bluuebunny/crossref_metadata_2025 huggingface dataset:
Can Machine Learning Revolutionize Directed Evolution of Selective Enzymes?
Authors: Li Guangyue , Dong Yijie , Reetz Manfred T.
Published: March 2019

Machine learning as a form of artificial intelligence consists of algorithms and statistical models for improving computer performance for different tasks. Training data are utilized for making decisions and predictions. Since directed evolution of enzymes produces huge amounts of potential training data, machine learning seems to be ideally suited to support this protein engineering technique. Machine learning has been used in protein science for a long time with different purposes. This mini‐review focuses on the utility of machine learning as an aid in the directed evolution of selective enzymes. Recent studies have shown that the algorithms ASRA and Innov'SAR are well suited as guides when performing saturation mutagenesis at sites lining the binding pocket for enhancing stereoselectivity and activity.

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The dynamics of monocytes in the process of collateralization
Authors: Liao Long‐Sheng , Bai Yong‐Ping
Published: March 2019

Collateralization is an important way for patients with coronary heart disease to supply blood flow to the ischemic area. At present, research on the mechanism of collateral circulation mainly focuses on the inflammatory response. Monocytes are the kernel of inflammatory response during arteriogenesis. Therefore, we reviewed the recent developments in this field in terms of the dynamic changes of monocytes during collateralization. We searched and scanned PubMed for the following terms until November 2018: collateral, collateralization, monocyte, macrophage, and arteriogenesis. Articles were obtained and examined to figure out the dynamics of monocytes in the progress of collateralization. Substantial research shows that recruitment, infiltration, and phenotypic transformation of monocytes can affect function in various ways, respectively. Mechanical or chemical factors that can produce effects on collateral development may be due partly to impact on dynamics of monocytes. Although mechanisms of dynamics of monocytes during arteriogenesis are not elucidated clearly, there is no doubt that deeper exploration of the underlying mechanisms will contribute to pharmaceutical development aiming for promoting collateral development.
The association between patterns of physical activity and sedentary time with frailty in relation to cardiovascular disease
Authors: Kehler Dustin Scott , Clara Ian , Hiebert Brett , Stammers Andrew Nicholas , Hay Jacqueline , Schultz Annette , Arora Rakesh Christopher , Tangri Navdeep , Duhamel Todd Ashley
Published: March 2019

Objective

The associations of moderate‐vigorous physical activity (MVPA) bouts and patterns of sedentary time (ST) with frailty according to cardiovascular disease (CVD) status are unknown.

Methods

Accelerometry in adults ≥50 years old from the 2003‐2004 and 2005‐2006 National Health and Nutrition Examination Survey were used. Bouted and sporadic MVPA in ≥10‐minute or <1‐minute bouts were assessed based on meeting a percentage of physical activity guidelines of 150 minutes/wk, respectively. ST patterns included: prolonged ST lasting ≥30 minutes, and the frequency, intensity, and duration of breaks from ST. A 46‐item frailty index defined frailty. Multivariable linear regression was used.

Results

There were 827 and 1490 CVD‐free and CVD participants, respectively. Meeting a higher percentage of the physical activity guidelines through bouted MVPA was associated with lower frailty in CVD‐only participants (P < 0.05 for CVD interaction). Sporadic MVPA was associated with lower frailty levels in both groups. Prolonged ST was associated with worse frailty in CVD (P > 0.05 for CVD interaction). Frequency of ST breaks was not associated with frailty. Average ST break intensity was protective in both groups. The duration of breaks in ST was associated with lower frailty in CVD participants only (P > 0.05 for CVD interaction).

Conclusion

Insufficient MVPA and prolonged ST are detrimental despite CVD status.
Height growth velocity during infancy and childhood in achondroplasia
Authors: del Pino Mariana , Fano Virginia , Adamo Paula
Published: March 2019

There is a lack of knowledge about longitudinal growth during childhood in achondroplasia. We report patterns of linear growth and height growth velocity references. The sample consisted of 84 children, 41 girls and 43 boys. Growth data was collected from birth until mid‐childhood. The median (interquartile range) number of measurements per child was 13.5 (12, 15). Individual growth curves were estimated by fitting the Reed 1st model to each individual's height for age data. Height growth velocities references for age centiles were calculated by LMS method.

Mean (SD) birth length was 46.14 cm (2.17) and 45.53 cm (2.16), for boys and girls respectively. Individual growth curves were analyzed. Shifts in growth channels were seen: out of 84 infants, 41 (48.8%) changed more than 1 SDS between birth to 5 years old. The numbers of infants shifting upward were similar (20/84) to the infants shifting downward (21/84). Height growth velocity curves show that after a period of fast decreasing growth velocity since birth, with a mean of 15.5 cm/year and 9.5 cm/year at 6 month and 1 year old, the growth velocity is stable in late preschool years, with a mean of 4.3 cm/year. Shifts in growth channels were seen between birth and 5 years old. Professionals who follow up them must consider this phenomenon during infancy. ACH children experienced a period of fast decreasing growth during infancy and the growth curve was similar in shape and lesser in magnitude than the general population.
Accelerated and Noise‐Resistant Protocol of Dissipation‐Based Knill–Laflamme–Milburn State Generation with Lyapunov Control
Authors: Wang Yu , Hu Chang‐Sheng , Shi Zhi‐Cheng , Huang Bi‐Hua , Song Jie , Xia Yan
Published: March 2019

