bluuebunny/crossref_metadata_2025_split huggingface dataset:
Angiographic predictors of 2‐year stent thrombosis in patients receiving drug‐eluting stents: Insights from the ADAPT‐DES study
Authors: Généreux Philippe , Redfors Björn , Witzenbichler Bernhard , Maehara Akiko , Yadav Mayank , Weisz Giora , Francese Dominic P. , Parvataneni Rupa , Brener Sorin J. , Mehran Roxana , Kirtane Ajay J. , Stone Gregg W. 
Published: January 2016

ObjectivesWe sought to identify angiographic predictors of 2‐year stent thrombosis (ST) in the ADAPT‐DES study.BackgroundA strong relationship between platelet reactivity and ST after implantation of drug‐eluting stents (DES) was recently confirmed in the prospective, multicenter ADAPT‐DES study.MethodsIn a pre‐specified analysis of patients enrolled in ADAPT‐DES, an independent angiographic core laboratory performed detailed angiographic analyses for all cases of ST. Patients with Academic Research Consortium definite/probable target‐lesion ST were matched with controls in a 1:2 ratio, and multivariable Cox regression models identified angiographic predictors of 2‐year ST.ResultsAmong 8,582 patients who had successful percutaneous coronary intervention (PCI) and were included in the ADAPT‐DES study, 92 (1.1%) patients had ST at 2‐year follow‐up. Target lesion‐related ST was identified in 77 patients (82 lesions) who were clinically matched with 153 patients (196 lesions) without ST. Patients with ST were more likely to have longer target lesions, thrombus, moderate/severe calcification, American College of Cardiology/American Heart Association (ACC/AHA) type C lesions, and saphenous vein grafts. After adjustment for clinical covariates the angiographic variables that predicted ST were lesion complexity (ACC/AHA type C lesion, adjusted HR: 1.97, 95% CI: 1.19 to 3.26, P = 0.01) and presence of thrombus on index PCI (HR: 2.25, 95% CI: 1.40 to 3.59, P < 0.01).ConclusionsAnatomically complex lesions and the presence of thrombus are strong predictors of 2‐year ST in the DES era. © 2016 Wiley Periodicals, Inc.
A New, Simple and Versatile Strategy for the Synthesis of Short Segments of Zigzag‐Type Carbon Nanotubes
Authors: André Etienne , Boutonnet Baptiste , Charles Pauline , Martini Cyril , Aguiar‐Hualde Juan‐Manuel , Latil Sylvain , Guérineau Vincent , Hammad Karim , Ray Priyanka , Guillot Régis , Huc Vincent 
Published: January 2016

AbstractShort segments of zigzag single‐walled carbon nanotubes (SWCNTs) were obtained from a calixarene scaffold by using a completely new, simple and expedited strategy that allowed fine‐tuning of their diameters. This new approach also allows for functionalised short segments of zigzag SWCNTs to be obtained; a prerequisite towards their lengthening. These new SWCNT short segments/calixarene composites show interesting behaviour in solution. DFT analysis of these new compounds also suggests interesting photophysical behaviour. Along with the synthesis of various SWCNTs segments, this approach also constitutes a powerful tool for the construction of new, radially oriented π systems.
Capturing Transient Endoperoxide in the Singlet Oxygen Oxidation of Guanine
Authors: Lu Wenchao , Liu Jianbo 
Published: January 2016

AbstractThe chemistry of singlet O2 toward the guanine base of DNA is highly relevant to DNA lesion, mutation, cell death, and pathological conditions. This oxidative damage is initiated by the formation of a transient endoperoxide through the Diels–Alder cycloaddition of singlet O2 to the guanine imidazole ring. However, no endoperoxide formation was directly detected in native guanine or guanosine, even at −100 °C. Herein, gas‐phase ion–molecule scattering mass spectrometry was utilized to capture unstable endoperoxides in the collisions of hydrated guanine ions (protonated or deprotonated) with singlet O2 at ambient temperature. Corroborated by results from potential energy surface exploration, kinetic modeling, and dynamics simulations, various aspects of endoperoxide formation and transformation (including its dependence on guanine ionization and hydration states, as well as on collision energy) were determined. This work has pieced together reaction mechanisms, kinetics, and dynamics data concerning the early stage of singlet O2 induced guanine oxidation, which is missing from conventional condensed‐phase studies.
Solid‐State NMR and DFT Studies on the Formation of Well‐Defined Silica‐Supported Tantallaaziridines: From Synthesis to Catalytic Application
Authors: Hamzaoui Bilel , Pelletier Jérémie D. A. , Abou‐Hamad Edy , Chen Yin , El Eter Mohamed , Chermak Edrisse , Cavallo Luigi , Basset Jean‐Marie 
Published: January 2016

