bluuebunny/crossref_metadata_2025 huggingface dataset:
A Facile Method to Fine‐Tune Polymer Aggregation Properties and Blend Morphology of Polymer Solar Cells Using Donor Polymers with Randomly Distributed Alkyl Chains
Authors: Yao Huatong , Li Yunke , Hu Huawei , Chow Philip C. Y. , Chen Shangshang , Zhao Jingbo , Li Zhengke , Carpenter Joshua H. , Lai Joshua Yuk Lin , Yang Guofang , Liu Yuhang , Lin Haoran , Ade Harald , Yan He
Published: October 2017

The device performance of polymer solar cells (PSCs) is strongly dependent on the blend morphology. One of the strategies for improving PSC performance is side‐chain engineering, which plays an important role in controlling the aggregation properties of the polymers and thus the domain crystallinity/purity of the donor–acceptor blends. In particular, for a family of high‐performance donor polymers with strong temperature‐dependent aggregation properties, the device performances are very sensitive to the size of alkyl chains, and the best device performance can only be achieved with an optimized odd‐numbered alkyl chain. However, the synthetic route of odd‐numbered alkyl chains is costly and complicated, which makes it difficult for large‐scale synthesis. Here, this study presents a facile method to optimize the aggregation properties and blend morphology by employing donor polymers with a mixture of two even‐numbered, randomly distributed alkyl chains. In a model polymer system, this study suggests that the structural and electronic properties of the random polymers comprising a mixture of 2‐octyldodecyl and 2‐decyltetradecyl alkyl chains can be systematically tuned by varying the mixing ratio, and a high power conversion efficiency (11.1%) can be achieved. This approach promotes the scalability of donor polymers and thus facilitates the commercialization of PSCs.
Inorganic CsPbI3 Perovskite Coating on PbS Quantum Dot for Highly Efficient and Stable Infrared Light Converting Solar Cells
Authors: Zhang Xiaoliang , Zhang Jindan , Phuyal Dibya , Du Juan , Tian Lei , Öberg Viktor A. , Johansson Malin B. , Cappel Ute B. , Karis Olof , Liu Jianhua , Rensmo Håkan , Boschloo Gerrit , Johansson Erik M. J.
Published: October 2017

Solution‐processed colloidal quantum dot (CQD) solar cells harvesting the infrared part of the solar spectrum are especially interesting for future use in semitransparent windows or multilayer solar cells. To improve the device power conversion efficiency (PCE) and stability of the solar cells, surface passivation of the quantum dots is vital in the research of CQD solar cells. Herein, inorganic CsPbI3 perovskite (CsPbI3‐P) coating on PbS CQDs with a low‐temperature, solution‐processed approach is reported. The PbS CQD solar cell with CsPbI3‐P coating gives a high PCE of 10.5% and exhibits remarkable stability both under long‐term constant illumination and storage under ambient conditions. Detailed characterization and analysis reveal improved passivation of the PbS CQDs with the CsPbI3‐P coating, and the results suggest that the lattice coherence between CsPbI3‐P and PbS results in epitaxial induced growth of the CsPbI3‐P coating. The improved passivation significantly diminishes the sub‐bandgap trap‐state assisted recombination, leading to improved charge collection and therefore higher photovoltaic performance. This work therefore provides important insight to improve the CQD passivation by coating with an inorganic perovskite ligand for photovoltaics or other optoelectronic applications.
The promotion of Argon and water molecule on direct synthesis of H2O2from H2and O2
Authors: Yi Yanhui , Wang Li , Yu Juan , Guo Hongchen , Zhang Jialiang , Meng Changgong
Published: October 2017

