bluuebunny/crossref_metadata_2025 huggingface dataset:
Carbamodithioate‐based fluorescent chemosensor for Hg(II): a staged response approach and investigation into the sensing mechanism
Authors: Cheng Xiaohong , Zhong Zhicheng , Ye Tingting , Zhang Bingjie
Published: September 2016

Carbamodithioate‐based compound C1 was designed and synthesized as a new fluorescent probe for Hg2+ ions. Upon the addition of Hg2+ ions, it displayed a rare staged response: the emission spectra of C1 first showed an apparent red‐shift, followed by a dramatic decrease. To investigate the sensing mechanism, control compounds C2 with the same phenanthroimidazole unit and C3 with the same carbamodithioate functionality were synthesized. On comparison, the first step sensing process was ascribed to decreasing photoinduced electron transfer on the coordination of Hg2+ with the lone pair electrons of the nitrogen atom on the phenanthroimidazole ring. The affinity of Hg2+ and the carbamodithioate unit with four sulfur atoms then induced changes in intramolecular charge transfer efficiency and the second step fluorescent response.
Teaching and learning data structure concepts via Visual Kinesthetic Pseudocode with the aid of a constructively aligned app
Authors: Odisho Ogen , Aziz Mark , Giacaman Nasser
Published: September 2016

Data Structures is an integral topic for any Computer Science or Software Engineering degree, identified as a Core Tier‐1 topic of the ACM/IEEE Computer Science Curricula. The underlying concepts are inherently abstract, making them especially difficult to understand for novice programmers. This paper proposes a cognitively challenging technique to help students understand the thought process that the learning outcomes of fundamental data structure units aim to achieve. The development of this thought process is using a technique we term Visual Kinesthetic Pseudocode, with the overarching goal of helping students code without coding, yet providing the necessary scaffold to guide them in implementing the data structures with real code. This was implemented in the form of INTERACTIVEDS, an app for students and teachers to guide the learning of fundamental data structure concepts. The evaluations demonstrate that students strongly credited INTERACTIVEDS in aiding their understanding of concepts and confidence in applying data structure concepts in practice. The study is also a step forward in revealing potential threshold concepts pertaining to data structure modules. © 2016 Wiley Periodicals, Inc. Comput Appl Eng Educ 24:926–933, 2016; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21768
A client focused perspective of the effectiveness of Counselling for Depression (CfD)
Authors: Goldman Stacey , Brettle Alison , McAndrew Sue
Published: September 2016

Background

In the UK, only one in four people with a diagnosis of depression receive any form of treatment. To address this, the Improving Access to Psychological Therapies (IAPT) programme was established with the main therapeutic approach being cognitive behavioural therapy (CBT). This raised concern regarding client choice, prompting the development of a new evidence‐based manualised therapy, namely ‘Counselling for Depression’ [CfD]. To date, the client's view of the effectiveness of CfD has not been researched.

Aims

The aims of this study were twofold: (1) to explore and evaluate CfD from the perspective of the client and (2) to inform the counselling profession of the client's perception of what is occurring within this therapeutic approach.

Methodology

This qualitative study used Interpretative Phenomenological Analysis, the ideographic aspect valuing each individual narrative and the contribution it makes towards a larger account of the phenomenon from a small group of people. Twelve participants receiving CfD completed a Helpful Aspects of Therapy questionnaire after each counselling session, with ten participating in a semi‐structured interview post counselling.

Findings

Four superordinate themes were identified: A helpful process, Client's view of a counsellor, Gains and Negative aspects. Participants perceived this model of therapy as helpful, feeling understood by their counsellors and able to work through issues in a safe therapeutic relationship. Negative findings related to counselling being ‘hard work’ and a dislike of the time limitation that curtailed the work.

Implications

Participants believed this type of counselling met their needs, reassuring practitioners that CfD is helpful to their clients.
The effects of telepsychology format on empathic accuracy and the therapeutic alliance: An analogue counselling session
Authors: Reese Robert J. , Mecham Mary R. , Vasilj Igor , Lengerich Alex J. , Brown Holly M. , Simpson Nicholas B. , Newsome Benjamin D.
Published: September 2016

Objective

The primary purpose of this study was to evaluate whether psychotherapy format (videoconferencing, telephone or in‐person) influenced therapist empathic accuracy and clients’ perceptions of the therapeutic alliance. We also evaluated whether client attitudes towards using telepsychology influenced the therapeutic alliance in the telepsychology formats. A secondary purpose was to determine whether empathic accuracy predicted the therapeutic alliance differently across service delivery formats.

Method

A randomised block design was used to assign volunteer clients (N = 58) to receive one session of psychotherapy in a videoconferencing, telephonic or in‐person format. Clients completed two therapeutic alliance measures and a telepsychology attitudes measure, and both therapists and clients completed an empathic accuracy measure.

Results

There were no statistically significant differences between the conditions on therapist empathic accuracy or therapeutic alliance. Attitudes towards telepsychology and empathic accuracy were both significant predictors of alliance in the telepsychology delivery formats. Interestingly, empathic accuracy did not predict the therapeutic alliance for clients in the in‐person condition.