AbstractSingle‐site, well‐defined, silica‐supported tantallaaziridine intermediates [≡Si‐O‐Ta(η2‐NRCH2)(NMe2)2] [R=Me (2), Ph (3)] were prepared from silica‐supported tetrakis(dimethylamido)tantalum [≡Si‐O‐Ta(NMe2)4] (1) and fully characterized by FTIR spectroscopy, elemental analysis, and 1H,13C HETCOR and DQ TQ solid‐state (SS) NMR spectroscopy. The formation mechanism, by β‐H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C−H activation of the dimethylamide ligand is favored for R=Ph. The results from catalytic testing in the hydroaminoalkylation of alkenes were consistent with the N‐alkyl aryl amine substrates being more efficient than N‐dialkyl amines.
Activity Enhancement of G‐Quadruplex/Hemin DNAzyme by Flanking d(CCC)
Authors: Chang Tianjun , Gong Hongmei , Ding Pi , Liu Xiangjun , Li Weiguo , Bing Tao , Cao Zehui , Shangguan Dihua 
Published: January 2016

AbstractG‐quadruplex (G4)/hemin DNAzymes have been extensively applied in bioanalysis and molecular devices. However, their catalytic activity is still much lower than that of proteinous enzymes. The G4/hemin DNAzyme activity is correlated with the G4 conformations and the solution conditions. However, little is known about the effect of the flanking sequences on the activity, though they are important parts of G4s. Here, we report sequences containing d(CCC), flanked on both ends of the G4‐core sequences remarkably enhance their DNAzyme activity. By using circular dichroism and UV‐visible spectroscopy, the d(CCC) flanking sequences were demonstrated to improve the hemin binding affinity to G4s instead of increasing the parallel G4 formation, which might explain the enhanced DNAzyme activity. Meanwhile, the increased hemin binding ability promoted the degradation of hemin within the DNAzyme by H2O2. Furthermore, the DNAzyme with d(CCC) flanking sequences showed strong tolerance to pH value changes, which makes it more suitable for applications requiring wide pH conditions. The results highlight the influence of the flanking sequences on the DNAzyme activity and provide insightful information for the design of highly active DNAzymes.
Drop forming as a basis for scaling up of the in situ coating process
Authors: Abouzeid Ahmed , Petersen Sandra , Ulrich Joachim 
Published: January 2016

AbstractCutting the costs of tablet manufacture is one of the many advantages melt crystallization offers as a technology for producing pharmaceutical coated tablets, compared to conventional tableting procedure. Other advantages include the lower number of steps needed for production, which increases productivity; the lower energy and workforce requirements; and the decreased need for stricter post‐production quality control measures while maintaining quality. The scientific term for maintaining quality is ensuring the reproducibility of experimental results. The main focus of this study is to scale up the drop‐forming process of coating, in this case of ibuprofen tablets using Lutrol. The main emphasis therefore focuses on transferring the respective optimized conditions that work for the respective system onto the industrial device. This results in the production of tablets with consistent quality in terms of geometry and coat purity. This goes in hand with the extensive modifications applied to the device for the purpose of process scale‐up. The final outcome is represented in a scaled‐up production of the coated pharmaceutical tablets through the process of melt crystallization, the reproducibility of which as a tablet manufacturing method is also proven.
A new model based on coupling of MEP/CFD/ILIA for prediction of primary atomization
Authors: Hosseinalipour Seyed Mostafa , Karimaei Hadiseh 
Published: January 2016