A protocol to generate steady Knill–Laflamme–Milburn (KLM) states of two Rydberg atoms with dissipation and Lyapunov control is proposed. Herein, combining with the quantum Zeno dynamics and the Rydberg antiblockade, a unique and steady solution of the master equation of the system is obtained, which satisfies the definition of KLM states. Furthermore, to polish the convergence rate, well‐designed additional coherent control (ACC) fields with Lyapunov control are added into the traditional dissipation process. Numerical simulation reveals that the steady target state generation is prominently accelerated and the protocol is robust against the stochastic noise errors caused by laser fields. It is hoped that the work may provide an alternative protocol to polish the generation of entanglement.
Selektive Synthese von Iridium(III)‐Metalla[2]catenanen durch Präorganisation der Komponenten über π‐π‐Wechselwirkungen
Authors: Shan Wei‐Long , Lin Yue‐Jian , Hahn F. Ekkehardt , Jin Guo‐Xin
Published: March 2019

Eine Reihe von molekularen Metalla[2]catenanen mit Cp*Ir‐Eckbausteinen wurde in einer templatfreien Selbstorganisation aus zweikernigen Iridiumakzeptoren und 1,5‐Bis[2‐(4‐pyridyl)ethinyl]anthracen‐Donoren erhalten. Die Metalla[2]catenane bilden sich beim Einsatz ausgewählter Brückenliganden, die Sandwich‐artige π‐π‐Wechselwirkungen ausbilden. Im Festkörper können die [2]Catenane zwei unterschiedliche Konfigurationen annehmen, die durch Halogenatome an den zweikernigen Brückenliganden bestimmt werden. Veränderungen des Lösungsmittels, der Konzentration sowie die Zugabe von Gastmolekülen erlauben die kontrollierte Umwandlung von Metalla[2]catenanen in molekulare Metalla‐Rechtecke.
Intermolekulare radikalische C(sp3)‐H‐Aminierung unter Iod‐Katalyse
Authors: Bosnidou Alexandra E. , Muñiz Kilian
Published: March 2019

Die direkte Aminierung von aliphatischen C‐H‐Bindungen stellt eine der attraktivsten Umwandlungen in der organischen Chemie dar. Wir berichten hier über ein einzigartiges Katalysatorsystem, das die bislang schwierige intermolekulare C(sp3)‐H‐Aminierung möglich macht. Diese praktische Synthesestrategie eröffnet den Zugang zu aminierten Bausteinen und fördert die innovative mehrfache C‐H‐Aminierung innerhalb eines neuen Zugangs zu aminierten Heterocyclen. Der synthetische Nutzen wird anhand der Synthesen von vier relevanten Pharmazeutika demonstriert.
Intermolekulare, verzweigt‐selektive und redoxneutrale Cp*IrIII‐katalysierte allylische C‐H‐Amidierung
Authors: Knecht Tobias , Mondal Shobhan , Ye Jian‐Heng , Das Mowpriya , Glorius Frank
Published: March 2019

Wir berichten über die redoxneutrale, intermolekulare und verzweigt‐selektive Amidierung von allylischen C‐H‐Bindungen durch Cp*IrIII‐Katalyse. Eine Vielzahl leicht verfügbarer Carbonsäuren wurde in die entsprechenden Dioxazolone umgewandelt und effizient mit terminalen und internen Olefinen in hohen Ausbeuten und Selektivitäten gekuppelt. Mechanistische Untersuchungen stützen die Bildung eines nukleophilen IrIII‐Allyl‐Intermediats und nicht die direkte Insertion einer Ir‐Nitrenoidspezies in die allylische C‐H‐Bindung.
Dissecting FOXP2 Oligomerization and DNA Binding
Authors: Häußermann Katharina , Young Gavin , Kukura Philipp , Dietz Hendrik
Published: March 2019

Protein–protein and protein–substrate interactions are critical to function and often depend on factors that are difficult to disentangle. Herein, a combined biochemical and biophysical approach, based on electrically switchable DNA biochips and single‐molecule mass analysis, was used to characterize the DNA binding and protein oligomerization of the transcription factor, forkhead box protein P2 (FOXP2). FOXP2 contains domains commonly involved in nucleic‐acid binding and protein oligomerization, such as a C2H2‐zinc finger (ZF), and a leucine zipper (LZ), whose roles in FOXP2 remain largely unknown. We found that the LZ mediates FOXP2 dimerization via coiled‐coil formation but also contributes to DNA binding. The ZF contributes to protein dimerization when the LZ coiled‐coil is intact, but it is not involved in DNA binding. The forkhead domain (FHD) is the key driver of DNA binding. Our data contributes to understanding the mechanisms behind the transcriptional activity of FOXP2.
Esters as Radical Acceptors: β‐NHC‐Borylalkenyl Radicals Induce Lactonization by C−C Bond Formation/Cleavage on Esters
Authors: Shimoi Masaki , Maeda Katsuhiro , Geib Steven J. , Curran Dennis P. , Taniguchi Tsuyoshi
Published: March 2019

Substituted propargyl acetates are converted into 4‐boryl‐2(5H)‐furanones upon thermolysis in the presence of an N‐heterocyclic carbene borane (NHC‐borane) and di‐tert‐butyl peroxide. The acetyl methyl group is lost during the reaction as methane. Evidence suggests that the reaction proceeds by a sequence of radical events including: 1) addition of an NHC‐boryl radical to the triple bond; 2) cyclization of the resultant β‐borylalkenyl radical to the ester carbonyl group; 3) β‐scission of the so‐formed alkoxy radical to provide the 4‐boryl‐2(5H)‐furanone and a methyl radical; and 4) hydrogen abstraction from the NHC‐borane to return the initial NHC‐boryl radical and methane.
Bimetallic Cooperative Cleavage of Dinitrogen to Nitride and Tandem Frustrated Lewis Pair Hydrogenation to Ammonia
Authors: Doyle Laurence R. , Wooles Ashley J. , Liddle Stephen T.
Published: March 2019

