factor into consideration. However, previous studies focused mainly on a silo analysis of a discipline using either citation‐or content‐oriented approaches, and no attempt was made to analyze topical journal ranking and its change over time in a seamless and integrated manner. To address this issue, we propose a journal‐time‐topic model, an extension of Dirichlet multinomial regression, which we applied to the field of bioinformatics to understand journal contribution to topics in a field and the shift of topic trends. The journal‐time‐topic model allows us to identify which journals are the major leaders in what topics and the manner in which their topical focus. It also helps reveal an interesting distinct pattern in the journal impact factor of high‐ and low‐ranked journals. The study results shed a new light for understanding topic specific journal rankings and shifts in journals' concentration on a subject.
Impact of fluidic agitation on human pluripotent stem cells in stirred suspension culture
Authors: Nampe Daniel , Joshi Ronak , Keller Kevin , zur Nieden Nicole I. , Tsutsui Hideaki
Published: May 2017

The success of human pluripotent stem cells (hPSCs) as a source of future cell therapies hinges, in part, on the availability of a robust and scalable culture system that can readily produce a clinically relevant number of cells and their derivatives. Stirred suspension culture has been identified as one such promising platform due to its ease of use, scalability, and widespread use in the pharmaceutical industry (e.g., CHO cell‐based production of therapeutic proteins) among others. However, culture of undifferentiated hPSCs in stirred suspension is a relatively new development within the past several years, and little is known beyond empirically optimized culture parameters. In particular, detailed characterizations of different agitation rates and their influence on the propagation of hPSCs are often not reported in the literature. In the current study, we systematically investigated various agitation rates to characterize their impact on cell yield, viability, and the maintenance of pluripotency. Additionally, we closely examined the distribution of cell aggregates and how the observed culture outcomes are attributed to their size distribution. Overall, our results showed that moderate agitation maximized the propagation of hPSCs to approximately 38‐fold over 7 days by keeping the cell aggregates below the critical size, beyond which the cells are impacted by the diffusion limit, while limiting cell death caused by excessive fluidic forces. Furthermore, we observed that fluidic agitation could regulate not only cell aggregation, but also expression of some key signaling proteins in hPSCs. This indicates a new possibility to guide stem cell fate determination by fluidic agitation in stirred suspension cultures. Biotechnol. Bioeng. 2017;114: 2109–2120. © 2017 Wiley Periodicals, Inc.
Development and validation of a liquid chromatography tandem mass spectrometry method for the measurement of urinary catecholamines in diagnosis of pheochromocytoma
Authors: Shen Ying , Cheng Liming , Guan Qing , Li Huijun , Lu Jie , Wang Xu
Published: May 2017

The measurement of catecholamines in human body fluids is requested frequently for the differential diagnosis and monitoring of pheochromocytoma. The methods in most clinical laboratories focus on high‐performance liquid chromatography coupled with electrochemical detection, which suffers from high background noise, low sensitivity, and poor separation. We reported and developed a robust high‐throughput liquid chromatography tandem mass spectrometry method in routine clinical laboratories for the measurement of urinary catecholamines for diagnosis of pheochromocytoma. The method was validated for consistent linearity, good recovery (88–112%), excellent stability and low carryover. Intra‐ and inter‐assay precision values for catecholamines were all below 3.35 and 4.83% respectively. Dilution linearity was investigated with satisfactory linearly dependent coefficients (r > 0.9988). The reference intervals were obtained from 310 results derived from patients in which the diagnosis of pheochromocytoma was excluded. This method was successfully used in our laboratory. The clinical characteristics of patients have been explored with satisfactory sensitivity and specificity. Therefore, we have developed a reliable assay for the liquid chromatography tandem mass spectrometry measurement of catecholamines in a routine clinical laboratory. The assay requires a small volume of urine, and all analytes are measured simultaneously. The assay is rapid and reliable to be executed, offering the potential for routine clinical laboratories.
PC‐based control and simulation of an electro‐hydraulic system
Authors: Erzan Topçu Elif
Published: May 2017