Conclusions

Although preliminary, the results suggest that the technology‐mediated psychotherapy processes of empathic accuracy and therapeutic alliance seem to be similar to in‐person psychotherapy. Empathic accuracy, however, may be a more salient process for clients who receive services in a telepsychology format. Process‐focused research may highlight important distinctions in technology‐mediated psychological services that inform both practice and policy.
Long‐term outcomes and re‐interventions following balloon aortic valvuloplasty in pediatric patients with congenital aortic stenosis: A single‐center study
Authors: Sullivan Patrick M. , Rubio Agustin E. , Johnston Troy A. , Jones Thomas K.
Published: September 2016

Objectives

To describe long‐term risk of mortality, aortic insufficiency (AI), and re‐intervention following balloon aortic valvuloplasty (BAV) in pediatric patients and to identify risk factors for re‐intervention.

Background

Few studies report long‐term outcomes following BAV in infants and children.

Methods

Kaplan‐Meier estimates and proportional hazards regression were used in a retrospective study of 154 patients undergoing BAV from 1993 to 2013.

Results

Seventy‐six (49%) patients were neonates. Aortic stenosis (AS) gradients were reduced by 38 ± 19 mm Hg. Moderate or severe AI developed acutely in 19 (12%) patients. Estimates of fifteen‐year transplant‐free survival were 85% (95%CI: 73–92%) in neonates, 94% (95%CI: 80–96%) in infants, and 100% in older patients. Neonates had an elevated long‐term risk of AI (P < 0.001) and left heart re‐interventions (P = 0.02). At 15 years, an estimated 32% (95%CI: 15–50%) of neonates and 44% (95%CI: 20–65%) of non‐neonates remained free from re‐intervention; an estimated 45% (95% CI: 26–63%) of neonates and 62% (95% CI: 40–77%) of non‐neonates remained free of aortic valve replacement (AVR). Neonatal age, additional left heart lesions, higher pre‐ and post‐dilation gradients, and acute AI were associated with LVOT re‐interventions. Post‐dilation gradient ≥30 mm Hg and acute AI were associated with AVR. Patients with moderate or severe acute AI but a residual AS gradient <30 mm Hg had a greater risk of AVR compared to patients with a residual AS gradient ≥30 mm Hg but mild or less AI (HR: 2.98 [95% CI: 1.01–8.77]).

Conclusions

While post‐BAV survival is excellent, long‐term risks of AI and re‐intervention are significant. Acute AI is a more strongly associated with AVR than residual AS. © 2016 Wiley Periodicals, Inc.
Prevalence, indications and management of balloon uncrossable chronic total occlusions: Insights from a contemporary multicenter US registry
Authors: Karacsonyi Judit , Karmpaliotis Dimitri , Alaswad Khaldoon , Jaffer Farouc A. , Yeh Robert W. , Patel Mitul , Bahadorani John , Doing Anthony , Ali Ziad A. , Karatasakis Aris , Danek Barbara A. , Rangan Bavana V. , Alame Aya J. , Banerjee Subhash , Brilakis Emmanouil S.
Published: September 2016

Background

Balloon uncrossable lesions can be challenging to treat, requiring specialized techniques and equipment.

Methods

We examined the prevalence, clinical and angiographic characteristics, management and procedural outcomes of balloon uncrossable lesions in a multicenter chronic total occlusion (CTO) percutaneous coronary intervention (PCI) registry.

Results

Between 2012 and 2016, 718 CTO PCIs (in which the occlusion was successfully crossed with a guidewire) were performed in 701 patients at 11 US centers. Mean age was 65.6 ± 10 years and 84% of the patients were men. Balloon uncrossable lesions represented 9% of all CTOs. Balloon uncrossable CTOs had more moderate/severe calcification (82% vs. 52%, P < 0.0001), moderate/severe tortuosity (61% vs. 35% P < 0.0001) and higher J‐CTO score (2.95 ± 1.32 vs. 2.43 ± 1.23, P = 0.005) as compared with the remaining lesions. Technical and procedural success was significantly lower for balloon uncrossable lesions (90.5% vs. 98.3%, P < 0.0001 and 88.9% vs. 96.6% P = 0.004), respectively, but the incidence of major adverse events was similar (1.6% vs. 2.2%, P = 0.751). Balloon uncrossable lesions required longer procedure (208 [interquartile range: 135, 258] vs. 135 [94, 194] min, P < 0.0001) and fluoroscopy (77 [52, 100] vs. 45 min [27, 75], P < 0.0001) time. Techniques used to treat balloon uncrossable lesions included balloon‐assisted microdissection (23%), excimer laser atherectomy (18%), and rotational atherectomy (16%). Excimer laser atherectomy and balloon‐assisted microdissection were associated with the highest technical and procedural success rates.

Conclusions

Balloon uncrossable CTOs are common, are associated with high rates of technical failure, and require specialized techniques for successful treatment. © 2016 Wiley Periodicals, Inc.
Intracardiac versus transesophageal echocardiography for left atrial appendage occlusion with watchman
Authors: Frangieh Antonio H. , Alibegovic Jasmina , Templin Christian , Gaemperli Oliver , Obeid Slayman , Manka Robert , Holy Erik W. , Maier Willibald , Lüscher Thomas F. , Binder Ronald K.
Published: September 2016

Background: Left atrial appendage occlusion (LAAO) is mostly performed by transesophageal echocardiography (TEE) guidance. Intracardiac echocardiography (ICE) may be an alternative imaging modality for LAAO that precludes the need for general anesthesia or sedation.

