bluuebunny/crossref_metadata_2025_split huggingface dataset:
Evolution of Density Parameters on a Smooth Embedded Universe
Authors: Capistrano Abraão J.S. 
Published: October 2017

AbstractIn this paper we examine the evolution of cosmic density parameters in a four‐dimensional space‐time embedded in a five‐dimensional bulk space. We show that the extrinsic curvature is an independent spin‐2 field governed by the Gupta equations. Without evoking a dark energy fluid, the corresponding cosmological model is compared with the phenomenological XCDM model and shows a good concordance with recent cosmological datasets from Planck Collaboration and the latest Baryons Acoustic Oscillations/Cosmic Microwave Background (BAO/CMBR) + SNIa studying the evolution of density parameters. In addition, a discussion on the coincidence problem is also proposed.
Lysosome‐Targeting Amplifiers of Reactive Oxygen Species as Anticancer Prodrugs
Authors: Daum Steffen , Reshetnikov M. S. Viktor , Sisa Miroslav , Dumych Tetyana , Lootsik Maxim D. , Bilyy Rostyslav , Bila Evgenia , Janko Christina , Alexiou Christoph , Herrmann Martin , Sellner Leopold , Mokhir Andriy 
Published: October 2017

AbstractCancer cells produce elevated levels of reactive oxygen species, which has been used to design cancer specific prodrugs. Their activation relies on at least a bimolecular process, in which a prodrug reacts with ROS. However, at low micromolar concentrations of the prodrugs and ROS, the activation is usually inefficient. Herein, we propose and validate a potentially general approach for solving this intrinsic problem of ROS‐dependent prodrugs. In particular, known prodrug 4‐(N‐ferrocenyl‐N‐benzylaminocarbonyloxymethyl)phenylboronic acid pinacol ester was converted into its lysosome‐specific analogue. Since lysosomes contain a higher concentration of active ROS than the cytoplasm, activation of the prodrug was facilitated with respect to the parent compound. Moreover, it was found to exhibit high anticancer activity in a variety of cancer cell lines (IC50=3.5–7.2 μm) and in vivo (40 mg kg−1, NK/Ly murine model) but remained weakly toxic towards non‐malignant cells (IC50=15–30 μm).
Zweidimensionale Chemie jenseits von Graphen: das aufstrebende Gebiet der Funktionalisierung von Molybdändisulfid und schwarzem Phosphor
Authors: Hirsch Andreas , Hauke Frank 
Published: October 2017

AbstractDer aktuelle Wissensstand über die chemische Funktionalisierung dreier 2D‐Materialien – Graphen, Molybdändisulfid und schwarzer Phosphor – wird zusammengefasst. Diese 2D‐Polymere repräsentieren derzeit ein aufstrebendes Forschungsgebiet an der Schnittstelle zwischen Synthesechemie, Physik und Materialwissenschaften. Die kovalente und die nicht‐kovalente Funktionalisierung von Schichtstrukturen ermöglichen eine systematische Modifizierung ihrer Eigenschaften, z. B. die Verbesserung der Löslichkeit und Prozessierbarkeit, die Vermeidung von Reaggregation oder eine Änderung der Bandlücke. Außer erfolgreichen Funktionalisierungskonzepten werden auch grundlegende Schwierigkeiten angesprochen. Dazu zählen die Unlöslichkeit und Polydispersität der meisten 2D‐Schichtsysteme, die Identifizierung effektiver Strategien zur Bildung einer chemischen Bindung und die Regioselektivität von Additionsreaktionen in einer Basalebene. Im vorliegenden Aufsatz werden die wichtigsten und vielversprechendsten Konzepte zur Bewältigung dieser Probleme vorgestellt.
General and Efficient Intermolecular [2+2] Photodimerization of Chalcones and Cinnamic Acid Derivatives in Solution through Visible‐Light Catalysis
Authors: Lei Tao , Zhou Chao , Huang Mao‐Yong , Zhao Lei‐Min , Yang Bing , Ye Chen , Xiao Hongyan , Meng Qing‐Yuan , Ramamurthy Vaidhyanathan , Tung Chen‐Ho , Wu Li‐Zhu 
Published: October 2017