Although reductive cleavage of dinitrogen (N2) to nitride (N3−) and hydrogenation with dihydrogen (H2) to yield ammonia (NH3) is accomplished in heterogeneous Haber–Bosch industrial processes on a vast scale, sequentially coupling these elementary reactions together with a single metal complex remains a major challenge for homogeneous molecular complexes. Herein, we report that the reaction of a chloro titanium triamidoamine complex with magnesium effects complete reductive cleavage of N2 to give a dinitride dititanium dimagnesium ditriamidoamine complex. Tandem H2 splitting by a phosphine–borane frustrated Lewis pair (FLP) shuttles H atoms to the N3−, evolving NH3. Isotope labelling experiments confirmed N2 and H2 fixation. Though not yet catalytic, these results give unprecedented insight into coupling N2 and H2 cleavage and N−H bond formation steps together, highlight the importance of heterobimetallic cooperativity in N2 activation, and establish FLPs in NH3 synthesis.
Boran‐Addukte von Stickstoffwasserstoffsäure und Organischen Aziden: Intermediate bei der Bildung von Aminoboranen
Authors: Bläsing Kevin , Bresien Jonas , Labbow René , Michalik Dirk , Schulz Axel , Thomas Max , Villinger Alexander
Published: March 2019

Die Reaktion von HN3 mit der starken Lewis‐Säure B(C6F5)3 führte zur Bildung des sehr labilen Addukts HN3−B(C6F5)3, das oberhalb von −20 °C unter Freisetzung von molekularem Stickstoff und gleichzeitiger Migration einer C6F5‐Gruppe von Bor zu Stickstoff zu einem Aminoboran, H(C6F5)NB(C6F5)2, zerfällt. Die intermediäre Bildung von Azid‐Boran‐Addukten mit B(C6F5)3 und deren Staudinger‐ähnliche Zersetzung mit C6F5‐Gruppenmigration wurde ebenfalls für eine Reihe verschiedener organischer Azide R−N3 (R=Me3Si=TMS, Ph, 3,5‐(CF3)2C6H3=Btp) nachgewiesen. In Übereinstimmung mit dem Experiment ergaben Berechnungen, dass die hochlabilen Azidaddukte relativ kleine Barrieren für die Freisetzung von Stickstoff für alle organischen Substituenten außer R=Me3Si (Schmelzpunkt 120 °C, TZers.=189 °C) aufweisen. Die Hydrolyse der Aminoborane lieferte C6F5‐substituierte Amine, HN(R)(C6F5), in guter Ausbeute.
Synthesis of Eight‐Membered Lactams through Formal [6+2] Cyclization of Siloxy Alkynes and Vinylazetidines
Authors: Wu An , Feng Qiang , Sung Herman H. Y. , Williams Ian D. , Sun Jianwei
Published: March 2019

A new approach for the efficient synthesis of eight‐membered lactams through formal [6+2] cyclization of siloxy alkynes and vinylazetidines has been developed. Evidence from a chirality transfer experiment suggests that the reaction proceeds via a [3,3]‐sigmatropic rearrangement from a ketene intermediate. This insight led to the development of alternative conditions and use of acyl chlorides as ketene precursors for the [6+2] reaction with vinylazetidines.
Exploding Chemical Gardens: A Phase‐Change Clock Reaction
Authors: Ding Yang , Gutiérrez‐Ariza Carlos M. , Ignacio Sainz‐Díaz C. , Cartwright Julyan H. E. , Cardoso Silvana S. S.
Published: March 2019

Chemical gardens and clock reactions are two of the best‐known demonstration reactions in chemistry. Until now these have been separate categories. We have discovered that a chemical garden confined to two dimensions is a clock reaction involving a phase change, so that after a reproducible and controllable induction period it explodes.
Protection‐Group‐Free Synthesis of Sequence‐Defined Macromolecules via Precision λ‐Orthogonal Photochemistry
Authors: Konrad Waldemar , Fengler Christian , Putwa Sarrah , Barner‐Kowollik Christopher
Published: March 2019

An advanced light‐induced avenue to monodisperse sequence‐defined linear macromolecules via a unique photochemical protocol is presented that does not require any protection‐group chemistry. Starting from a symmetrical core unit, precision macromolecules with molecular weights up to 6257.10 g mol−1 are obtained via a two‐monomer system: a monomer unit carrying a pyrene functionalized visible light responsive tetrazole and a photo‐caged UV responsive diene, enabling an iterative approach for chain growth; and a monomer unit equipped with a carboxylic acid and a fumarate. Both light‐induced chain growth reactions are carried out in a λ‐orthogonal fashion, exciting the respective photosensitive group selectively and thus avoiding protecting chemistry. Characterization of each sequence‐defined chain (size‐exclusion chromatography (SEC), high‐resolution electrospray ionization mass spectrometry (ESI‐MS), and NMR spectroscopy), confirms the precision nature of the macromolecules.
Synthesis, X‐ray characterization and density functional theory studies of N6‐benzyl‐N6‐methyladenine–M(II) complexes (M = Zn, Cd): The prominent role of π–π, C–H···π and anion–π interactions
Authors: Pons Roser , Ibáñez Cristina , Buades Ana B. , Franconetti Antonio , Garcia‐Raso Angel , Fiol Juan J. , Terrón Angel , Molins Elies , Frontera Antonio
Published: March 2019