Direct synthesis of hydrogen peroxide (H2O2) from H2and O2is an ideal route. H2/O2plasma has a great potential for direct synthesis of high purity H2O2without purification operations. However, low yield and high energy consumption limits the application of H2/O2plasma in industry. This article reports that gas state Ar and H2O molecule serving as molecular catalysts promoted the synthesis of H2O2from H2/O2/Ar/H2O plasma dramatically: the H2O2yield was enhanced by 244% and the energy consumption was reduced by 70.9%. Ar not only increased the electron density, but also selectively accelerated the dissociation of H2toward the formation of •HO2, a key intermediate species in H2O2synthesis. While H2O facilitated the formation of •HO2radical and stabilized it by forming a HO2•H2O complex, resulting in enhancing the H2O2production. This single molecular catalysis reduced the cost of H2O2synthesis more than 50%. © 2017 American Institute of Chemical EngineersAIChE J, 64: 981–992, 2018
Short‐term resource allocation during extensive athletic competition
Authors: Longman Daniel P. , Prall Sean P. , Shattuck Eric C. , Stephen Ian D. , Stock Jay T. , Wells Jonathan C. K. , Muehlenbein Michael P.
Published: October 2017

Objectives

Following predictions from life history theory, we sought to identify acute trade‐offs between reproductive effort (as measured by psychological arousal) and somatic maintenance (via functional measures of innate immunity) during conditions of severe energetic imbalance.

Methods

Sixty‐six male ultramarathon runners (ages 20 to 37 years) were sampled before and after a lengthy race. Saliva and sera were collected for testosterone and immunological analyses (hemolytic complement activity and bacterial killing ability). Lean body mass was assessed by bioelectrical impedance, and libido was measured using a slideshow of arousing and neutral images.

Results

Following predictions, there was a significant decrease in salivary testosterone levels (109.59 pg/mL versus 97.61 pg/mL, P < .001) and arousal scores in response to provocative images (5.40 versus 4.89, P = .001) between prerace and postrace time points. Additionally, participant bacterial killing ability (P = .035) and hemolytic complement activity (P = .021) increased between prerace and postrace.

Conclusions

Decreased libido and testosterone with concomitant heightened innate immune responses suggest a shift in energetic priorities away from reproduction and toward maintenance/defense during a period of energetic stress.
AnthropMMD: An R package with a graphical user interface for the mean measure of divergence
Authors: Santos Frédéric
Published: October 2017

The mean measure of divergence is a dissimilarity measure between groups of individuals described by dichotomous variables. It is well suited to datasets with many missing values, and it is generally used to compute distance matrices and represent phenograms. Although often used in biological anthropology and archaeozoology, this method suffers from a lack of implementation in common statistical software. A package for the R statistical software, AnthropMMD, is presented here. Offering a dynamic graphical user interface, it is the first one dedicated to Smith's mean measure of divergence. The package also provides facilities for graphical representations and the crucial step of trait selection, so that the entire analysis can be performed through the graphical user interface. Its use is demonstrated using an artificial dataset, and the impact of trait selection is discussed. Finally, AnthropMMD is compared to three other free tools available for calculating the mean measure of divergence, and is proven to be consistent with them.
Peripheral nerve involvement in multiple sclerosis: Demonstration by magnetic resonance neurography
Authors: Jende Johann M. E. , Hauck Gesa H. , Diem Ricarda , Weiler Markus , Heiland Sabine , Wildemann Brigitte , Korporal‐Kuhnke Mirjam , Wick Wolfgang , Hayes John M. , Pfaff Johannes , Pham Mirko , Bendszus Martin , Kollmer Jennifer
Published: October 2017

Objective

To detect and quantify peripheral nerve lesions in multiple sclerosis (MS) by magnetic resonance neurography (MRN).

Methods

Thirty‐six patients diagnosed with MS based on the 2010 McDonald criteria (34 with the relapsing–remitting form, 2 with clinically isolated syndrome) with and without disease‐modifying treatment were compared to 35 healthy age‐/sex‐matched volunteers. All patients underwent detailed neurological and electrophysiological examinations. Three Tesla MRN with large anatomical coverage of both legs and the lumbosacral plexus was performed by using 2‐dimensional (2D) fat‐saturated, T2‐weighted (T2w) and dual echo turbo spin echo sequences as well as a 3D T2‐weighted, fat‐saturated SPACE sequence. Besides qualitative visual nerve assessment, a T2w signal quantification was performed by calculation of proton spin density and T2 relaxation time. Nerve diameter was measured as a morphometric criterion.