Abstract[2+2] Photocycloaddition, for example, the dimerization of chalcones and cinnamic acid derivatives, is a unique strategy to construct cyclobutanes, which are building blocks for a variety of biologically active molecules and natural products. However, most attempts at the above [2+2] addition have focused on solid‐state, molten‐state, or host–guest systems under ultraviolet‐light irradiation in order to overcome the competition of facile geometric isomerization of nonrigid olefins. We report a general and simple method to realize the intermolecular [2+2] dimerization reaction of these acyclic olefins to construct cyclobutanes in a highly regio‐ and diastereoselective manner in solution under visible light, which provides an efficient solution to a long‐standing problem.
Characterization of the Conjugation Pattern in Large Polysaccharide–Protein Conjugates by NMR Spectroscopy
Authors: Giuntini Stefano , Balducci Evita , Cerofolini Linda , Ravera Enrico , Fragai Marco , Berti Francesco , Luchinat Claudio 
Published: October 2017

AbstractCarbohydrate‐based vaccines are among the safest and most effective vaccines and represent potent tools for prevention of life‐threatening bacterial infectious diseases, like meningitis and pneumonia. The chemical conjugation of a weak antigen to protein as a source of T‐cell epitopes generates a glycoconjugate vaccine that results more immunogenic. Several methods have been used so far to characterize the resulting polysaccharide–protein conjugates. However, a reduced number of methodologies has been proposed for measuring the degree of saccharide conjugation at the possible protein sites. Here we show that detailed information on large proteins conjugated with large polysaccharides can be achieved by a combination of solution and solid‐state NMR spectroscopy. As a test case, a large protein assembly, l‐asparaginase II, has been conjugated with Neisseria meningitidis serogroup C capsular polysaccharide and the pattern and degree of conjugation were determined.
A Three‐Dimensionally π‐Conjugated Diradical Molecular Cage
Authors: Gu Xiao , Gopalakrishna Tullimilli Y. , Phan Hoa , Ni Yong , Herng Tun Seng , Ding Jun , Wu Jishan 
Published: October 2017

Abstractπ‐Conjugated molecular cages are very challenging targets in structural organic chemistry, supramolecular chemistry, and materials science. The synthesis and physical characterizations are reported of the first three‐dimensionally π‐conjugated diradical molecular cage PTM‐C, in which two polychlorotriphenylmethyl (PTM) radicals are linked by three bis(3,6‐carbazolyl) bridges. This cage compound was synthesized mainly by intermolecular Yamamoto coupling followed by deprotonation and oxidation. It is stable and its structure was confirmed by X‐ray crystallographic analysis. The two carbon‐centered PTM radicals are weakly coupled through electronic interactions with the carbazole spacers, as revealed by optical, electronic, and magnetic measurements as well as theoretical calculations.
Post‐Graphene 2D Chemistry: The Emerging Field of Molybdenum Disulfide and Black Phosphorus Functionalization
Authors: Hirsch Andreas , Hauke Frank 
Published: October 2017

AbstractThe current state of the chemical functionalization of three types of single sheet 2D materials, namely, graphene, molybdenum disulfide (MoS2), and black phosphorus (BP) is summarized. Such 2D sheet polymers are currently an emerging field at the interface of synthetic chemistry, physics, and materials science. Both covalent and non‐covalent functionalization of sheet architectures allows a systematic modification of their properties, that is, an improvement of solubility and processability, the prevention of re‐aggregation, or band‐gap tuning. Next to successful functionalization concepts, fundamental challenges are also addressed. These include the insolubility and polydispersity of most 2D sheet polymers, the development of suitable characterization tools, the identification of effective binding strategies, the chemical activation of the usually rather unreactive basal planes for covalent addend binding, and the regioselectivity of plane addition reactions. Although a number of these questions remain elusive in this Review, the first promising concepts to overcome such hurdles are presented.
Selective Activation of C−H Bonds in a Cascade Process Combining Photochemistry and Biocatalysis
Authors: Zhang Wuyuan , Burek Bastien O. , Fernández‐Fueyo Elena , Alcalde Miguel , Bloh Jonathan Z. , Hollmann Frank 
Published: October 2017

AbstractSelective oxyfunctionalizations of inert C−H bonds can be achieved under mild conditions by using peroxygenases. This approach, however, suffers from the poor robustness of these enzymes in the presence of hydrogen peroxide as the stoichiometric oxidant. Herein, we demonstrate that inorganic photocatalysts such as gold–titanium dioxide efficiently provide H2O2 through the methanol‐driven reductive activation of ambient oxygen in amounts that ensure that the enzyme remains highly active and stable. Using this approach, the stereoselective hydroxylation of ethylbenzene to (R)‐1‐phenylethanol was achieved with high enantioselectivity (>98 % ee) and excellent turnover numbers for the biocatalyst (>71 000).
Partite hallux sesamoid bones: Relationship with sesamoid bones at other metatarsophalangeal joints
Authors: Sun Tao , Zhao Haitao , Wang Lingxiang , Wu Wenjuan 
Published: October 2017