This article addresses the development of a control system design methodology to make control courses easier to understand. The methodology can be handled in four stages: Modeling, controller design and tuning of the controller gains, simulation, and experimental studies. A PC‐based control system environment is chosen to help students/researchers understand the control system both theoretically and experimentally. An electro‐hydraulic system is used for training. Such fluid power systems are widely used in the industrial area and combine different engineering system properties. First, a system is defined by a mathematical model and simulated using the MATLAB/Simulink environment. An easy to use toolbox, Simscape/Simhydraulics, is used to facilitate the modeling phase in simulation of the hydraulic system. Next, the design of the feedback controller is proposed. Basic controllers in control education, such as proportional + derivative + integral (PID) and a Fuzzy Logic Controller (FLC), are utilized, and the gains of the controllers are tuned with a simplified method according to the given design criteria. The proposed tuning method can also be useful for overdamped or first‐order systems. Time and frequency responses of the system are obtained and evaluated. The experimental studies are conducted on a hydraulic control system at the Automatic Control Laboratory of the Mechanical Engineering Department of Uludağ University. This work aims to train engineering students/researchers both theoretically and practically regarding PC‐based control system design and fluid power systems.
Acute and midterm results following perventricular device closure of muscular ventricular septal defects: A multicenter PICES investigation
Authors: Gray Robert G. , Menon Shaji C. , Johnson Joyce T. , Armstrong Aimee K. , Bingler Michael A. , Breinholt John P. , Kenny Damien , Lozier John , Murphy Joshua J. , Sathanandam Shyam K. , Taggart Nathaniel W. , Trucco Sara M. , Goldstein Bryan H. , Gordon Brent M.
Published: May 2017

Objectives

To describe acute and mid‐term results of hybrid perventricular device closure of muscular ventricular septal defects (mVSDs).

Background

Perventricular device closure of mVSDs can mitigate technical limitations of percutaneous closure and need for cardiopulmonary bypass or ventriculotomy with a surgical approach.

Methods

This is a multicenter retrospective cohort study of patients undergoing hybrid perventricular mVSD device closure from 1/2004 to 1/2014. Procedural details, adverse events, outcomes, and follow‐up data were collected. Patients were divided into two groups: (1) simple (mVSD closure alone) and (2) complex (mVSD closure with concomitant cardiac surgery).

Results

Forty‐seven patients (60% female) underwent perventricular mVSD device closure at a median age of 5.2 months (IQR 1.8–8.9) and weight of 5.1 kg (IQR 4.0–6.9). Procedural success was 91% [100% (n = 22) simple and 84% (n = 21/25) complex]. Adverse events occurred in 19% (9/47) [9% (2/22) simple and 28% (7/25) complex]. Hospital length of stay (LOS) was shorter in the simple vs. complex group (4 vs. 14 days, P < 0.01). At mid‐term follow‐up of 19.2 months (IQR 2.3–43) 90% of pts had complete mVSD closure; none developed late heart block, increased atrioventricular (AV) valve insufficiency or ventricular dysfunction.

Conclusions

Perventricular device closure of simple mVSD was associated with a high rate of procedural success, few adverse events, and short hospital LOS. Procedural adverse events were associated with the presence of concomitant complex surgery. Residual mVSD, AV valve insufficiency, or ventricular dysfunction were uncommon at mid‐term follow‐up. © 2017 Wiley Periodicals, Inc.
A High‐Throughput Composite Catalyst based on Nickel Carbon Cubes for the Hydrogenation of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran
Authors: Mani Christian Mbaya , Braun Max , Molinari Valerio , Antonietti Markus , Fechler Nina
Published: May 2017

A high‐throughput composite catalyst is prepared from porous carbon with an unconventional nanocube morphology decorated with nickel nanoparticles. Owing to the advantageous properties of the designed carbon support, the composite combines a high surface area and a hierarchical pore structure with high functionality. Furthermore, the regularly shaped nanocubes allow for a good packing of a fixed‐bed flow reactor, in which the internal transport pores cannot be blocked and stay open for efficient column performance. The composite is employed as a catalyst in the hydrogenation of 5‐hydroxymethylfurfural (HMF) to 2,5‐dimethylfuran (DMF), showing good catalytic performance and overcoming the conventional problem of column blocking.
A Novel Experimental Setup for Kinetic Studies of Toluene Oxidation in the Homogeneous Liquid Phase
Authors: Gast Sebastian , Matthies Jörn H. , Tuttlies Ute S. , Nieken Ulrich
Published: May 2017