Methods and Results: All consecutive single center, single operator LAAO candidates were analyzed. Baseline clinical and procedural characteristics and in‐hospital outcomes were compared between patients in whom a Watchman was implanted with ICE vs. TEE guidance. In 76 consecutive patients the Watchman device was deployed under ICE in 32 patients (42%) and under TEE guidance in 44 patients (58%). Baseline characteristics were comparable between groups, except that patients in the TEE group were older (81 [75–85] years vs. 75 [68–80] years, P = 0.007). Total injected contrast media as well as fluoroscopy time were comparable between groups (90 ml [54–140] vs. 85 ml [80–110], P = 0.86 and 7.9 min [6.4–15.5] vs. 9.8 min [7.0–13.2], P = 0.51, for TEE vs. ICE, respectively). However, time from femoral venous puncture to transseptal puncture and to closure was longer in the ICE group (14 min [7.3–20] vs. 6 min [3.3–11], P = 0.007 and 48 min [40–60] vs. 34.5 min [27–44], P = 0.003, respectively). In the TEE group one patient suffered esophageal erosion with bleeding, which was managed conservatively and one non‐LAAO related in‐hospital mortality occurred in an 88‐year‐old patient. Device implantation success rate was 100% in both groups. No device embolization, no significant peri‐device leak, no tamponade, no stroke, and no access site bleeding occurred in any patient. Total hospital stay for stand‐alone LAAO was comparable between groups (2 days [2–2] vs. 2 days [2–3.3], P = 0.17, in ICE vs. TEE, respectively).

Conclusions: ICE guidance for LAAO with the Watchman device is feasible and comparable to TEE and may become the preferred imaging modality for LAAO. © 2016 Wiley Periodicals, Inc.
Influence of experience on procedure steps, safety, and functional results in edge to edge mitral valve repair—a single center study
Authors: Hamm Karsten , Zacher Michael , Hautmann Martina , Gietzen Frank , Halbfass Philipp , Kerber Sebastian , Diegeler Anno , Schieffer Bernhard , Barth Sebastian
Published: September 2016

Objectives: We sought to determine the effects of experience on the Mitraclip® procedure steps as well as procedure safety and functional results.

Background: MR has proven deleterious in heart failure. Mitraclip® therapy evolved an important option in patients with severely reduced left ventricular function (LVEF).

Methods: Between 2011 and 2016, 126 consecutive patients were grouped in three groups and investigated in a prospective observational study. We evaluated the duration of procedural steps, safety endpoints, and functional results.

Results: The median logistic EuroScore was 32% (7–40%). Ninety‐five percent of patients were in NYHA‐stage ≥III and 51% had a LVEF <30%. Groups were homogeneous as to their baseline NYHA status and right heart catheterization data. Echocardiography data are comparable, albeit with a decreasing effective regurgitant orifice area (0.44 ± 0.21 group I vs. 0.34 ± 0.22 group III, P = 0.02). Frailty was less frequent and baseline 6 min walking test results improved from group I to group III. Duration of a first clip placement decreased from 106 ± 50 to 50 ± 21 min (P < 0.001). Total procedure time decreased from 221 ± 70 to 144 ± 68 (P < 0.001). The number of clips implanted increased from 66 to 79 (P = 0.02). MitraClip® implantation was effective in either group but the combined safety endpoint was reached less frequent in group III (P = 0.01). There was no difference in MACCE rate, 30 day‐ or intrahospital‐mortality between groups.

Conclusion: Safety and duration of procedure steps improved substantially with experience. MR reduction was sustained from the beginning without further improvement. Patient selection is a key factor for success. © 2016 Wiley Periodicals, Inc.
The health care experience of patients with cancer during the last year of life: Analysis of the SEER‐CAHPS data set
Authors: Halpern Michael T. , Urato Matthew P. , Kent Erin E.
Published: September 2016

BACKGROUND

Providing high‐quality medical care for individuals with cancer during their last year of life involves a range of challenges. An important component of high‐quality care during this critical period is ensuring optimal patient satisfaction. The objective of the current study was to assess factors influencing health care ratings among individuals with cancer within 1 year before death.

METHODS

The current study used the Surveillance, Epidemiology, and End Results (SEER)‐Consumer Assessment of Healthcare Providers and Systems (CAHPS) data set, a new data resource linking patient‐reported information from the CAHPS Medicare Survey with clinical information from the National Cancer Institute's SEER program. The study included 5102 Medicare beneficiaries diagnosed with cancer who completed CAHPS between 1998 and 2011 within 1 year before their death. Multivariable logistic regression analyses examined associations between patient demographic and insurance characteristics with 9 measures of health care experience.

RESULTS

Patients with higher general or mental health status were significantly more likely to indicate excellent experience with nearly all measures examined. Sex, race/ethnicity, and education also were found to be significant predictors for certain ratings. Greater time before death predicted an increased likelihood of higher ratings for health plan and specialist physician. Clinical characteristics were found to have few significant associations with experience of care. Individuals in fee‐for‐service Medicare plans (vs Medicare Advantage) had a greater likelihood of excellent experience with health plans, getting care quickly, and getting needed care.