We report the synthesis and X‐ray characterization of the N6‐benzyl‐N6‐methyladenine ligand (L) and three metal complexes, namely [Zn(HL)Cl3]·H2O (1), [Cd(HL)2Cl4] (2) and [H2L]2[Cd3(μ‐L)2(μ‐Cl)4Cl6]·3H2O (3). Complex1consists of the 7H‐adenine tautomer protonated at N3 and coordinated to a tetrahedral Zn(II) metal centre through N9. The octahedral Cd(II) in complex2is N9‐coordinated to two N6‐benzyl‐N6‐methyladeninium ligands (7H‐tautomer protonated at N3) that occupy apical positions and four chlorido ligands form the basal plane. Compound3corresponds to a trinuclear Cd(II) complex, where the central Cd atom is six‐coordinated to two bridging μ‐L and four bridging μ‐Cl ligands. The other two Cd atoms are six‐coordinated to three terminal chlorido ligands, to two bridging μ‐Cl ligands and to the bridging μ‐L through N3. Essentially, the coordination patterns, degree of protonation and tautomeric forms of the nucleobase dominate the solid‐state architectures of1–3. Additionally, the hydrogen‐bonding interactions produced by the endocyclic N atoms and NH groups stabilize high‐dimensional‐order supramolecular assemblies. Moreover, energetically strong anion–π and lone pair (lp)–π interactions are important in constructing the final solid‐state architectures in1–3. We have studied the non‐covalent interactions energetically using density functional theory calculations and rationalized the interactions using molecular electrostatic potential surfaces and Bader's theory of atoms in molecules. We have particularly analysed cooperative lp–π and anion–π interactions in1and π+–π+interactions in3.
Synthesis and characterization of eco‐friendly siloxane‐semifluorinated polyurethane coatings for underwater application
Authors: Yesudass Sebastin Anthony , Mohanty Smita , Nayak Sanjay K.
Published: March 2019

Siloxane‐semifluorinated polyurethane coatings were prepared for robust underwater application. Initially, acrylic polyol (FS‐GPTACP)‐containing fluoroalkoxysilane (1H,1H,2H,2H‐Perfluorooctyltrimethoxysilane) pendant group was synthesized by the free‐radical polymerization method. Different weight percentages of polydimethylsiloxane (0, 10, and 20 wt %) were added to the polyol to tune the mechanical and the surface energy of the coating. Subsequently, this polyol mixture was cured with 4, 4′‐methylenebis(cyclohexyl isocyanate) (H12MDI) to prepare a series of siloxane‐semifluorinated polyurethane–urea hybrid coatings (APUS 0%, APUS 10%, and APUS 20%). The synthesized coating showed low surface energy, hydrophobicity with exceptional water, and alkali resistance. Moreover, the coating displayed excellent mechanical properties with low pseudobarnacle adhesion strength. The coatings also showed nontoxicity against gram‐positive and gram‐negative bacterial strains. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47720.
Meeting the 24‐hr movement guidelines: An update on US youth with autism spectrum disorder from the 2016 National Survey of Children's Health
Authors: Healy Seán , Aigner Carrie J. , Haegele Justin A. , Patterson Freda
Published: March 2019

The purpose of this study was to examine how adherence to the physical activity (PA), screen‐time (ST), and sleep duration guidelines differ between youth with autism spectrum disorder (ASD) and youth with typical development (TD). A secondary objective was to assess how PA, ST, and sleep duration varied among youth with ASD by age and ASD severity. Utilizing the 2016 National Survey of Children's Health data, parental reports of time spent by youth in PA, ST, and sleep were used to determine adherence to the 24‐hr movement guidelines for 1008 youth with ASD and 34 489 youth with TD. Multivariate logistic regression analyses determined that children with ASD were less likely to meet the guidelines for PA, ST, and sleep duration, and adolescents with ASD were less likely to meet the guidelines for PA and ST than participants with TD. Furthermore, logistic regression analyses determined adolescents with severe ASD to be less likely to meet the sleep guideline compared to adolescents with mild ASD. Overall, youth with ASD were significantly less likely to adhere to all three guidelines. The findings highlight the breadth of health behaviors that require intervention to counteract the poorer health status among youth with ASD. Autism Res 2019, 12: 941–951. © 2019 International Society for Autism Research, Wiley Periodicals, Inc.

Lay Summary

New health recommendations suggest children and adolescents should have at least 1 hr of physical activity, no more than 2 hr of screen‐time (e.g., television), and 9–11 hr of sleep (or 8–10 hr for children aged 14 or older) every day. This article looked at how children and adolescents with autism meet these new guidelines. The two main results were that: (a) children with autism were less likely to meet all three guidelines compared to children without autism, and (b) adolescents with autism were less likely to meet the guidelines for physical activity and screen‐time.
Hierarchically Designed CNF/S−Cu/CNF Nonwoven Electrode as Free‐Standing Cathode for Lithium−Sulfur Batteries
Authors: Bian Zihao , Xu Ying , Yuan Tao , Peng Chengxin , Pang Yuepeng , Yang Junhe , Zheng Shiyou
Published: March 2019

A flexible lithium−sulfur (Li−S) battery cathode is prepared through uniformly depositing sulfur solution into an electrospun N‐rich and Cu‐decorated nonwoven carbon nanofiber (CNF) film to form sandwich structured CNF/S−Cu/CNF film electrodes. As a free‐standing cathode of Li−S battery, the unique structural CNF/S−Cu/CNF composite cathodes exhibit high capacity and rate capability as well as long cycling stability. The electrodes can deliver a reversible capacity of 1295 mAh g−1 at a current density of 0.1 A g−1, and maintain more than 530 mAh g−1 even at a high current rate of 1 A g−1 after 300 cycles along with a Coulombic efficiency close to 100 %. The exceptional performance of CNF/S−Cu/CNF as cathode in Li−S batteries is attributed to a synergistic contribution from the CNF layers, the decorated‐Cu nanoparticles and the doped N element in CNF, which can physically and chemically stabilize S and provide fast electronic conductivity. This facile strategy will pave the way to construct high‐performance flexible Li−S batteries.
Analysis of kombucha to teach biochemical concepts and techniques to undergraduate students
Authors: Applegate Kaitlin B. , Cheek Patrick R. , Inlow Jennifer K.
Published: March 2019