AbstractThe maximum entropy principle (MEP) is one of the first methods which was used to predict droplet size and velocity distributions of sprays. Due to some drawbacks of this model, the predicted results are not well matched with experimental data. This paper presents a different approach to improve the MEP model. It is suggested that improving the available energy source in the MEP model equation be made by numerical solution of the flow inside the injector based on CFD. This will enhance the accuracy of turbulent kinetic energy calculation of sprays. The forces acting on a liquid‐gas interface lead to the growth of disturbances originating inside the injector. In this paper, the instability analysis of wave motion on the surface of a swirling liquid sheet exposed to inner and outer gas streams is presented. However, the linear instability analysis used is different from prior analyses. A cylindrical annular liquid sheet was considered in previous studies, but in this study the instability theory is implemented on a cone‐shaped annular liquid sheet for different cone angles. Applying these procedures enhances the model predictions. The liquid sheet properties found by CFD analysis and the results of improved linear instability analysis (ILIA) are also applied to calculate the momentum source in the MEP model. By coupling these models, the MEP model can be run independently of experimental data. The proposed model was applied to predict the droplet size and velocity distributions of a hollow‐cone spray. The results show close agreement with experimental data.
High‐Efficiency Perovskite Solar Cells Employing a S,N‐Heteropentacene‐based D–A Hole‐Transport Material
Authors: Bi Dongqin , Mishra Amaresh , Gao Peng , Franckevičius Marius , Steck Christopher , Zakeeruddin Shaik Mohammed , Nazeeruddin Mohammad Khaja , Bäuerle Peter , Grätzel Michael , Hagfeldt Anders 
Published: January 2016

AbstractWe developed a new donor–π–acceptor‐type hole‐transport material (HTMs) incorporating S,N‐heteropentacene as π‐spacer, triarylamine as donor, and dicyanovinylene as acceptor. In addition to appropriate frontier molecular orbital energies, the new HTM showed high photo absorptivity in the visible region. Without the use of p‐dopants, solution‐processed mixed perovskite devices using the HTM achieved power conversion efficiencies of up to 16.9% and high photocurrents of up to 22.2 mA cm−2. These results demonstrate that heteroacene can be an excellent building block to prepare alternative HTMs for perovskite solar cells and hold promise for further advancement through fine‐tuning the molecular structure.
Theoretical study and optimisation of a standard deviation estimator circuit for adaptive threshold spike detection
Authors: Rummens François , Ygorra Stéphane , Mayiss Boussamba Hol C. , Renaud Sylvie , Lewis Noëlle 
Published: January 2016

SummaryThis paper presents a theoretical study and the resulting architecture of an analogue‐based standard deviation (SD) estimator, typically used in biomedical spike detectors to assess the noise level of bioelectrical recordings online. This well‐known circuit generated a significant inaccuracy, so the aim was to increase the efficiency of spike detection through proper calculation of the noise SD, by developing a rigorous, original theoretical study. The approach consisted of establishing behavioural models for the SD estimation circuit to obtain a transfer function and compare different controllers. This modelling approach also highlighted the parameters available and the impact of their relationships on design optimisation. The behavioural models, inherently based on approximations, were then initially validated by comparing them with actual circuit behaviour, obtained using discrete components. These comparisons revealed that the models matched the actual circuit measurements. Finally, taking into account the conclusions of our theoretical study, an integrated version of this adaptive threshold spike detector was designed using 0.35‐µm complementary metal–oxide–semiconductor technology. Simulations of this circuit revealed that the proposed controller eliminated the static error and ensured efficient spike detection. Copyright © 2016 John Wiley & Sons, Ltd.
Pitfalls in diagnosing diabetic foot infections
Authors: Peters Edgar J. 
Published: January 2016