CONCLUSIONS

Among patients with cancer within 1 year before death, experience with health plans, physicians, and medical care were found to be associated with sociodemographic, insurance, and clinical characteristics. These findings provide guidance for the development of programs to improve the experience of care among individuals with cancer. Cancer 2017;123:336–344. © 2016 American Cancer Society.
Expression of Cys‐loop receptor subunits and acetylcholine binding protein in the mechanosensory neurons, glial cells, and muscle tissue of the spider Cupiennius salei
Authors: Liu Hongxia , French Andrew S. , Torkkeli Päivi H.
Published: September 2016

The central and peripheral nervous system transcriptomes of the spider Cupiennius salei have 15 Cys‐loop receptor subunits and an acetylcholine‐binding protein (AChBP). Twelve subunits are predicted to form anion channels gated by γ‐aminobutyric acid (GABA), glutamate, histamine, or changes in pH, and three are putative ACh‐gated cation channels. Spiders have a variety of mechanosensilla and proprioceptive organs that are innervated by efferents in their peripherally located parts, and efferents also innervate muscle fibers. We investigated Cys‐loop gene expression in muscle tissue by qPCR and localized this expression in mechanosensilla via in situ hybridization. The cuticular mechanosensory neurons had only CsGABArdl and CspHCl2 subunits, whereas the muscle tissue expressed a wider variety of subunits, especially CsGABAgrd, CsGABAAβ, CsGluCl1 and CspHCl, but very low levels of the CsGABArdl or CsnACh subunits. An nACh non‐α subunit was expressed in a group of unidentified cells in the hypodermis and at low level in the muscle tissue, but the physiological function of this subunit is unknown. The CsnAChα subunit was not expressed in sensory neurons and was expressed at extremely low level in the muscle tissue. None of the probes gave signals in proprioceptive joint receptors, suggesting that efferent innervation to this sense organ employs other receptor types. CsAChBP and a glia‐specific homeodomain CsREPO were both expressed in glial cells that surround sensory neurons and also in muscle tissue, probably around the nerve endings of the neuromuscular junction. These locations have large numbers of synapses, suggesting that AChBP may have a function in modulating synaptic transmission. J. Comp. Neurol. 525:1139–1154, 2017. © 2016 Wiley Periodicals, Inc.
Reversible Electrocatalytic Activity of Carbon‐Supported PtxNi1−x in Hydrogen Reactions
Authors: Dessources Samuel , Morais Claudia , Napporn Têko W. , Kokoh K. Boniface
Published: September 2016

Hydrogen oxidation and evolution reactions (HOR and HER) are studied on PtxNi1−x/C materials synthesized by the bromide anion exchange method. Physicochemical characterization shows that this surfactant‐free method enables the preparation of well‐dispersed and effective catalysts for the processes involved in the anode of H2/O2 fuel cells (HOR) and the cathode of water electrolyzers (HER). The Pt‐based materials are modified with different Ni contents to decrease the amount of costly precious metal in the electrode materials. These modified Pt‐based materials are found to be electroactive for both reactions without additional overpotential. Kinetic parameters such as the Tafel slope, exchange (j0) and kinetic current densities, and the rate‐determining steps of the reaction mechanisms are determined for each Pt–Ni catalyst and compared to those obtained at the Pt/C surface in alkaline medium. The high j0 values that are obtained indicate a probable contribution of the surface structure of the catalysts due to their roughness and the presence of oxygenated Ni species even at low potentials.
Anticancer RuII and RhIII Piano‐Stool Complexes that are Histone Deacetylase Inhibitors
Authors: Cross Jasmine M. , Blower Tim R. , Gallagher Natalie , Gill Jason H. , Rockley Kimberly L. , Walton James W.
Published: September 2016

The first examples of RuII and RhIII piano‐stool complex histone deacetylase (HDAC) inhibitors are presented. The novel complexes have antiproliferative activity against H460 non‐small‐cell lung carcinoma cells that is comparable to the clinically used HDAC inhibitor suberoylanilide hydroxamic acid (SAHA). Strong evidence for HDAC inhibition as a primary mechanism of action is provided. The complexes reported here represent an important step towards the design of highly active and selective HDAC inhibitors.
“Threshold‐crossing”: A Useful Way to Establish the Counterfactual in Clinical Trials?
Authors: Eichler H‐G , Bloechl‐Daum B , Bauer P , Bretz F , Brown J , Hampson LV , Honig P , Krams M , Leufkens H , Lim R , Lumpkin MM , Murphy MJ , Pignatti F , Posch M , Schneeweiss S , Trusheim M , Koenig F
Published: September 2016

A central question in the assessment of benefit/harm of new treatments is: how does the average outcome on the new treatment (the factual) compare to the average outcome had patients received no treatment or a different treatment known to be effective (the counterfactual)? Randomized controlled trials (RCTs) are the standard for comparing the factual with the counterfactual. Recent developments necessitate and enable a new way of determining the counterfactual for some new medicines. For select situations, we propose a new framework for evidence generation, which we call “threshold‐crossing.” This framework leverages the wealth of information that is becoming available from completed RCTs and from real world data sources. Relying on formalized procedures, information gleaned from these data is used to estimate the counterfactual, enabling efficacy assessment of new drugs. We propose future (research) activities to enable “threshold‐crossing” for carefully selected products and indications in which RCTs are not feasible.
Critical Role of pH Evolution of Electrolyte in the Reaction Mechanism for Rechargeable Zinc Batteries
Authors: Lee Boeun , Seo Hyo Ree , Lee Hae Ri , Yoon Chong Seung , Kim Jong Hak , Chung Kyung Yoon , Cho Byung Won , Oh Si Hyoung
Published: September 2016