ABSTRACTPartite hallux sesamoids are clinically meaningful but their association with other sesamoids is not clear. The objective was to relate the prevalence of the partite hallux sesamoid bones to sesamoid bones at other metatarsophalangeal (MTP) joints. We conducted a retrospective review of plain radiographs of 7946 adult feet between November 2005 and September 2012 to identify partite hallux sesamoids and sesamoids at other MTP joints. Coexistence patterns of the partition and extra sesamoids were studied. Presence or absence of sesamoids at other MTP joints as well as sex and laterality were compared between the feet with and without partite hallux sesamoids using Pearson Chi‐square test. Association between age and partition was evaluated using Spearman's correlation coefficient. Overall partite prevalence rate is 6.82%, and coexistence with extra MTP sesamoids was 0.42%. One pattern was partition in hallux sesamoid only, and 4 patterns were coexistence with extra sesamoids. The prevalence rates of partite hallux sesamoids were 7.17% (508/7081) and 3.93% (34/865) in feet without and with extra sesamoids, respectively. The relative risk of 1.889 (95% CI, 1.325–2.693) of partite hallux sesamoids was noted in feet without than with extra sesamoids (Χ2 = 12.759, P < 0.001). A negative correlation between age and distribution of partition was identified (r = −0.061, P < 0.001). Partition of hallux sesamoid bones is a developmental variation, it can coexist with sesamoids at other MTP joints following a certain pattern; and its prevalence rate is almost twice higher in feet without than with extra MTP sesamoids. Anat Rec, 2017. © 2017 Wiley Periodicals, Inc. Anat Rec, 301:34–38, 2018. © 2017 Wiley Periodicals, Inc.
The Relationship Between Linear Osteological and Radiographic Measurements of the Human Calcaneus and Talus
Authors: Agoada David 
Published: October 2017

ABSTRACTPlain radiographs of the foot are a common form of examination in individuals when medical evaluation is indicated. Their availability makes them useful for studying human variation where large sample sizes are crucial. Calcaneal and talar morphology are critical in the understanding of human foot form and function, but few studies have examined the accuracy of linear measurements of these bones taken from radiographs. If linear measurements are to be used in quantitative analysis, their accuracy must first be demonstrated. For this study, 54 human feet from amputated limbs were imaged in standard radiographic views and skeletonized. Selected linear measurements were made on each skeletonized talus and calcaneus. Corresponding landmarks were identified on the radiographic images and the distances between these points determined. Using the measurements taken from the physical bone, the accuracy of the radiographic measurements was evaluated employing paired Student's t‐tests and correlation analysis. Most measurements were not significantly different (P ≥ 0.05). Overall, the sagittal plane measurements were correlated (r2 > 0.61–0.88, all P < 0.001) with the radiographic measurements; transverse plane measurements less so (r2 = 0.20–0.63, P < 0.001). These results demonstrate that measurements from radiographic images provide useful information concerning both the calcaneus and talus, indicating that radiographs of living individuals can be evaluated quantitatively and compared to osteology collections of modern humans. This information can be applied to the understanding of functional anatomy of the modern human foot, interpreting the hominin fossil pedal record, and establishing identification in forensic analysis. Anat Rec, 2017. © 2017 Wiley Periodicals, Inc. Anat Rec, 301:21–33, 2018. © 2017 Wiley Periodicals, Inc.
Sodium Iodide (NaI)‐Catalyzed Cross‐Coupling for C−S Bond Formation via Oxidative Dehydrogenation: Cheap, Direct Access to Unsymmetrical Aryl Sulfides
Authors: Wang Hui‐Hong , Shi Tao , Gao Wei‐Wei , Wang Yong‐Qiang , Li Jun‐Fang , Jiang Yi , Hou Yong Sheng , Chen Chen , Peng Xue , Wang Zhen 
Published: October 2017

AbstractA simple and practical NaI‐catalyzed direct C−H sulfenylation of arenes has been developed under air. In this reaction, aryl sulfides were obtained in moderate to excellent yields with high regioselectivity from readily available aromatic compounds and aryl/alkyl thiols, even on gram scale. To demonstrate the practicability of this reaction, two bioactive compound skeletons were synthesized in good yields. This method can also be used to late‐stage modification of curcumin.
High frequency of brain metastases after adjuvant therapy for high‐risk melanoma
Authors: Samlowski Wolfram E. , Moon James , Witter Merle , Atkins Michael B. , Kirkwood John M. , Othus Megan , Ribas Antoni , Sondak Vernon K. , Flaherty Lawrence E. 
Published: October 2017