Accurate measurements of gas‐liquid reactions are difficult and often impossible to obtain owing to the effects of mass transfer, mixing, and a high risk of explosion in cases when oxygen is involved. In this work, a novel reactor concept is introduced that allows the accurate determination of gas‐liquid reaction kinetics in a homogeneous liquid phase without the influence of mass transport or mixing effects. Both effects can be bypassed, and the risk of explosion minimized, through the instant dissolution of gaseous oxygen by using a strongly elevated pressure. This work presents an experimental proof of concept of this system with the example of the oxidation of toluene.
Co‐reactant Electrogenerated Chemiluminescence of Iridium(III) Complexes Containing an Acetylacetonate Ligand
Authors: Chen Lifen , Doeven Egan H. , Wilson David J. D. , Kerr Emily , Hayne David J. , Hogan Conor F. , Yang Wenrong , Pham Tien T. , Francis Paul S.
Published: May 2017

We examine the electrogenerated chemiluminescence (ECL) of three Ir(
)2(acac) complexes, where acac=acetylacetonate anion and
=2‐phenylpyridine (ppy), 2‐phenylbenzothiazole (bt), or 2‐phenylquinoline (pq) anions, with tri‐n‐propylamine co‐reactant in acetonitrile under a range of chemical and instrumental conditions; this follows somewhat conflicting recent claims of the ECL intensities from complexes of this type. Relevant electrochemical, spectroscopic, and ECL properties are evaluated in direct comparison with those of Ir(ppy)3 and [Ru(bpy)3](PF6)2, as well as data from previous publications. DFT calculations on the Ir(
)2(acac) complexes show the HOMOs to be composed of both the metal and the
ligand, and the LUMOs almost exclusively on the
ligand. The ECL intensities of the Ir(
)2(acac) complexes (relative to [Ru(bpy)3](PF6)2) were dependent on experimental conditions and, in some cases, the ECL intensities reported for iridium complexes may have been derived using conditions that unintentionally disadvantaged the reference electrochemiluminophore.
Tandem Tetrahydroisoquinoline‐4‐carboxylic Acid/β‐Alanine as a New Construct Able To Induce a Flexible Turn
Authors: Bucci Raffaella , Bonetti Andrea , Clerici Francesca , Contini Alessandro , Nava Donatella , Pellegrino Sara , Tessaro Davide , Gelmi Maria Luisa
Published: May 2017

Tetrahydroisoquinoline‐4‐carboxylic acid, a constrained β2‐amino acid named β‐TIC, was synthesised for the first time in enantiopure form. The biocatalytic route applied herein represents one of the few successful examples of enzymatic resolution of β2‐amino acids. Model tetrapeptides, namely, Fmoc‐l‐Ala‐β‐TIC‐β‐Ala‐l‐Val‐OBn (Fmoc=fluorenylmethyloxycarbonyl, Bn=benzyl), containing both isomers of β‐TIC, were prepared. Both computational and NMR spectroscopy studies were performed. A reverse‐turn conformation was observed in the case of (R)‐β‐TIC enantiomer that was obtained in 99 % enantiomeric excess by enzymatic resolution. The β‐TIC/β‐Ala construct represents the first example of a flexible turn mimetic containing a cyclic and an acyclic β‐amino acid. Furthermore, the presence of an aromatic ring of β‐TIC could facilitate non‐covalent interactions to increase the potential of this scaffold for the preparation of protein–protein interaction modulators.
Solvent Geometry Regulated Cooperative Supramolecular Polymerization
Authors: Kar Haridas , Ghosh Goutam , Ghosh Suhrit
Published: May 2017