The reaction mechanism of α‐MnO2 having 2×2 tunnel structure with zinc ions in a zinc rechargeable battery, employing an aqueous zinc sulfate electrolyte, was investigated by in situ monitoring structural changes and water chemistry alterations during the reaction. Contrary to the conventional belief that zinc ions intercalate into the tunnels of α‐MnO2, we reveal that they actually precipitate in the form of layered zinc hydroxide sulfate (Zn4(OH)6(SO4)⋅5 H2O) on the α‐MnO2 surface. This precipitation occurs because unstable trivalent manganese disproportionates and is dissolved in the electrolyte during the discharge process, resulting in a gradual increase in the pH value of the electrolyte. This causes zinc hydroxide sulfate to crystallize from the electrolyte on the electrode surface. During the charge process, the pH value of the electrolyte decreases due to recombination of manganese on the cathode, leading to dissolution of zinc hydroxide sulfate back into the electrolyte. An analogous phenomenon is also observed in todorokite, a manganese dioxide polymorph with 3×3 tunnel structure that is an indication for the critical role of pH changes of the electrolyte in the reaction mechanism of this battery system.
Design of Surface Doping for Mitigating Transition Metal Dissolution in LiNi0.5Mn1.5O4 Nanoparticles
Authors: Lim Jin‐Myoung , Oh Rye‐Gyeong , Kim Duho , Cho Woosuk , Cho Kyeongjae , Cho Maenghyo , Park Min‐Sik
Published: September 2016

In lithium‐ion batteries (LIBs) comprising spinel cathode materials, the dissolution of transition metals (TMs) in the cathodes causes severe cyclic degradation. We investigate the origin and mechanism of surface TM dissolution in high‐voltage spinel oxide (LiNi0.5Mn1.5O4) nanoparticles to find a practical method for its mitigation. Atomic structures of the LiNi0.5Mn1.5O4 surfaces are developed, and the electronic structures are investigated by first‐principles calculations. The results indicate that titanium is a promising dopant for forming a more stable surface structure by reinforcing metal–oxygen bonds in LiNi0.5Mn1.5O4. Experimentally synthesized LiNi0.5Mn1.5O4 with titanium surface doping exhibits improved electrochemical performance by suppressing undesirable TM dissolution during cycles. The theoretical prediction and experimental validation presented here suggest a viable method to suppress TM dissolution in LiNi0.5Mn1.5O4.
Highly Productive and Enantioselective Enzyme Catalysis under Continuous Supported Liquid–Liquid Conditions Using a Hybrid Monolithic Bioreactor
Authors: Sandig Bernhard , Buchmeiser Michael R.
Published: September 2016

Enzyme‐containing ionic liquids (ILs) were immobilized in cellulose‐2.5‐acetate microbeads particles embedded in a porous monolithic polyurethane matrix. This bioreactor was used under continuous liquid‐liquid conditions by dissolving the substrates in a nonpolar organic phase immiscible with the ILs, thereby creating a biphasic system. Lipases (candida antarctica lipase B, CALB, candida rugosa lipase, CRL) were used to catalyze the enantioselective transesterification of racemic (R,S)‐1‐phenylethanol with vinyl butyrate and vinyl acetate, the esterification of (+/‐)‐2‐isopropyl‐5‐methylcyclohexanol with propionic anhydride and the amidation of (R,S)‐1‐phenylethylamine with ethyl methoxyacetate. With this unique setup, very high productivities, that is, turnover numbers (TONs) up to 5.1×106 and space‐time yields (STYs) up to 28 g product L−1 h−1, exceeding the corresponding values for batch‐type reactions by a factor of 3100 and 40, respectively, were achieved while maintaining or even enhancing enantioselectivity compared to batch reactions via kinetic resolution. To our best knowledge, this is the first continuously operated bioreactor using supported liquid‐liquid conditions that shows these features in the synthesis of chiral esters and amides.
Electrochemical Dealloying of PdCu3 Nanoparticles to Achieve Pt‐like Activity for the Hydrogen Evolution Reaction
Authors: Jana Rajkumar , Bhim Anupam , Bothra Pallavi , Pati Swapan K. , Peter Sebastian C.
Published: September 2016

Manipulating the d‐band center of the metal surface and hence optimizing the free energy of hydrogen adsorption (ΔGH) close to the optimal adsorption energy (ΔGH=0) for hydrogen evolution reaction (HER), is an efficient strategy to enhance the activity for HER. Herein, we report a oleylamine‐mediated (acting as the solvent, stabilizer, and reducing agent) strategy to synthesize intermetallic PdCu3 nanoparticles (NPs) without using any external reducing agent. Upon electrochemical cycling, PdCu3 transforms into Pd‐rich PdCu (ΔGH=0.05 eV), exhibiting remarkably enhanced activity (with a current density of 25 mA cm−2 at ∼69 mV overpotential) as an alternative to Pt for HER. The first‐principle calculation suggests that formation of low coordination number Pd active sites alters the d‐band center and hence optimal adsorption of hydrogen, leading to enhanced activity. This finding may provide guidelines towards the design and development of Pt‐free highly active and robust electrocatalysts.
A unified approach of simultaneous state estimation and anomalous node detection in distributed wireless sensor networks
Authors: Chatterjee Aditi , Venkateswaran Palaniandavar , Mukherjee Debaprasad
Published: September 2016