AbstractThe incidence ofCNSprogression in patients with high‐risk regional melanoma (stagesIIIAN2a‐IIIC) is not well characterized. Data from the S0008 trial provided an opportunity to examine the role ofCNSprogression in treatment failure and survival. All patients were surgically staged. Following wide excision and full regional lymphadenectomy, patients were randomized to receive adjuvant biochemotherapy (BCT) or high‐dose interferon alfa‐2B (HDI).CNSprogression was retrospectively identified from data forms. Survival was measured from date ofCNSprogression. A total of 402 eligible patients were included in the analysis (BCT: 199,HDI: 203). Median follow‐up (if alive) was over 7 years (range: 1 month to 11 years). The site of initial progression was identifiable in 80% of relapsing patients.CNSprogression was a component of systemic melanoma relapse in 59/402 patients (15% overall). In 34/402 patients (9%)CNSprogression represented the initial site of treatment failure.CNSprogression was a component of initial progression in 27% of all patients whose melanoma relapsed (59/221). The risk ofCNSprogression was highest within 3 years of randomization. The difference inCNSprogression rates between treatment arms was not significant (BCT = 25,HDI = 34,P = 0.24). Lymph node macrometastases strongly associated withCNSprogression (P = 0.001), while ulceration and head and neck primaries were not significant predictors. This retrospective analysis of the S0008 trial identified a high brain metastasis rate (15%) in regionally advanced melanoma patients. Further studies are needed to establish whether screening plus earlier treatment would improve survival followingCNSprogression.
A Conjugate of an Anti‐Epidermal Growth Factor Receptor (EGFR) VHH and a Cell‐Penetrating Peptide Drives Receptor Internalization and Blocks EGFR Activation
Authors: van Lith Sanne A. M. , van den Brand Dirk , Wallbrecher Rike , van Duijnhoven Sander M. J. , Brock Roland , Leenders William P. J. 
Published: October 2017

AbstractOverexpression of (mutated) receptor tyrosine kinases is a characteristic of many aggressive tumors, and induction of receptor uptake has long been recognized as a therapeutic modality. A conjugate of a synthetically produced cell‐penetrating peptide (CPP), corresponding to amino acids 38–59 of human lactoferrin, and the recombinant llama single‐domain antibody (VHH) 7D12, which binds the human epidermal growth factor receptor (EGFR), was generated by sortase A mediated transpeptidation. The conjugate blocks EGF‐mediated EGFR activation with higher efficacy than that of both modalities alone; a phenomenon that is caused by both effective receptor blockade and internalization. Thus, the VHH–CPP conjugate shows a combination of activities that implement a highly powerful new design principle to block receptor activation by its clearance from the cell surface.
Two‐year clinical outcomes of patients treated with overlapping absorb scaffolds: An analysis of the ABSORB EXTEND single‐arm study
Authors: Costa J Ribamar , Abizaid Alexandre , Bartorelli Antonio L. , Whitbourn Robert , Serruys Patrick W. , Smits Pieter C. ,   on behalf of the ABSORB EXTEND investigators
Published: October 2017