Laboratory exercises for undergraduate biochemistry students are described in which changes in sugar content during fermentation of the trendy beverage kombucha are analyzed by three methods: thin layer chromatography, a 3,5‐dinitrosalicylic acid assay, and a standard commercial blood glucose meter. Each of the three analyses can be completed in a typical laboratory session lasting two to three hours. The exercises are designed to reinforce concepts typically covered in an undergraduate biochemistry course as well as to teach a variety of laboratory techniques. The exercises have been used with positive results in an upper level biochemistry laboratory course for junior/senior students majoring in chemistry or biology. © 2019 International Union of Biochemistry and Molecular Biology, 47(4):459–467, 2019.
Exploring environmental, social, and governance disclosure effects on the S&P 500 financial performance
Authors: Minutolo Marcel C. , Kristjanpoller Werner D. , Stakeley John
Published: March 2019

Much of the literature measuring the relationship between environmental, social, and governance (ESG) scores and firm performance treats the score as a measure of sustainability performance. In this study, we treat a firm's ESG score as a demonstration of strategic choice in the level of transparency that results in increased firm performance as measured by Tobin's Q and return on assets. Performance differences are a result of choice moderated by the size of the firm as measured by employees and sales. We analyze 467 firms in the S&P 500 from 2009 to 2015. Applying legitimacy and stakeholder theory, we find that there is significant difference between groups with respect to disclosure and performance. The results of quartile analysis by sales, capitalization, and Tobin's Q are relevant to understand the influence that the ESG score has on financial performance. ESG influences on Tobin's Q are greatest for large firms as measured by sales, as opposed to the ESG affects on Tobin's Q and return on asset for smallest firms as measured by market capitalization.
Gene Expression Inside Liposomes: From Early Studies to Current Protocols
Authors: Stano Pasquale
Published: March 2019

Synthesizing proteins inside liposomes and other microcompartments is a well‐established practice. However, the origin of this research is not from the distant past, dating back to 1999–2004, when the first successful attempts were published. Protein synthesis inside artificial compartments is now under strong expansion in the context of synthetic biology (in bottom‐up approaches), and, in particular, it strongly contributes to the construction of artificial cell‐like systems. These systems, often called “synthetic cells”, can be used to model cellular processes, including membrane‐centered ones. They are very innovative models that complement traditional studies and promise future applications. This review does not discuss all current directions in synthetic cell research; in particular, it does not include all kinds of artificial compartments. Instead, it is uniquely dedicated to the analysis of historical and technical developments of protein synthesis inside liposomes, highlighting a selected list of open questions. One of the goals is to note the importance of mastering liposome technology together with cell‐free systems for the successful realization of this specific type of synthetic cell. With this aim, four currently employed protocols are compared and discussed, with a major emphasis on the droplet transfer method, which is attractive due to its simplicity and encapsulation efficiency.
Formation of the Charge‐Localized Dimer Radical Cation of 2‐Ethyl‐9,10‐dimethoxyanthracene in Solution Phase
Authors: Choi Jungkweon , Ahn Doo‐Sik , Fujitsuka Mamoru , Tojo Sachiko , Ihee Hyotcherl , Majima Tetsuro
Published: March 2019

Although dimer radical ions of aromatic molecules in the liquid‐solution phase have been intensely studied, the understanding of charge‐localized dimers, in which the extra charge is localized in a single monomer unit instead of being shared between two monomer units, is still elusive. In this study, the formation of a charge‐localized dimer radical cation of 2‐ethyl‐9,10‐dimethoxyanthracene (DMA), (DMA)2.+ is investigated by transient absorption (TA) and time‐resolved resonance Raman (TR3) spectroscopic methods combined with a pulse radiolysis technique. Visible‐ and near‐IR TA signals in highly concentrated DMA solutions supported the formation of non‐covalent (DMA)2.+ by association of DMA and DMA.+. TR3 spectra obtained from 30 ns to 300 μs time delays showed that the major bands are quite similar to those of DMA except for small transient bands, even at 30 ns time delay, suggesting that the positive charge of non‐covalent (DMA)2.+ is localized in a single monomer unit. From DFT calculations for (DMA)2.+, our TR3 spectra showed the best agreement with the calculated Raman spectrum of charge‐localized edge‐to‐face T‐shaped (DMA)2.+, termed DT.+, although the charge‐delocalized asymmetric π‐stacked face‐to‐face (DMA)2.+, termed DF3.+, is the most stable structure of (DMA)2.+ according to the energetics from DFT calculations. The calculated potential energy curves for the association between DMA.+ and DMA showed that DT.+ is likely to be efficiently formed and contribute significantly to the TR3 spectra as a result of the permanent charge‐induced Coulombic interactions and a dynamic equilibrium between charge localized and delocalized structures.
Halogen Bonds of Halotetrafluoropyridines in Crystals and Co‐crystals with Benzene and Pyridine
Authors: Schwabedissen Jan , Trapp Pia C. , Stammler Hans‐Georg , Neumann Beate , Lamm Jan‐Hendrik , Vishnevskiy Yury V. , Körte Leif A. , Mitzel Norbert W.
Published: March 2019