Detection of anomalous node in distributed wireless sensor networks is extremely important for powerful inference and network reliability. In this paper, we propose a powerful linear statistical model for estimating the state values of the sensor nodes longitudinally, and the estimated state values are used for detecting the anomalous nodes. Our proposed approach is powerful because it considers the effect of the nearest neighbors on the current state values and then detects the anomalous nodes based on the estimated state values. Our method can estimate the missing state values of the sensor nodes, which are kept in sleep mode for energy conservation. We also propose an alternative Bayesian model that is computationally faster for state estimation and anomaly detection. The effectiveness of the proposed model is investigated through extensive simulation studies, and the usefulness of our algorithm is numerically assessed. The performance of the proposed approach is compared to that of the traditional approaches through simulation studies. The proposed model can be effectively used in security surveillance, pattern recognition, habitat monitoring, etc.
Enhancing the Cytotoxic Activity of Anticancer PtIV Complexes by Introduction of Lonidamine as an Axial Ligand
Authors: Nosova Yulia N. , Foteeva Lidia S. , Zenin Ilia V. , Fetisov Timur I. , Kirsanov Kirill I. , Yakubovskaya Marianna G. , Antonenko Taisya A. , Tafeenko Viktor A. , Aslanov Leonid A. , Lobas Anna A. , Gorshkov Mikhail V. , Galanski Mathea Sophia , Keppler Bernhard K. , Timerbaev Andrei R. , Milaeva Elena R. , Nazarov Alexey A.
Published: September 2016

The synthesis and in vitro cytotoxicity of a series of PtIV complexes with lonidamine as a ligand coordinated in axial position are described. Lonidamine was found to affect strongly the in vitro cytotoxic activity of these new complexes, lowering the IC50 values down to the nanomolar range. Lipophilicity assessed in terms of log P showed no direct correlation with cytotoxicity.
Host–Guest and Electrostatic Interactions in Supramolecular Nanoparticle Clusters
Authors: Graña‐Suárez Laura , Verboom Willem , Egberink Richard J. M. , Sarkar Shyam , Mahalingam Venkataramanan , Huskens Jurriaan
Published: September 2016

The influence of the charge, structure, and host–guest interactions of different soft polymeric components on their assembly with negatively charged inorganic gold and up‐converting nanoparticles (NPs) functionalized with cyclodextrins (CD‐AuNPs and CD‐UCNPs) was studied. The inter‐/intramolecular interplay was evaluated by changing the morphology and the charge of the polymeric component. Use of a linear, anionic guest‐functionalized polymer resulted in the formation of thin coating layers around the CD‐AuNPs and CD‐UCNPs without further NP aggregation. When the branched cationic polymer poly(ethylene imine) (PEI) was used instead, small clusters were obtained before the electrostatic neutralization point, whereas large NP aggregates were obtained above the neutralization point. When branched cationic guest‐functionalized dendrimers were used, clusters were obtained at a 1:1 host/guest stoichiometry. In this case, self‐assembly occurred when still far away from the neutrality point, indicating that this cluster formation is driven by supramolecular host–guest interactions. The luminescence of the CD‐UCNPs with the linear polymer was quenched due to C–H vibrational modes of the guest polymer, whereas in the case of electrostatic cluster formation by PEI the luminescence of CD‐UCNPs was enhanced after the neutralization point, due to the formation of densely packed NP assemblies. These findings should be useful for the design of hybrid polymeric–inorganic assemblies for sensing and biomedical applications.
No evidence of potentiation of buprenorphine by milnacipran in healthy subjects using a nociceptive test battery
Authors: Okkerse P. , Alvarez‐Jimenez R. , Hay J.L. , Tehim A. , Kumar R. , de Kam M.L. , Groeneveld G.J.
Published: September 2016

Background

Serotonin–norepinephrine reuptake inhibitors inhibit the reuptake of serotonin and noradrenalin and are used in the treatment of neuropathic pain. Animal studies suggest that milnacipran co‐administered with opioids may potentiate the analgesic effect of μ‐opioid receptor agonists. This study hypothesized that co‐administration of milnacipran and buprenorphine would have a synergistic effect in evoked pain models in healthy subjects.

Methods

This was a randomized double‐blinded, placebo‐controlled, four‐way cross‐over, multiple dose clinical trial to investigate the analgesic effects of buprenorphine (placebo, 0.5, 1 and 3 μg/kg) in combination with milnacipran (placebo, 25 and 50 mg) in healthy subjects.

Results

11 healthy men were enrolled in the study. Buprenorphine alone showed a dose–response relationship indicative of anti‐nociception in the pain tests. Following milnacipran administration, no changes were seen in the pharmacodynamic measurements for pain, psychomotor function, body stability or eye movements. For the electrical tests, cold pressor test and pressure pain test, buprenorphine alone was superior when compared with buprenorphine plus milnacipran. No differences in pharmacodynamic variables, besides an increase in pupil/iris ratio, were observed after repeated administration of milnacipran 50 mg. Single and multiple doses of 25 or 50 mg milnacipran did not further potentiate the anti‐nociceptive effects of buprenorphine.

Conclusions

Buprenorphine showed dose‐dependent effects consistent with its pharmacological profile. Milnacipran alone did not affect any of the pain variables. The combination of both buprenorphine and milnacipran did not potentiate or show a synergistic effect on the pain models used in this study.