Results

T2w hyperintense nerve lesions were detectable in all MS patients, with a mean lesion number at thigh level of 151.5 ± 5.7 versus 19.1 ± 2.4 in controls (p < 0.0001). Nerve proton spin density was higher in MS (tibial/peroneal: 371.8 ± 7.7/368.9 ± 8.2) versus controls (tibial/peroneal: 266.0 ± 11.0/276.8 ± 9.7, p < 0.0001). In contrast, T2 relaxation time was significantly higher in controls (tibial/peroneal: 82.0 ± 2.1/78.3 ± 1.7) versus MS (tibial/peroneal: 64.3 ± 1.0/61.2 ± 0.9, p < 0.0001). Proximal tibial and peroneal nerve caliber was higher in MS (tibial: 52.4 ± 2.1mm2, peroneal: 25.4 ± 1.3mm2) versus controls (tibial: 45.2 ± 1.4mm2, p < 0.0015; peroneal: 21.3 ± 0.7mm2, p = 0.0049).

Interpretation

Peripheral nerve lesions could be visualized and quantified in MS in vivo by high‐resolution MRN. Lesions are defined by an increase of proton spin density and a decrease of T2 relaxation time, indicating changes in the microstructural organization of the extracellular matrix in peripheral nerve tissue in MS. By showing involvement of the peripheral nervous system in MS, this proof‐of‐concept study may offer new insights into the pathophysiology and treatment of MS. Ann Neurol 2017;82:676–685
Prediction of phenotypic severity in mucopolysaccharidosis type IIIA
Authors: Knottnerus Suzan J. G. , Nijmeijer Stephanie C. M. , IJlst Lodewijk , te Brinke Heleen , van Vlies Naomi , Wijburg Frits A.
Published: October 2017

Objective

Mucopolysaccharidosis IIIA or Sanfilippo disease type A is a progressive neurodegenerative disorder presenting in early childhood, caused by an inherited deficiency of the lysosomal hydrolase sulfamidase. New missense mutations, for which genotype–phenotype correlations are currently unknown, are frequently reported, hampering early prediction of phenotypic severity and efficacy assessment of new disease‐modifying treatments. We aimed to design a method to determine phenotypic severity early in the disease course.

Methods

Fifty‐three patients were included for whom skin fibroblasts and data on disease course and mutation analysis were available. Patients were phenotypically characterized on clinical data as rapidly progressing or slowly progressing. Sulfamidase activity was measured in fibroblasts cultured at 37 °C and at 30 °C.

Results

Sulfamidase activity in fibroblasts from patients homozygous or compound heterozygous for a combination of known severe mutations remained below the limit of quantification under both culture conditions. In contrast, sulfamidase activity in fibroblasts from patients homozygous or compound heterozygous for a known mild mutation increased above the limit of quantification when cultured at 30 °C. With division on the basis of the patients' phenotype, fibroblasts from slowly progressing patients could be separated from rapidly progressing patients by increase in sulfamidase activity when cultured at 30 °C (p < 0.001, sensitivity = 96%, specificity = 93%).

Interpretation

Phenotypic severity strongly correlates with the potential to increase sulfamidase activity in fibroblasts cultured at 30 °C, allowing reliable distinction between patients with rapidly progressing or slowly progressing phenotypes. This method may provide an essential tool for assessment of treatment effects and for health care and life planning decisions. Ann Neurol 2017;82:686–696
Age, vascular health, and Alzheimer disease biomarkers in an elderly sample
Authors: Vemuri Prashanthi , Lesnick Timothy G. , Przybelski Scott A. , Knopman David S. , Lowe Val J. , Graff‐Radford Jonathan , Roberts Rosebud O. , Mielke Michelle M. , Machulda Mary M. , Petersen Ronald C. , Jack Clifford R.
Published: October 2017

Objective

To investigate the associations between age, vascular health, and Alzheimer disease (AD) imaging biomarkers in an elderly sample.