This article discloses hydrogen‐bonding driven supramolecular polymerization of a core‐substituted naphthalene‐diimide derivative NDI‐1, which exhibits J‐aggregation in all tested hydrocarbon solvents; however, spontaneous gelation was noticed only in linear alkanes in contrast to free flowing solution in their cyclic analogs. Mechanistic investigation by variable‐temperature UV/Vis studies and analyzing the data by using an appropriate model(s) elucidates a highly cooperative self‐assembly pathway in linear hydrocarbons (heptane, octane, nonane, or decane) in sharp contrast to cyclohexane or methylcyclohexane in which an ill‐defined polymerization was noticed. This is attributed to the direct participation of linear alkanes in the nucleation process by favorable mixing with the peripheral alkyl chains of the NDI monomer, which appears not to be the case for cyclic alkanes owing to geometry mismatch. Although all tested linear hydrocarbons induced nucleation–elongation growth, the thermodynamic parameters were found to depend on the chain length of the alkane. The morphology of the self‐assembled polymer was strongly dependent on the growth mechanism as we noticed fibrillar networks and short‐length rods, respectively, in decane and methylcyclohexane (MCH). However, in the presence of a small amount of additive (preformed fiber in decane; added in situ or post self‐assembly) a fibrillar structure was noticed also in MCH, corroborating the self‐assembly in solution, which adopted a cooperative mechanism similar to linear alkanes.
Photocatalytic CO2 Reduction by Periodic Mesoporous Organosilica (PMO) Containing Two Different Ruthenium Complexes as Photosensitizing and Catalytic Sites
Authors: Kuramochi Yusuke , Sekine Masato , Kitamura Kyohei , Maegawa Yoshifumi , Goto Yasutomo , Shirai Soichi , Inagaki Shinji , Ishida Hitoshi
Published: May 2017

A periodic mesoporous organosilica (PMO) containing 2,2′‐bipyridine (bpy) ligands within the framework (BPy‐PMO) has great potential for designing novel catalysts by modifying metal complexes. A photosensitizing site (Ru(PS)) was introduced by treating cis‐[Ru(bpy)2(dimethylsulfoxide)Cl]Cl with BPy‐PMO. Then a catalytic site (Ru(Cat)) was brought in Ru(PS)x‐BPy‐PMO by reaction with a ruthenium polymer [Ru(CO)2Cl2]n. The stepwise modification of BPy‐PMO successfully affords a novel photocatalyst Ru(PS)x‐Ru(Cat)y‐BPy‐PMO. The molar fractions (x, y) of Ru(PS) and Ru(Cat) were determined by energy dispersive X‐ray (EDX) measurement and quantification of the amount of CO emitted in the photo‐decarbonylation of Ru(Cat), respectively. Photochemical CO2 reduction (λex>430 nm) by Ru(PS)x‐Ru(Cat)y‐BPy‐PMO in a CO2‐saturated N,N‐dimethylacetamide/water solution containing 1‐benzyl‐1,4‐dihydronicotinamide catalytically produced CO and formate. The total turnover frequency of CO and formate reached more than 162 h−1 on x=0.11 and y=0.0055. The product selectivity (CO/formate) became large when the ratio of Ru(PS)‐to‐Ru(Cat) (x/y) was increased. The photocatalysts can be recycled at least three times without losing their catalytic activity, demonstrating that the Ru(PS) and Ru(Cat) units were strongly immobilized on the BPy‐PMO framework.
Catalytically Active Silicon Oxide Nanoclusters Stabilized in a Metal–Organic Framework
Authors: Rimoldi Martino , Gallington Leighanne C. , Chapman Karena W. , MacRenaris Keith , Hupp Joseph T. , Farha Omar K.
Published: May 2017

Post‐synthetic modification of the zirconium‐based metal–organic framework (MOF) NU‐1000 by atomic layer deposition (ALD), using tetramethoxysilane (Si(OMe)4) as a precursor, led to the incorporation and stabilization of silicon oxide clusters composed of only a few silicon atoms in the framework's pores. The resulting SiOx functionalized material (Si‐NU‐1000) was found to be catalytically active despite the inactivity of related bulk silicon dioxide (SiO2), thus demonstrating the positive effects of having nanosized clusters of SiOx. Moreover, Si‐NU‐1000 showed activity greater than that found for aluminum oxide based catalysts—oxides known for their high acidity—such as an aluminum oxide functionalized MOF (Al‐NU‐1000) and bulk γ‐Al2O3. X‐ray photoelectron spectroscopy and infrared spectroscopy measurements unmasked the electron donating nature of Si‐NU‐1000, explaining the unusual electronic properties of the nanosized SiOx clusters and supporting their high catalytic activity.
Design of functional macromonomer derivatives of poly(isobutylene‐co‐isoprene)
Authors: Rodrigo Antonio C. , Shanmugan Karthik Vikram Siva , Whitney Ralph A. , Parent J. Scott
Published: May 2017