The structures of the three para‐substituted halotetrafluoropyridines with chlorine, bromine, and iodine have been determined in the solid state (X‐ray diffraction). The structures of these compounds and that of pentafluoropyridine were also determined in the gas phase (electron diffraction). Structures in the solid state of the bromine and iodine derivatives exhibit halogen bonding as a structure‐determining motif. On the way to an investigation of halogen bond formation of halotetrafluoropyridines in the solid state with the stronger Lewis base pyridine, co‐crystals of benzene adducts were investigated to gain an understanding of the influence of aryl–aryl interactions. These co‐crystals showed halogen bonding only for the two heavier halotetrafluoropyridines. In the pyridine co‐crystals halogen bonding was observed for all three para‐halotetrafluoropyridines. The formation of homodimers and heterodimers with pyridine is also supported by quantum‐chemical calculations of electron density topologies and natural bond orbitals.
Low‐Valent Group 14 NHC‐Stabilized Phosphinidenide ate Complexes and NHC‐Stabilized K/P‐Clusters
Authors: Balmer Markus , Weigend Florian , von Hänisch Carsten
Published: March 2019

The N‐heterocyclic carbene (NHC)‐stabilized phosphinidenide, SIMesPK [SIMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolidine‐2‐ylidene], was used as an (NHC)P‐transfer reagent for the synthesis of the low‐valent Group 14 ate complexes K[(SIMesP)3E] (E=Ge: 2, Sn: 3, Pb: 4), which were characterized by 1H NMR, 31P NMR, IR spectroscopy as well as elemental and X‐ray analysis. Furthermore, SIMesPK was used in reactions with potassium amides and alkoxides to form the molecular phosphorus–potassium clusters [K4(SIMesP)2(hmds)2] [5, hmds=N(SiMe3)2] and [K6(SIMesP)2(OtBu)4] (6). Finally, the reaction of SIMesPK with Li[Al(OC4F9)4] led to the potassium‐rich ionic compound [(SIMesP)4K5][Al(OC4F9)4] (7).
Exfoliating a CdII–Purine Framework: Conversion of Nanosheets‐to‐Nanofibers and Studies of Elastic and Capacitive Properties
Authors: Avasthi Ilesha , Kulkarni Manish M. , Verma Sandeep
Published: March 2019

Layered bulk crystals are amenable to exfoliation to yield 2D nanosheets through isolation and intercalation processes, which could be further converted to 1D nanoscale structures. The latter inherit gross morphological and physical properties associated with the precursor structures. Herein, we report three purine‐based crystal structures 1, 2, and 3, where 3 is obtained by a single‐crystal‐to‐single‐crystal transformation from 2 and is a conformational polymorph of 1. Next, we describe the sonication‐assisted liquid exfoliation of 1, a CdII–purine coordination framework, into nanosheets and nanofibers in a solvent‐dependent process. The exfoliation was carefully studied at low temperatures to ascertain this unique conversion. This work also features the determination of the Young's modulus and surface potential of the bioinspired CdII‐based nanostructures by using amplitude modulation–frequency modulation atomic force microscopy and Kelvin probe force microscopy, respectively, revealing their interesting elastic and capacitive properties for their possible use in electronics and energy devices. Electron impedance spectroscopy measurements further established a higher value of capacitance for the exfoliated CdII framework as compared to the ligand alone.
Biphasic Enantioselective Fluorescent Recognition of Amino Acids by a Fluorophilic Probe
Authors: Zhu Yuan‐Yuan , Wu Xue‐Dan , Abed Mehdi , Gu Shuang‐Xi , Pu Lin
Published: March 2019

A fluorophilic fluorescent probe based on a perfluoroalkyl‐substituted bis(binaphthyl) compound was designed and synthesized. It displayed a highly enantioselective fluorescence response toward structurally diverse amino acids in a biphasic fluorous/aqueous system with enantiomeric fluorescent enhancement ratio (ef; ΔID/ΔIL) values up to 45.2 (histidine). It can be used to determine the enantiomeric compositions of amino acids and also allows the amino acid enantiomers to be visually discriminated. NMR and mass‐spectroscopic investigations provided insights into the observed high enantioselectivity. This biphasic fluorescent recognition was used to determine the enantiomeric composition of the crude phenylalanine products generated by an enzyme‐catalyzed asymmetric hydrolysis under various reaction conditions. The fluorous‐phase‐based fluorescence measurement under the biphasic conditions was able to minimize the interference of other reaction components and thus has potential in asymmetric reaction screening.
Noncancer mortality among adolescents and young adults with cancer
Authors: Anderson Chelsea , Lund Jennifer L. , Weaver Mark A. , Wood William A. , Olshan Andrew F. , Nichols Hazel B.
Published: March 2019

Background

Relative to the general population, cancer patients and survivors may have an elevated risk of mortality from noncancer causes, such as cardiovascular disease and infections, but few studies have examined rates of noncancer mortality among patients diagnosed as adolescents and young adults (AYAs) (ages 15‐39 years).

Methods

The Surveillance, Epidemiology, and End Results database was used to identify AYA patients who were diagnosed with a first malignant cancer between 1973 and 2015. Rates of mortality from noncancer causes among AYAs with cancer were compared with those in the general US population using standardized mortality ratios (SMRs), adjusted for age, sex, race, and calendar year.

Results

Among 235,541 AYAs with cancer, a total of 12,948 deaths from noncancer causes occurred over 3.1 million total person‐years of follow‐up. Overall, noncancer mortality was significantly increased among AYAs with cancer relative to the general population (SMR, 1.84; 95% CI, 1.80‐1.87). SMRs were particularly elevated for infectious diseases (SMR, 5.13; 95% CI, 4.95‐5.32), cardiovascular disease (SMR, 1.55; 95% CI, 1.50‐1.60), and renal diseases (SMR, 2.40; 95% CI, 2.12‐2.71). These associations persisted for more than 20 years after cancer diagnosis. Cancer types associated with the highest SMRs for all noncancer mortality included leukemias (SMR, 5.26), Hodgkin lymphoma (SMR, 3.12), non‐Hodgkin lymphoma (SMR, 6.33), central nervous system tumors (SMR, 3.38), head and neck cancers (SMR, 2.09), and cervical/uterine cancers (SMR, 2.03).