Methods

We identified 430 individuals along the cognitive continuum aged >60 years with amyloid positron emission tomography (PET), tau PET, and magnetic resonance imaging (MRI) scans from the population‐based Mayo Clinic Study of Aging. A subset of 329 individuals had fluorodeoxyglucose (FDG) PET. We ascertained presently existing cardiovascular and metabolic conditions (CMC) from health care records and used the summation of presence/absence of hypertension, hyperlipidemia, cardiac arrhythmias, coronary artery disease, congestive heart failure, diabetes mellitus, and stroke as a surrogate for vascular health. We used global amyloid from Pittsburgh compound B PET, entorhinal cortex tau uptake (ERC‐tau) from tau‐PET, and neurodegeneration in AD signature regions from MRI and FDG‐PET as surrogates for AD pathophysiology. We dichotomized participants into CMC = 0 (CMC−) versus CMC > 0 (CMC+) and tested for age‐adjusted group differences in AD biomarkers. Using structural equation models (SEMs), we assessed the impact of vascular health on AD biomarker cascade (amyloid leads to tau leads to neurodegeneration) after considering the direct and indirect age, sex, and apolipoprotein E effects.

Results

CMC+ participants had significantly greater neurodegeneration than CMC− participants but did not differ by amyloid or ERC‐tau. The SEMs showed that (1) vascular health had a significant direct and indirect impact on neurodegeneration but not on amyloid; and (2) vascular health, specifically the presence of hyperlipidemia, had a significant direct impact on ERC‐tau.

Interpretation

Vascular health had quantifiably greater impact on neurodegeneration in AD regions than on amyloid deposition. Longitudinal studies are warranted to clarify the relationship between tau deposition and vascular health. Ann Neurol 2017;82:706–718
Imaging spinal cord atrophy in progressive myelopathies: HTLV‐I‐associated neurological disease (HAM/TSP) and multiple sclerosis (MS)
Authors: Azodi Shila , Nair Govind , Enose‐Akahata Yoshimi , Charlip Emily , Vellucci Ashley , Cortese Irene , Dwyer Jenifer , Billioux B. Jeanne , Thomas Chevaz , Ohayon Joan , Reich Daniel S. , Jacobson Steven
Published: October 2017

Objective

Previous work measures spinal cord thinning in chronic progressive myelopathies, including human T‐lymphotropic virus 1 (HTLV‐1)‐associated myelopathy/tropical spastic paraparesis (HAM/TSP) and multiple sclerosis (MS). Quantitative measurements of spinal cord atrophy are important in fully characterizing these and other spinal cord diseases. We aimed to investigate patterns of spinal cord atrophy and correlations with clinical markers.

Methods

Spinal cord cross‐sectional area was measured in individuals (24 healthy controls [HCs], 17 asymptomatic carriers of HTLV‐1 (AC), 47 HAM/TSP, 74 relapsing‐remitting MS [RRMS], 17 secondary progressive MS [SPMS], and 40 primary progressive MS [PPMS]) from C1 to T10. Clinical disability scores, viral markers, and immunological parameters were obtained for patients and correlated with representative spinal cord cross‐sectional area regions at the C2 to C3, C4 to C5, and T4 to T9 levels. In 2 HAM/TSP patients, spinal cord cross‐sectional area was measured over 3 years.

Results

All spinal cord regions are thinner in HAM/TSP (56 mm2 [standard deviation, 10], 59 [10], 23 [5]) than in HC (76 [7], 83 [8], 38 [4]) and AC (71 [7], 78 [9], 36 [7]). SPMS (62 [9], 66 [9], 32 [6]) and PPMS (65 [11], 68 [10], 35 [7]) have thinner cervical cords than HC and RRMS (73 [9], 77 [10], 37 [6]). Clinical disability scores (Expanded Disability Status Scale [p = 0.009] and Instituto de Pesquisas de Cananeia [p = 0.03]) and CD8+ T‐cell frequency (p = 0.04) correlate with T4 to T9 spinal cord cross‐sectional area in HAM/TSP. Higher cerebrospinal fluid HTLV‐1 proviral load (p = 0.01) was associated with thinner spinal cord cross‐sectional area. Both HAM/TSP patients followed longitudinally showed thoracic thinning followed by cervical thinning.