The development of new peroxide‐curable poly(isobutylene‐co‐isoprene) (IIR) elastomers is described, wherein pendant oligomerizable C=C groups are introduced in combination with a range of serviceable functional groups. Ring‐opening of itaconic anhydride with functional alcohols or amines, followed by esterification of the resulting acids with brominated IIR, yield macromonomers that crosslink efficiently under the action of dicumyl peroxide alone. More importantly, the additional graft functionality improves the physical and chemical properties of the resulting thermosets. The introduction of fluorocarbon functionality is shown to lower surface energy and improve the material's extrusion characteristics, and trialkoxysilane functionality is used to improve filler dispersion within silica‐reinforced composites. This strategy is extended to prepare thermosets bearing polymer‐bound phenolic antioxidant. Details of macromonomer production are followed by demonstrations of their utility as engineering materials.
Prognostic impact of diastolic dysfunction in systolic heart failure—A cross‐project analysis from the German Competence Network Heart Failure
Authors: Lüers Claus , Edelmann Frank , Wachter Rolf , Pieske Burkert , Mende Meinhard , Angermann Christiane , Ertl Georg , Düngen Hans‐Dirk , Störk Stefan
Published: May 2017

Background

We investigated the modifying role and prognostic importance of diastolic dysfunction (DD) in patients with heart failure and systolic dysfunction (SD).

Hypothesis

The echocardiographic evaluation of diastolic function in patients with SD provides further prognostic information.

Methods

From the German Competence Network Heart Failure, 1046 heart failure patients with reduced left ventricular ejection fraction (LVEF; <50%) were echocardiographically studied and followed for a median of 5 years. SD was subdivided into nonsevere (LVEF 36%–49%) and severe (LVEF ≤35%); DD was subdivided into nonsevere (E/E′ <15) and severe (E/E′ ≥15).

Results

In general, severe SD was associated with higher hazard ratios (HRs; 2‐fold to 3.5‐fold) for all endpoints (all‐cause death, cardiac death, cardiovascular hospitalization, duration of hospitalization). Patients with severe SD had a 2.5‐fold risk of death (95% confidence interval [CI]: 1.84‐3.47, P < 0.001), and patients with severe DD showed a 1.8‐fold risk (95% CI: 1.17‐2.61, P = 0.004). Furthermore, we observed a strong interaction of SD and DD: concomitant severe DD in patients with moderate SD increased risk substantially (HR: 1.73, 95% CI: 1.16‐2.6, P = 0.007); by contrast, in patients with severe SD, additional presence of severe DD added little or no risk (HR for interaction: 0.5–1.2).

Conclusions

In heart failure patients with reduced LVEF, the evaluation of diastolic function provides additional prognostic information. Although severe SD generally increased the risk for all endpoints, the degree of DD and its impact as a prognostic marker for overall and cardiovascular mortality appeared of particular relevance in subjects with nonsevere SD.
Dysphagia in oropharyngeal squamous cell carcinoma in perspective
Authors: Koch Wayne
Published: May 2017

Swallowing problems occur universally in patients who are treated for oropharyngeal cancer. Transoral robotic surgery contributes to immediate problems, but its impact on long‐term functional outcomes remains uncertain.