Conclusions

AYAs with cancer have an elevated burden of mortality from noncancer causes that persists many years after cancer diagnosis, highlighting the importance of comprehensive, long‐term follow‐up care for noncancer conditions throughout survivorship.
Follow‐up with histopathology and HPV testing on LSIL cytology in China’s largest academic woman’s hospital
Authors: Tao Xiang , Zhang Huina , Zhang Hao , Xiao Jianan , Li Juan , Zhou Xianrong , Wang Li , Zhao Chengquan
Published: March 2019

Background

Cervical cancer remains a major health problem in China. To provide baseline data for establishing the appropriate screening strategy, the authors investigated the histopathologic follow‐up and human papillomavirus (HPV) testing results of low‐grade squamous intraepithelial lesion (LSIL) cytology in the Chinese Largest Women Hospital.

Methods

Women with LSIL cytology, human papillomavirus (HPV) testing, and immediate histopathologic follow‐up between 2011 and 2016 were analyzed.

Results

The frequency of LSIL among 1,095,022 Papanicolaou (Pap) tests was 1.4%, and was significantly higher in cases using liquid‐based cytology (LBC; 1.5%‐1.6%) compared with conventional Pap smears (CPS; 0.5%). The CPS method had performance for predicting cervical intraepithelial neoplasia (CIN) that was comparable to that of LBC (75% vs 69.1% and 71.9%). Among 8079 LSIL cases with an immediate histopathologic diagnosis, CIN‐2/3 or higher (CIN‐2/3+) was found in 11.9% of cases and carcinoma in 0.3% of cases. A total of 158 patients (15.7%) with HPV‐positive LSIL had a diagnosis of CIN‐2/3 compared with 18 patients (5.5%) with HPV‐negative LSIL. In postmenopausal women with LSIL cytology, the detection rate for CIN‐2/3 in HPV‐negative patients was significant lower than that in HPV‐positive patients. Furthermore, HPV type 16 (HPV‐16) was the most common genotype noted in patients with CIN‐2+ lesions, whereas HPV‐18 was the most common in patients with CIN‐1.

Conclusions

Although its reporting rate is lower than that of LBC, CPS is useful due to its low cost and comparable predictive value. HPV testing is helpful for stratifying postmenopausal women with LSIL into lower and higher risk groups. HPV‐16 is the most commonly identified genotype in CIN‐2+ lesions diagnosed in Chinese women with LSIL cytology, whereas HPV‐18 is the most commonly identified genotype in patients with CIN‐1 lesions.
Meta‐analysis of management effects on biodiversity in plantation and secondary forests of Japan
Authors: Spake Rebecca , Yanou Sakiko , Yamaura Yuichi , Kawamura Kazuhiro , Kitayama Kanehiro , Doncaster C. Patrick
Published: March 2019

Conservation of temperate forest biodiversity has historically focused on natural old‐growth. Less than 3% of the world's temperate forests remain unmodified by humans, however, and much of temperate‐forest biodiversity is held in the predominating planted and secondary forests. Japan provides a widely applicable model for examining how to maximize biodiversity in managed temperate forests, because of its richness of forestry research generated from its vast forest area, albeit largely in Japanese, and the wide practice of its dominant management interventions across the northern temperate zone. Management for plantations includes thinning, extended rotation cycles and clear‐cutting. For secondary forests regenerating from past clearance, traditional management varies in its intensities, from clear‐cutting as coppices to small‐scale understory clearance. Here we provide a first synthesis of published research on biodiversity in planted and secondary forests of Japan, relevant to management of these types of forest in northern temperate regions. Systematic review and meta‐analyses of papers published in English and Japanese quantified management impacts on species richness and abundance of several taxa, in relation to moderator variables including stand age and management intensity. Plantation thinning substantially increases the richness and abundance of several taxa. Effect sizes decline with time since thinning for the abundance of regenerating saplings and seedlings, necessitating repeated thinning treatments every 6 years to sustain this positive effect. Taxonomic groups exhibit variable relationships with stand age in both planted and secondary forests, indicating a need to include both young and old forest stands in managed forest mosaics. We find an insufficient evidence base is available to allow for a meaningful synthesis of low‐intensity management effects in historically managed secondary forests, with studies varying widely in scale and reported outcomes. We outline an agenda for the research community to achieve a systematic evaluation of scale‐dependent effects of traditional forest management on biodiversity.
Comparison of self‐adaptive dynamic differential evolution and particle swarm optimization for smart antennas in wireless communication
Authors: Chiu Chien‐Ching , Tong Yi‐Xiang , Cheng Yu‐Ting
Published: March 2019

In this paper, ultrawide band (UWB) communication systems with eight transmitting and receiving ring antenna arrays are implemented to test the bit error rate and capacity performance. By using the ray‐tracing technique to compute any given indoor wireless environment, the impulse response of the system can be calculated. The synthesized beamforming problem can be reformulated into a multiobjective optimization problem. Self‐adaptive dynamic differential evolution (SADDE) and particle swarm optimization (PSO) are used to find the excitation current and the feed line length of each antenna to form the appropriate beam pattern. This pattern can then reduce the bit error rate and increase the channel capacity and receiving energy. Numerical results show that the fitness value and the convergence speed by the SADDE are better than those by the PSO. Moreover, the SADDE had better results for both line‐of‐sight and nonline‐of‐sight cases. In other words, compared with PSO, SADDE has improved more effectively the main beam radiation energy and reduced the multipath interference.
The new normal: Disability inclusion in health science education
Authors: Meeks Lisa M.
Published: March 2019