Significance

Buprenorphine is known to be a potent opioid agonist. Animal studies suggest that milnacipran co‐administered with opioids may potentiate the analgesic effect of μ‐opioid receptor agonists. Here, we found that buprenorphine showed a dose‐dependent analgesic effect, but that no potentiation or synergy on a battery of evoked pain tasks could be observed after co‐administration of both milnacipran and buprenorphine.
Differential Pulse Anodic Stripping Voltammetric Determination of Lead (II) Using Poly Xylenol Orange Modified Electrode
Authors: Manikandan Ramalingam , Sriman Narayanan Sangilimuthu
Published: September 2016

In this work a method for sensitive anodic stripping voltammetric determination of Pb(II) ions using a poly xylenol orange film modified electrode (PXOFME) has been proposed. Poly xylenol orange film (PXOF) was formed on a paraffin impegrenated graphite electrode (PIGE) using electro polymerization method by scanning the potential between −0.5 V to 1.3 V, at a scan rate of 50 mV/s for 30 segments in 0.1 M phosphate buffer solution (PBS) of pH 7. The PXOFME was characterized by scanning electron microscopy (SEM), ATR‐IR spectroscopy, cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). The modified electrode has been used to develop a sensitive method for the determination of Pb(II) ions by anodic stripping voltmmetry (ASV). The PXOFME was used to preconcentrate Pb(II) ions through complexation, the complexed metal ions were reduced electrochemically and then stripped anodically from the surface of the electrode. A linear range of 5 μg/L to 413 μg/L with a limit of detection (S/N=3) of 1.6 μg/L was observed for the determination of Pb(II) ions. The method was applied to lead determination in sea water and tap water samples and the results were found to be satisfactory.
A green alternative method for analysis of ivermectin and moxidectin in environmental water samples using automatized preconcentration previous MEEKC
Authors: Felici Emiliano , Casado Cristian , Wang Chien C. , Raba Julio , Gomez María R.
Published: September 2016

Antiparasitic drugs derived from macrocyclic lactones (MLs) are widely used in livestock activities around the world. An increasing concern for local authorities is the environmental pollution as a consequence of veterinary drugs widely used in rural areas. The purpose of environmental analysis is to monitor low levels of pollutant analytes in a large number of samples. Also, due to the lipophilic characteristic of these lactones, long‐chain solvents are usually required for performing sample treatment before and during the analysis. Therefore, sensitive, specific, robust, and environmentally friendly analytical methods are still required. In this paper, a new automatized preconcentration methodology followed by microemulsion electrokinetic chromatography analysis was developed for the simultaneous separation and determination of the most used MLs, ivermectin (IVM) and moxidectin (MXD) in environmental water. XAD‐4 resin was employed as an adsorbent for the preconcentration process and ethanol was used as the eluent. In contrast to traditional analysis for IVM and MXD, in this methodology nonpolluting solvents were involved during the whole process and therefore, it could be considered as a contribution to green analytical chemistry. Under optimal experimental conditions, LOD obtained for IVM and MXD were of 3 × 10−3 and 3.6 × 10−3 μg/L, respectively.
Why and where you should recruit international students
Authors: Dennis Marguerite J.
Published: September 2016

No one knows for certain the impact of the British referendum to leave the European Union on higher education, but what is certain is that there will be changes in how and where international students are recruited and where they will enroll.
Waffle production: influence of batter ingredients on sticking of waffles at baking plates—Part II: effect of fat, leavening agent, and water
Authors: Huber Regina , Schoenlechner Regine
Published: September 2016

Fresh egg waffles are continuously baked in tunnel baking ovens in industrial scale. Waffles that partly or fully stick to the baking plates cause significant product loss and increased costs. The aim of this study was, therefore, to investigate the effect of different recipe ingredients on the sticking behavior of waffles. In this second part, ingredients investigated were different leavening agents (sodium acid pyrophosphate, ammonium bicarbonate, magnesium hydroxide carbonate, or monocalcium phosphate), different fat sources (rapeseed oil, cocos fat, butter, or margarine), and different water sources (tap water 12°dH and distilled water). Within the different types of fats, solid fats with high amount of short‐chain fatty acids (cocos fat or butter) decreased the number of sticking waffles compared to liquid oils (rapeseed oil). Regarding leavening agents, magnesium hydroxide carbonate and ammonium bicarbonate were superior to sodium acid pyrophosphate or monocalcium phosphate. Between the two water sources, effects were small.
Clean Energy Standards Show Promise but Need Substantial Backup
Authors: DeCotis Paul A.
Published: September 2016

Clean energy standards (CESs) are taking hold in many states—yet without significant investment in pipes and wires and conventional electricity generation, these standards risk never being met.
(Mis)understanding Science: The Problem with Scientific Breakthroughs
Authors: Evans James P.
Published: September 2016

On Saturday morning, February 28, 1953, the mystery of heredity appeared secure. Humans hadn't the faintest idea of how genetic information was transmitted—how the uncanny resemblance between mother and daughter, grandfather and grandson was conveyed across generations. Yet, by that Saturday afternoon, two individuals, James Watson and Francis Crick, had glimpsed the solution to these mysteries. The story of Watson and Crick's great triumph has been told and retold and has rightly entered the pantheon of scientific legend. But Watson and Crick's breakthrough was just that: a rupture and dramatic discontinuity in human knowledge that solved a deep mystery, the likes of which occurs, perhaps, a couple of times each century. And that's the problem. The story is just so good and so irresistible that it has misled generations of scientists about what to expect regarding a life in science. And more damaging, the resulting breakthrough mentality misleads the public, the media, and society's decision‐makers about how science really works, all to the detriment of scientific progress and our society's well‐being.
The Challenge of Defining Success in Bioethics’ Humanist Wing
Authors: Lauritzen Paul
Published: September 2016