See also pages 3132‐40.
On the Finite‐Time Blowup of a One‐Dimensional Model for the Three‐Dimensional Axisymmetric Euler Equations
Authors: Choi Kyudong , Hou Thomas Y. , Kiselev Alexander , Luo Guo , Sverak Vladimir , Yao Yao
Published: May 2017

In connection with the recent proposal for possible singularity formation at the boundary for solutions of three‐dimensional axisymmetric incompressible Euler's equations (Luo and Hou, Proc. Natl. Acad. Sci. USA (2014)), we study models for the dynamics at the boundary and show that they exhibit a finite‐time blowup from smooth data. © 2017 Wiley Periodicals, Inc.
Entropy, Chaos, and Weak Horseshoe for Infinite‐Dimensional Random Dynamical Systems
Authors: Huang Wen , Lu Kening
Published: May 2017

In this paper, we study the complicated dynamics of infinite‐dimensional random dynamical systems that include deterministic dynamical systems as their special cases in a Polish space. Without assuming any hyperbolicity, we prove if a continuous random map has a positive topological entropy, then it contains a topological horseshoe. We also show that the positive topological entropy implies the chaos in the sense of Li‐Yorke. The complicated behavior exhibited here is induced by the positive entropy but not the randomness of the system.© 2017 Wiley Periodicals, Inc.
The development of a change model of “exits” during cognitive analytic therapy for the treatment of depression
Authors: Sandhu Sundeep Kaur , Kellett Stephen , Hardy Gillian
Published: May 2017

Objectives

“Exits” in cognitive analytic therapy (CAT) are methods that change unhelpful patterns or roles during the final “revision” phase of the therapy. How exits are conceived and achieved is currently poorly understood. This study focussed on the revision stage to explore and define how change is accomplished in CAT.

Methods

Qualitative content analysis studied transcripts of sessions 6 and 7 of a protocol delivered 8‐session CAT treatment for depression. Eight participants met the study inclusion criteria, and therefore, 16 sessions were analysed.

Results

The exit model developed contained 3 distinct (but interacting) phases: (a) developing an observing self via therapist input or client self‐reflection, (b) breaking out of old patterns by creating new roles and procedures, and (c) utilisation of a range of methods to support and maintain change. Levels of interrater reliability for the exit categories that formed the model were good.

Conclusions

The revision stage of CAT emerged as a complex and dynamic process involving 3 interacting stages. Further research is recommended to understand how exits relate to durability of change and whether change processes differ according to presenting problem.

Key Practitioner Messages

Exit work in cognitive analytic therapy is a dynamic process that requires progression through stages of insight, active change, and consolidation.

Development of an “observing self” is an important foundation stone for change, and cognitive analytic therapists need to work within the client's zone of proximal development.

A number of aspects appear important in facilitating change, such as attending to the process and feelings generated by change talk.
Targets for Heart Failure With Preserved Ejection Fraction
Authors: Nanayakkara S , Kaye DM
Published: May 2017

Heart failure (HF) with preserved ejection fraction (HFPEF) is responsible for half of all HF cases and will be the most common form of HF within the next 5 years. Previous studies of pharmacological agents in HFPEF have proved neutral or negative, in part due to phenotypic heterogeneity and complex underlying mechanisms. This review summarizes the key molecular and cellular pathways characterized in HFPEF as well as current and future therapies that target these mechanisms.
Determining the Charge‐Transfer Direction in a p–n Heterojunction BiOCl/g‐C3N4 Photocatalyst by Ultrafast Spectroscopy
Authors: Chen Zongwei , Zhang Qun , Luo Yi
Published: May 2017

Type‐II heterostructures composed of p‐type BiOCl and n‐type g‐C3N4 have received much attention because of their high efficiencies of charge separation in photocatalysis. However, some ambiguity exists regarding the transfer direction of photogenerated charge carriers in the BiOCl(p)/g‐C3N4(n) system. Although it seems to have not posed an issue in terms of organic photodegradation applications, misinterpretation of the charge‐transfer direction and hence misjudgment of the redox sites in the hybrid system would be a serious problem for other photocatalytic reactions, especially for half reactions, in which the determination of the redox sites is crucial. To solve this problem, we carefully interrogated this topical heterojunction system formed between p‐type BiOCl and n‐type g‐C3N4 by means of ultrafast transient absorption spectroscopy. Our experimental results reveal that the photogenerated electrons are transferred, on a time scale of a few picoseconds, from the conduction band of BiOCl to that of g‐C3N4 and not in the opposite direction. This work enables us to eliminate the ambiguity in using two opposing mechanistic scenarios to describe the p–n heterojunction based photocatalysis mechanism, thereby providing instructive information for the rational design of photocatalytic nanosystems.