Last year, we witnessed tremendous growth toward the inclusion of persons with disabilities in health science programs. A major report from the Association of American Medical Colleges, in partnership with the University of California, San Francisco School of Medicine examined the lived experiences of learners with disabilities and offered considerations for improving policy and practice.
Use your office's website to counter myths for prospective students
Authors: Hamblet Elizabeth C.
Published: March 2019

In addition to working in a disability services office, I travel the country doing presentations and write about preparing students with disabilities for successful college transition. In my conversations with students, parents, and high school professionals, and in online forums, I read and hear a lot of things that people believe about accommodations at college that aren't correct.
Was student's disability a factor in denial of readmission application?
Authors: Gelpi Aileen
Published: March 2019

The plaintiff began attending the Louisiana State University School of Medicine in 2010. At the outset, the administration was made aware of her bipolar disorder.
The latitudinal herbivory hypothesis revisited: To be part is to be whole
Authors: Gao Jianguo , Fang Changming , Zhao Bin
Published: March 2019

As the big data accumulation in ecology picks up pace, we now have the opportunity to test several macroecological hypotheses, such as the latitudinal herbivory hypothesis (LHH) dated from the 1990s. The LHH proposes that plant–herbivore interactions decrease as latitude increases, that is, from lower latitudinal areas (i.e., the equator) to higher latitudinal areas (i.e., the poles). This hypothesis has been challenged in recent years. In this study, we used the greatest volume dataset of leaf herbivory from the study of Zhang et al. (Journal of Ecology, 104, 2016, 1089) to test the LHH at a global scale, based on a quantile regression model. We found that the mean annual temperature, mean annual precipitation, and potential net primary production were heterogeneously correlated with herbivory at different quantiles or variable intervals. Although the Northern Hemisphere (NH) and the global‐scale trends are in accordance with the expected latitudinal variation, the Southern Hemisphere (SH) was found to exhibit inverse trends. The latitude has a negative effect on plant–herbivore interactions in the NH and on a global scale; leaf herbivory decreased more at a given latitude in higher latitudinal areas, which is attributed to harsher survival conditions in these areas. The uniformity of leaf herbivory variability along the climate and latitude gradient in the NH and on a global scale motivates that the loosening of this herbivory variability in the SH is not significant enough to dismiss the prevalence of the LHH, a testable macroecology hypothesis.
Effects of urbanization on cougar foraging ecology along the wildland–urban gradient of western Washington
Authors: Robins Clint W. , Kertson Brian N. , Faulkner James R. , Wirsing Aaron J.
Published: March 2019

Humans have dramatically altered ecosystem structure through landscape manipulation, often leaving refuge patches of suitable habitat for wildlife amidst inhospitable terrain. Large carnivores are especially vulnerable to such habitat modification because they tend to have low population densities and wide‐ranging movements necessitated by their food requirements. Cougars (Puma concolor), unlike many other large carnivores, have demonstrated an ability to exploit resources in fragmented and managed landscapes. The influence of increasing landscape development on cougar foraging behavior, however, has yet to be fully elucidated. Accordingly, we investigated variation in cougar use of three prey types (synanthropes, ungulates, and rodents) along a wildland–urban gradient in western Washington to determine how urbanization affects the foraging ecology of this apex predator. We predicted that cougar diets would comprise more synanthropic prey (e.g., prolific urban species) and fewer deer as a function of increasing residential development. Generalized linear mixed model results showed that the odds of cougar predation on synanthropic prey did increase with urbanization. The odds of ungulate predation, however, remained relatively consistent across the wildland–urban gradient despite cougar use of black‐tailed deer (Odocoileus hemionus columbianus) and elk (Cervus canadensis) increasing over time. These results suggest that cougar–ungulate predator–prey systems can persist in landscapes with substantial human presence. The odds of forest‐associated rodent (Castor sp., Aplodontia sp.) predation decreased with increasing development, suggesting that urbanization may coincide with more intensive beaver management near residences and thereby reduce beaver and mountain beaver presence in exurban landscapes in western Washington. Most cougars exhibited similar diets, but certain individuals deviated significantly from the population averages characterizing use of all three major prey categories. This variation suggests that cougar population responses to urbanization are unlikely to be uniform and that cases of human–cougar conflict may be linked to individual cats, rather than the population as a whole.
Triazenido Complexes of Titanocene(III)
Authors: Beweries Torsten , Reiß Fabian , Rothe Julia , Schulz Axel , Villinger Alexander
Published: March 2019

Triazenido metal complexes have been extensively investigated for more than a century, especially transition metal complexes. However, in each of the known examples for titanium, the oxidation state of the metal is +4. Therefore, we sought to prepare a complex containing titanium(III). To achieve this goal, triazenes RNNN(H)R′ (1R, with R = R′ = Ph; Dipp; Ter; R = Mes*, R′ = mTol) and triazenido salts Li[RNNNR′] (R = R′ = Ter; R = Ter, R′ = mTol) were prepared. These were treated with suitable titanium precursors either from reaction with the alkyne complex Cp2Ti(η2‐Me3SiC2SiMe3) or in a salt metathesis with [Cp2TiCl]2 to give chelate complexes of the type Cp2Ti[RNNNR′] (2R, with R =R′ = Ph; Dipp; R = Ter; R′ = mTol). The synthesis, reactivity, and bonding of the titanocene triazenides were studied.