In “Reason and the Republic of Opinion,” Leon Wieseltier bemoaned an age that reduces reason to utilitarian calculation and requires almost ritual genuflection before the altar of numbers. The spirit of this age is at work in the field of bioethics where, as Debra Mathews and colleagues point out in “A Conceptual Model for the Translation of Bioethics Research and Scholarship,” researchers and scholars are increasingly “being asked to demonstrate and also forecast the value and impact of their work.” Despite the reductionism that typically accompanies the movements imbued with this spirit, the concern for accountability that stands behind the call for measuring success is legitimate. The bioethics community is thus fortunate to have such a distinguished group of scholars wrestling with these matters. Indeed, the effort of Mathews et al. to articulate a framework for determining success in bioethics research and scholarship is especially admirable precisely because they resist the temptation to reduce success to quantitative measures alone. That said, it is also important to say that it is nearly impossible to engage with the task these scholars have set for themselves and not succumb to a kind of data fetishism. It is well and good to talk about the complexity of bioethics as a field, but the language of “metrics,” “outputs,” “feedback loops,” “stakeholders,” and the like is not the language of the disciplines of history, literature, philosophy, or religious studies—all fields that Mathews et al. rightly credit with making important contributions to bioethics research and scholarship.
Methodology and Myopia? Some Praise, a Problem, and a Plea
Authors: Ives Jonathan
Published: September 2016

In “A Conceptual Model for the Translation of Bioethics Research and Scholarship,” Debra Mathews et al. aim to “begin an important discussion” about how to measure success in bioethics, and in doing so they set out a typology of bioethics research and scholarship with the arguably correct assumption that we cannot evaluate success in bioethics without first understanding what its goals are. I think the authors are correct in their claim that, in the current academic climate, having work in bioethics deemed a success is likely to hinge, in some way, on its being translated into practice and having impact. I want, however, to add a critical voice in the form of three considerations that I feel ought to be attended to before the work progresses further, the first being that the typology Mathews et al. propose is highly problematic. Although there is a burgeoning literature on “empirical bioethics” methodologies that blend empirical and conceptual work, the typology appears to ignore this.
Fostering Nurses’ Moral Agency and Moral Identity: The Importance of Moral Community
Authors: Liaschenko Joan , Peter Elizabeth
Published: September 2016

It may be the case that the most challenging moral problem of the twenty‐first century will be the relationship between the individual moral agent and the practices and institutions in which the moral agent is embedded. In this paper, we continue the efforts that one of us, Joan Liaschenko, first called for in 1993, that of using feminist ethics as a lens for viewing the relationship between individual nurses as moral agents and the highly complex institutions in which they do the work of nursing. Feminist ethics, with its emphasis on the inextricable relationship between ethics and politics, provides a useful lens to understand the work of nurses in context. Using Margaret Urban Walker's and Hilde Lindemann's concepts of identity, relationships, values, and moral agency, we argue that health care institutions can be moral communities and profoundly affect the work and identity and, therefore, the moral agency of all who work within those structures, including nurses. Nurses are not only shaped by these organizations but also have the power to shape them. Because moral agency is intimately connected to one's identity, moral identity work is essential for nurses to exercise their moral agency and to foster moral community in health care organizations. We first provide a brief history of nursing's morally problematic relationship with institutions and examine the impact institutional master narratives and corporatism exert today on nurses’ moral identities and agency. We close by emphasizing the significance of ongoing dialogue in creating and sustaining moral communities, repairing moral identities, and strengthening moral agency.
Institutional Ethics Resources: Creating Moral Spaces
Authors: Hamric Ann B. , Wocial Lucia D.
Published: September 2016

Since 1992, institutions accredited by The Joint Commission have been required to have a process in place that allows staff members, patients, and families to address ethical issues or issues prone to conflict. While the commission's expectations clearly have made ethics committees more common, simply having a committee in no way demonstrates its effectiveness in terms of the availability of the service to key constituents, the quality of the processes used, or the outcomes achieved. Beyond meeting baseline accreditation standards, effective ethics resources are requisite for quality care for another reason. The provision of care to the sick is a practice with profound moral dimensions. Clinicians need what Margaret Urban Walker has called “moral spaces,” reflective spaces within institutions in which to explore and communicate values and ethical obligations as they undergird goals of care. Walker proposed that ethicists needed to be concerned with the design and maintenance of these moral spaces. Clearly, that concern needs to extend beyond ethicists to institutional leaders. This essay uses Walker's idea of moral space to describe individuals and groups who are actual and potential ethics resources in health care institutions. We focus on four requisite characteristics of effective resources and the challenges to achieving them, and we identify strategies to build them. In our view, such moral spaces are particularly important for nurses and their colleagues on interprofessional teams and need to be expanded and strengthened in most settings.
From the Team to the Table: Nursing Societies and Health Care Organizational Ethics
Authors: Wiencek Clareen , Lavandero Ramón , Berlinger Nancy
Published: September 2016

Health care work is interprofessional work. Nurses and physicians, members of the professions whose close collaboration is foundational to health care delivery, continue to be educated separately in most academic institutions. Their work also is organized in ways that challenge interprofessional collaboration. Understanding workplace realities faced by nurses and physicians, separately and jointly, is a starting place for exploring how to support ethically sound interprofessional work. In this essay, we look most closely at the work of nurses and physicians who care for seriously ill hospitalized patients, a patient population closely associated with ethical challenges.