Interpretation

Group average spinal cord cross‐sectional area in HAM/TSP and progressive MS show spinal cord atrophy. We further hypothesize in HAM/TSP that is possible that neuroglial loss from a thoracic inflammatory process results in anterograde and retrograde degeneration of axons, leading to the temporal progression of thoracic to cervical atrophy described here. Ann Neurol 2017;82:719–728.
Chaos‐related Localization in Modulated Lattice Array
Authors: Li Liping , Wang Bo , Lü Xin‐You , Wu Ying
Published: October 2017

This paper will discuss the chaos‐related localization in a lattice array with an external periodical field acted on a boundary site that allows us to realize the controllable chaotic dynamics with a tunable driving frequency. Two types of chaos‐related localization, short‐term and long‐term localization, which are closely related to the degree of chaos are reported and may provide a way to realize switching from chaos‐related localization to chaos‐assisted tunneling. Interestingly, with the increase of nonlinearity, driving frequency or even second‐order coupling, there always exists a parameter window with sharp edges for long‐term localization which facilitates us to find the thresholds to control the system into or out of localization region. In addition, the numerical results further demonstrate that the initial phase of the driving field may greatly influence the degree of the chaos. These results can be extended to finite driven N‐site system and may deepen our understanding of chaos‐related localization in nonlinear driving system.
Evolution of Density Parameters on a Smooth Embedded Universe
Authors: Capistrano Abraão J.S.
Published: October 2017

In 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

Cancer 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

Der 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

[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

Carbohydrate‐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

π‐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

The 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

Selective 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

Partite 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

Plain 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.
The histopathologic reliability of tissue taken from cadavers within the gross anatomy laboratory
Authors: Rae Guenevere , Newman William P. , McGoey Robin , Donthamsetty Supriya , Karpinski Aryn C. , Green Jeffrey
Published: October 2017

The purpose of this study was to examine the histopathologic reliability of embalmed cadaveric tissue taken from the gross anatomy laboratory. Tissue samples from hearts, livers, lungs, and kidneys were collected after the medical students’ dissection course was completed. All of the cadavers were embalmed in a formalin‐based fixative solution. The tissue was processed, embedded in paraffin, sectioned at six micrometers, and stained with H&E. The microscope slides were evaluated by a board certified pathologist to determine whether the cellular components of the tissues were preserved at a high enough quality to allow for histopathologic diagnosis. There was a statistically significant relationship between ratings and organ groups. Across all organs, there was a smaller proportion of “poor” ratings. The lung group had the highest percentage of “poor” ratings (23.1%). The heart group had the least “poor” ratings (0.0%). The largest percentage of “satisfactory” ratings were in the lung group (52.8%), and the heart group contained the highest percentage of “good” ratings (58.5%) The lung group had the lowest percentage of “good” ratings (24.2%). These results indicate that heart tissue is more reliable than lung, kidney, or liver tissue when utilizing tissue from the gross anatomy laboratory for research and/or educational purposes. This information advises educators and researchers about the quality and histopathologic reliability of tissue samples obtained from the gross anatomy laboratory. Anat Sci Educ 11: 207–214. © 2017 American Association of Anatomists.
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

A 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.
Direct Production of (R)‐3‐Hydroxybutyric Acid of High Optical Purity by Halomonas sp. OITC1261 Under Aerobic conditions
Authors: Yokaryo Hiroto , Teruya Morimi , Hanashiro Ryuji , Goda Masahiro , Tokiwa Yutaka
Published: October 2017

The chiral compound (R)‐3‐hydroxybutyric acid (R‐3HB) has some important physiological functions in the human body and can also be applied as a functional material for industrial products. A novel Halomonas sp. OITC1261 isolated from a coastal sediment is selected for efficient production of R‐3HB. This strain secreted R‐3HB of high optical purity into the extracellular medium while maintaining poly(3‐hydroxybutyric acid) (PHB) inside the microbial cell under aerobic conditions. There is a possibility that R‐3HB is generated independently of PHB. Under aerobic cultivation, 58 g L−1 (0.65 g L−1 h−1) of R‐3HB was produced simultaneously with 27 g L−1 (0.30 g L−1 h−1) of PHB. This direct production method of R‐3HB contributes to the improvement of mass production technology.
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

The 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

Overexpression 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

Background

Preclinical 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.

Methods

ABSORB 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.

Results

Baseline 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).

Conclusions

In 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

Pulmonary 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

Objectives

The objective of this study was to determine the safety and efficacy of intracardiac echocardiography (ICE) to guide percutaneous paravalvular leak (PVL) closure.

Background

PVL 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.