AbstractAlthough the diagnosis of a diabetic foot infection is made based on clinical symptoms and signs, we also use blood laboratory, microbiological and radiological studies to make treatment decisions. All of these diagnostic studies have pitfalls that can lead to a delay in diagnosis. Such delays will likely lead to further tissue damage and to a higher chance of amputation.One of these pitfalls is that some clinicians rely on microbiological, rather than clinical data, to diagnose infection. Though subjective by nature, clinical signs predict outcome of foot infections accurately.Another pitfall is that microbiological data can be misleading. All wounds harbour microorganisms; therefore, a positive wound culture does not mean that a wound is infected. Furthermore, the outcome of cultures of wound swabs does not correlate well with culture results of tissue biopsies. Therapy guidance by wound swab will likely lead to overtreatment of non‐pathogenic organisms. Genotyping might have a role in identifying previously unrecognized (combinations of) pathogens in diabetic foot infection, bacteria in sessile phenotype and non‐culturable pathogens, e.g. in cases where antibiotics have already been administered.One more pitfall is that the diagnosis of osteomyelitis remains difficult. Although the result of percutaneous bone biopsy is the reference standard for osteomyelitis, some other diagnostic modalities can aid in the diagnosis. A combination of several of these diagnostic tests is probably a good strategy to achieve a higher diagnostic accuracy. Relying on a single test will likely lead to misidentification of patients with osteomyelitis with associated overtreatment and undertreatment. Copyright © 2016 John Wiley & Sons, Ltd.
Assessment of foot perfusion in patients with a diabetic foot ulcer
Authors: Forsythe Rachael O. , Hinchliffe Robert J. 
Published: January 2016

AbstractAssessment of foot perfusion is a vital step in the management of patients with diabetic foot ulceration, in order to understand the risk of amputation and likelihood of wound healing. Underlying peripheral artery disease is a common finding in patients with foot ulceration and is associated with poor outcomes. Assessment of foot perfusion should therefore focus on identifying the presence of peripheral artery disease and to subsequently estimate the effect this may have on wound healing. Assessment of perfusion can be difficult because of the often complex, diffuse and distal nature of peripheral artery disease in patients with diabetes, as well as poor collateralisation and heavy vascular calcification. Conventional methods of assessing tissue perfusion in the peripheral circulation may be unreliable in patients with diabetes, and it may therefore be difficult to determine the extent to which poor perfusion contributes to foot ulceration. Anatomical data obtained on cross‐sectional imaging is important but must be combined with measurements of tissue perfusion (such as transcutaneous oxygen tension) in order to understand the global and regional perfusion deficit present in a patient with diabetic foot ulceration. Ankle‐brachial pressure index is routinely used to screen for peripheral artery disease, but its use in patients with diabetes is limited in the presence of neuropathy and medial arterial calcification. Toe pressure index may be more useful because of the relative sparing of pedal arteries from medial calcification but may not always be possible in patients with ulceration. Fluorescence angiography is a non‐invasive technique that can provide rapid quantitative information about regional tissue perfusion; capillaroscopy, iontophoresis and hyperspectral imaging may also be useful in assessing physiological perfusion but are not widely available.There may be a future role for specialized perfusion imaging of these patients, including magnetic resonance imaging techniques, single‐photon emission computed tomography and PET‐based molecular imaging; however, these novel techniques require further validation and are unlikely to become standard practice in the near future. Copyright © 2016 John Wiley & Sons, Ltd.
Sedentary behaviour as a new behavioural target in the prevention and treatment of type 2 diabetes
Authors: Henson Joseph , Dunstan David W. , Davies Melanie J. , Yates Thomas 
Published: January 2016

AbstractOur modern day society encompasses an ecological niche in which sedentary behaviour, labour‐saving devices and energy dense foods have become the new reference of living. We now spend more time sedentary, defined as sitting, than in all other activities combined. It has recently been confirmed that the consequences of our modern chair dependency are substantial and a direct contributing factor to the ever increasing epidemic of chronic diseases witnessed within industrialized environments. Epidemiological evidence – from both cross‐sectional and prospective observational studies – has indicated that the time spent in sedentary behaviour is a distinct risk factor for several health outcomes, including type 2 diabetes mellitus, insulin resistance, all‐cause and cardiovascular disease mortality, depression and some types of cancer. Importantly, these detrimental associations remain even after accounting for time spent in moderate‐to‐vigorous physical activity, with the strongest and most persistent associations seen between sedentary time and type 2 diabetes mellitus. Importantly, experimental studies have started to confirm the observational associations, with mounting evidence showing that breaking prolonged sitting time with light ambulation is an effective strategy for improving postprandial glucose regulation. Indeed, there is even emerging evidence showing that simply substituting sitting for standing regularly throughout the day may be of sufficient stimulus to improve glucose regulation. We highlight some of the key definitions, issues and evidence underpinning the link between sedentary behaviour and chronic disease in order to better inform clinicians and patients about the importance of incorporating reduced sitting time into type 2 diabetes mellitus management and prevention pathways. Copyright © 2016 John Wiley & Sons, Ltd.
A new diabetic foot risk assessment tool: DIAFORA
Authors: Monteiro‐Soares M. , Dinis‐Ribeiro M. 
Published: January 2016