AbstractBackgroundPreclinical data showed that overlapping (OVP) scaffolds might result in delayed healing and strut coverage compared to nonOVP scaffold segments. Furthermore, OVP in patients could result in increased periprocedure myocardial infarction (MI) rate secondary to side branch occlusion; however, little is known whether this may have an impact on long‐term clinical outcomes.MethodsABSORB EXTEND is a prospective, single‐arm, open‐label clinical study in which 812 patients were enrolled at 56 sites. In this study, we compared the immediate and 2‐year clinical outcomes of patients with OVP scaffolds (n = 115) to those of patients with nonOVP scaffolds (n = 697). The primary objective was the comparison of major adverse cardiac event (MACE) (cardiac death, MI and ischemic‐driven target lesion revascularization [TLR]) and scaffold thrombosis (ST) rates up to 2 years.ResultsBaseline clinical and angiographic characteristics were comparable between cohorts except for longer lesions in the OVP patients as expected (16.7 ± 7.3 vs. 11.6 ± 4.4 mm, P < 0.0001), higher lesion complexity (B2) and numerically smaller vessel size. In‐hospital, there was a marked increase in MACE in the OVP cohort (7.0 vs. 0.9%, P = 0.002), exclusively driven by a higher rate of periprocedure MI (7.0 vs. 0.9%, P = 0.002). Long‐term MACE did not significantly differ between groups (10.4% in the OVP cohort vs. 6.6% in the no‐OVP group, P = 0.1) with comparable rates of cardiac death (0.9 vs. 1.2%, P = 1.0) and ischemia‐driven TLR (1.7 vs. 2.5%, P = 1.0). Cumulative incidence of MI was higher in the OVP cohort (7.8 vs. 3.0%, P = 0.02). Of note, the rate of MI between hospital discharge and 2‐year follow‐up was lower in the OVP cohort (0.8 vs. 2.1%, P = 0.04). Cumulative incidence of definite/probable ST was relatively low and comparable between groups (1.8 vs. 1.5%, P = 0.7).ConclusionsIn this low‐to‐moderate complex population treated with the ABSORB scaffold the OVP group showed a higher incidence of periprocedure MI with no immediate or long‐term increase in cardiac death, TLR or ST.
Fracturing a dysfunctional Edwards Perimount bioprosthetic valve to facilitate percutaneous valve‐in‐valve placement of SAPIEN 3 valve with modified delivery system
Authors: Shahanavaz Shabana , Rockefeller Toby , Nicolas Ramzi , Balzer David 
Published: October 2017

AbstractPulmonary valve replacement via surgical implantation of a bioprosthetic valve (BPV) is a well‐established treatment for patients with dysfunctional RV outflow tracts. BPVs are prone to structural deterioration, and will eventually require replacement. Recently, percutaneous valve‐in‐valve (VIV) placement of transcatheter valves has established itself as a safe and effective alternative to surgical revision. Unfortunately, VIV therapy is inherently limited by the inner diameter of the BPV, which restricts the number of eligible patients. Other centers have reported on the feasibility of cracking certain BPVs with ultra high‐pressure balloons in bench testing. We now report cracking an Edwards Perimount BPV in the pulmonary position to facilitate VIV placement of an Edwards SAPIEN 3. The ability to crack the Perimount valve allowed placement of a larger valve than previously considered and minimized the final valve gradient. In an effort to avoid the morbidity and mortality of surgical pulmonary valve replacement, this new strategy will expand the number of patients eligible for percutaneous VIV therapy.
Paravalvular leak closure under intracardiac echocardiographic guidance
Authors: Ruparelia Neil , Cao Jacob , Newton James D. , Wilson Neil , Daniels Matthew J. , Ormerod Oliver J. 
Published: October 2017

AbstractObjectivesThe objective of this study was to determine the safety and efficacy of intracardiac echocardiography (ICE) to guide percutaneous paravalvular leak (PVL) closure.BackgroundPVL following surgical valve replacement occurs in 2%–15% of patients. Percutaneous treatment is an accepted management strategy in patients deemed to be too high risk for redo surgery. This is most commonly performed with transesophageal (TOE) guidance requiring general anesthesia that both potentially further increase the risk of intervention. ICE can be used to guide intervention, facilitating procedures to be performed under local anesthesia without esophageal intubation potentially making procedures shorter and safer and further enabling the treatment of patients that may have been turned down for intervention.MethodsAll patients that underwent ICE‐guided percutaneous transcatheter PVL closure between 2006 and 2016 at the John Radcliffe Hospital, Oxford, United Kingdom were retrospectively analyzed.ResultsTwenty‐one procedures were performed in 18 patients during the study period. Fourteen patients (77.8%) underwent successful ICE guided PVL closure. There were no ICE‐related complications. Eleven patients (78.6%) reported symptomatic improvement of at least one New York Heart Association (NYHA) Class and the remaining 3 patients had no change. No patient demonstrated objective evidence of persistent hemolysis following successful closure. There was one death within 30 days of the procedure and 1 year survival was 71.4%.ConclusionsPercutaneous paravalvular leak closure guided by ICE without the requirement of general anesthesia is feasible, safe, and associated with acceptable procedural success rates.
Patterns of vascular calcification in patients with end‐stage renal disease and calcific uremic arteriolopathy
Authors: Koratala Abhilash , Leghrouz Muhannad , Phillips Melinda H. , Bhatti Vikrampal 
Published: October 2017

Key Clinical MessageCalcific uremic arteriolopathy or calciphylaxis is a rare and potentially fatal condition, which manifests as skin ischemia and necrosis, usually seen in patients with end‐stage renal disease. It is frequently associated with vascular calcification visible on plain radiographs, which can occur in various patterns.