Methods

All patients that underwent ICE‐guided percutaneous transcatheter PVL closure between 2006 and 2016 at the John Radcliffe Hospital, Oxford, United Kingdom were retrospectively analyzed.

Results

Twenty‐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%.

Conclusions

Percutaneous 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 Message

Calcific 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.
Enhanced Electrochemical Performance of a Tin−antimony Alloy/N‐Doped Carbon Nanocomposite as a Sodium‐Ion Battery Anode
Authors: Youn Duck Hyun , Park Hunmin , Loeffler Kathryn E. , Kim Jun‐Hyuk , Heller Adam , Mullins C. Buddie
Published: October 2017

A simple one‐pot process for producing 3.5 nm diameter uniformly dispersed SnSb nanoparticles on a nitrogen‐doped carbon composite (NC) is reported. An ethanol slurry of SnCl4, SbCl3, and nitrilotriacetic acid (NTA) is heated in air to 300 °C to form the mixed metal oxide NTA complex; heating to 650 °C under argon yields the SnSb/NC nanocomposites, comprising 3.5 nm diameter SnSb nanocrystals uniformly distributed in the conductive N‐doped carbon. After 200 cycles at a specific current of 0.1 Ag−1, the SnSb/NC nanocomposite sodium‐ion anode retains a reversible capacity of 244 mAh g−1. The similarly prepared Sn/NC and Sb/NC anodes retain lower capacities of 88 and 188 mAh g−1, respectively. The improved performance of the SnSb/NC electrode might be ascribed to the stepwise sodiation/desodiation process of Sn and Sb species in the SnSb/NC electrode, which could act as an inert buffer matrix for each other, according to the potentials, slowing the capacity fading.
Hemin‐Graphene Derivatives with Increased Peroxidase Activities Restrain Protein Tyrosine Nitration
Authors: Xu Huan , Yang Zhen , Li Hailing , Gao Zhonghong
Published: October 2017

Protein tyrosine nitration is implicated in the occurrence and progression of pathological conditions involving free radical reactions. It is well recognized that hemin can catalyze protein tyrosine nitration in the presence of nitrite and hydrogen peroxide. Generally, the catalytic efficiency is positively correlated to its peroxidase activity. In this study, however, it is found that the efficiency of hemin in catalyzing protein tyrosine nitration is largely suppressed after functionalization with graphene derivatives, even though its peroxidase‐like activity is more than quadrupled. Further studies show that the oxidation of tyrosine is still observed for these composites; dityrosine formation, however, is greatly inhibited. Furthermore, these composites also exhibit strong effects on the oxidation of nitrite into nitrate. Therefore, we propose a mechanism in which hemin‐graphene derivatives facilitate the oxidation of tyrosine and nitrite to produce tyrosyl radicals and nitrogen dioxide radicals in the presence of hydrogen peroxide, but graphene interlayers serve as barriers that hinder radical–radical coupling reactions; consequently, protein tyrosine nitration is restrained. This property of hemin‐graphene derivatives, by which they catalyze substrate oxidation but suppress radical–radical coupling reactions, shows their great potential in selective oxidation procedures for byproduct removal.
Highly Spin‐Frustrated Magnetism in the Topochemically Prepared Triangular Lattice Cluster Magnets Na3A2(MoO4)2Mo3O8 (A=In, Sc)
Authors: Haraguchi Yuya , Michioka Chishiro , Ueda Hiroaki , Yoshimura Kazuyoshi
Published: October 2017

The physical properties of novel cluster‐based triangular lattice antiferromagnets Na3A2(MoO4)2Mo3O8 (A=In, Sc), synthesized through a topochemical Na‐intercalation to nonmagnetic Na2A2(MoO4)2Mo3O8, are reported. The S=1/2 [Mo3]11+ clusters form a regular triangular lattice, which gives the magnetic system a strong geometrical spin frustration effect. Despite the strong antiferromagnetic couplings among [Mo3]11+ clusters, they show no long‐range magnetic orderings down to 0.5 K with the finite residual magnetic entropy. The ground states of Na3A2(MoO4)2Mo3O8 have been characterized as a quantum spin liquid, owing to the strong spin frustration of cluster spins on the triangular lattice.