AbstractAimsThis study aimed to derive a new model to classify subjects with diabetes and active diabetic foot ulcer by their risk of lower extremity amputation.MethodsA prospective cohort study was conducted that included all subjects with diabetic foot ulcer attending our Hospital Diabetic Foot Clinic from 2010 to 2013. Variables were collected at baseline. Subjects were followed up until healing, lower extremity amputation, death or for at least 3 months. Logistic regression was used to derive the new model, and the area under the receiver operating characteristic curve was assessed to propose the model with the greatest discrimination.ResultsA total of 293 participants were included and followed for a median of 91 days. In 23.2% amputation was required, 5.1% died and 3.1% were lost. Our final model included the variables most commonly used in clinical practice for diabetic foot risk assessment (presence of neuropathy, foot deformity, peripheral arterial disease and previous foot complications) in addition to multiple diabetic foot ulcer, infection, gangrene and bone involvement. This model had an area under the receiver operating characteristic curve of 0.91 [95% confidence interval (CI) 0.87–0.95] and as classification of 0.89 (95% CI 0.84–0.93) for lower extremity amputation prediction. The high‐risk group presented a positive likelihood ratio of 5 (95% CI 3–8) and predictive value of 58 (46–71). Only one minor lower extremity amputation occurred in the low‐risk group.ConclusionsWe propose a new classification: diabetic foot risk assessment (DIAFORA). This classification was equally or more accurate for lower extremity amputation prediction in diabetic foot ulcer patients when compared with the existing ones. Copyright © 2016 John Wiley & Sons, Ltd.
Reactivity of Me‐pma RhI and IrI Complexes upon Deprotonation and Their Application in Catalytic Carbene Carbonylation Reactions
Authors: Tang Zhou , Tejel Cristina , Martinez de Sarasa Buchaca Marc , Lutz Martin , van der Vlugt Jarl Ivar , de Bruin Bas 
Published: January 2016

AbstractDehydrogenative oxidation of amines is a relevant process in metal‐mediated catalysis, with the amines being either substrates or ligands. Transformation of amine‐ into imine‐type ligands in the coordination sphere of a transition metal can be an important catalyst activation process. The behaviour of secondary pyridin‐2‐ylmethanamine (pma) ligands in the corresponding rhodium and iridium complexes upon NH deprotonation varies, depending on a number of factors. In this paper the behaviour of the Me‐pma ligand [Me‐pma = N‐methyl‐1‐(pyridin‐2‐yl)methanamine] bound to [Rh(cod)]+ and [Ir(cod)]+ was studied. Whereas the iridium amido complex could be obtained upon NH deprotonation, the rhodium complex instantaneously disproportionated into a free pma ligand and an unusual dinuclear complex, adopting a structure with two RhI metal centres hosted by a dianionic (pma‐2H)2– ligand, and with the ligand coordinating to Rh2 as an “aza‐allyl” fragment. The study gives further proof for the effect of pyridine ligation on the previously observed charge‐transfer from the ligand to the metal. Furthermore, the catalytic activity of both the Ir and the Rh species with Me‐pma in carbene carbonylation reactions to generate ketenes was studied.
A Convergent Synthesis of Gonytolide C Using an Intramolecular Oxa‐Michael Addition
Authors: Li Freda F. , Atkinson Darcy J. , Furkert Daniel P. , Brimble Margaret A. 
Published: January 2016

AbstractA full account of the evolution of a convergent total synthesis of gonytolide C is reported. The assembly of the natural product core relies on a Horner–Wadsworth–Emmons (HWE) olefination followed by an intramolecular oxa‐Michael addition. Robust and efficient preparations of both HWE coupling partners were established. The synthesis enabled further investigation of an asymmetric oxa‐Michael cyclisation to prepare gonytolide C, demonstrating the utility of this strategy for synthesis of 2,2‐disubstituted chromanones.