bluuebunny/crossref_metadata_2025 huggingface dataset:
Stabilization and Topical Skin Delivery of Framework Nucleic Acids using Ionic Liquids
Authors: Tanner Eden E. L. , Wiraja Christian , Curreri Christina A. , Xu Chenjie , Mitragotri Samir
Published: April 2020

Framework nucleic acids (FNAs) are emerging nanocarriers owing to their inherent biocompatibility, precise assembly, and inherent compatibility with NA therapeutics. Topical administration of FNAs promises gene therapy of skin diseases. However, their stabilization and delivery efficiency across the stratum corneum remain a challenge. This work reports the use of choline carboxylic acid‐based ionic liquids to simultaneously address these two hurdles. First, the FNAs are assembled and solvated, and their structural stability is confirmed using fluorescence spectroscopy, dynamic light scattering, and gel electrophoresis. Of the six formulations tested, choline octenoate exhibits the best stabilizing properties at room temperature. Additionally, this formulation successfully transports FNAs into the lower dermis region in intact, ex vivo porcine skin.
Nanovortex‐Driven All‐Dielectric Optical Diffusion Boosting and Sorting Concept for Lab‐on‐a‐Chip Platforms
Authors: Canós Valero Adrià , Kislov Denis , Gurvitz Egor A. , Shamkhi Hadi K. , Pavlov Alexander A. , Redka Dmitrii , Yankin Sergey , Zemánek Pavel , Shalin Alexander S.
Published: April 2020

The ever‐growing field of microfluidics requires precise and flexible control over fluid flows at reduced scales. Current constraints demand a variety of controllable components to carry out several operations inside microchambers and microreactors. In this context, brand‐new nanophotonic approaches can significantly enhance existing capabilities providing unique functionalities via finely tuned light−matter interactions. A concept is proposed, featuring dual on‐chip functionality: boosted optically driven diffusion and nanoparticle sorting. High‐index dielectric nanoantennae is specially designed to ensure strongly enhanced spin−orbit angular momentum transfer from a laser beam to the scattered field. Hence, subwavelength optical nanovortices emerge driving spiral motion of plasmonic nanoparticles via the interplay between curl−spin optical forces and radiation pressure. The nanovortex size is an order of magnitude smaller than that provided by conventional beam‐based approaches. The nanoparticles mediate nanoconfined fluid motion enabling moving‐part‐free nanomixing inside a microchamber. Moreover, exploiting the nontrivial size dependence of the curled optical forces makes it possible to achieve precise nanoscale sorting of gold nanoparticles, demanded for on‐chip separation and filtering. Altogether, a versatile platform is introduced for further miniaturization of moving‐part‐free, optically driven microfluidic chips for fast chemical analysis, emulsion preparation, or chemical gradient generation with light‐controlled navigation of nanoparticles, viruses or biomolecules.
Shifting the odds of dryland farming: The career of B.A. Stewart
Authors: Evett Steven R. , Steiner Jean L.
Published: April 2020

Raised on a small dairy farm in semi‐arid western Oklahoma, Dr. B.A. Stewart was involved in agricultural challenges at an early age. Attending Oklahoma A&M College in Stillwater, he became enthralled by the power of chemistry and biology to address agricultural problems. He began a soil science career, first in Stillwater and later with the then new USDA Agricultural Research Service in Fort Collins, CO. Working on nitrogen pollution from feedlots, he developed new nitrogen assay methods, became involved in environmental work, and assisted in focusing the early work of the Environmental Protection Agency. In 1963, Stewart became Director of the USDA ARS Laboratory at Bushland, TX, where he developed programs in nitrogen and phosphorus management in dryland and irrigated agriculture, became a recognized proponent of soil and water conservation, worked with the beef cattle industry, and developed programs in dryland and irrigated cropping systems, including evapotranspiration measurement and modeling. Stewart became involved internationally through his work with USAID and ICARDA, service as Editor‐in‐Chief for the SSSA Journal, and editing of the book series, Advances in Soil Science, from 1985 to 2018. This led to the 1988 International Conference on Dryland Farming at Bushland. The 460 participants from 52 countries and 36 states defined the challenges in research and policy to develop future successful dryland farming. In 1993, Stewart retired from USDA ARS and became the first director of the Dryland Agriculture Institute at West Texas A&M University, teaching and researching with 74 successful M.S. and Ph.D. students over 24 years.
Acute mitral valve regurgitation causing severe alveolar hemorrhage
Authors: Sakamoto Ayaka , Enomoto Yuki , Watabe Hiroaki , Koyama Yasuaki , Matsumoto Yukei , Shimojo Nobutake , Marushima Aiki , Kawano Satoru , Inoue Yoshiaki
Published: April 2020

Background

Acute mitral regurgitation could occur without common symptoms like hemodynamic instability, but with dyspnea, hemoptysis, and right‐sided infiltration on radiography. We report a case of severe alveolar hemorrhage caused by acute mitral regurgitation, which occurred in the absence of shock.

Case Presentation

A 40‐year‐old man presented with dyspnea with bloody phlegm and hypoxia, despite being hemodynamically stable. Chest radiography revealed right‐sided infiltration, and bronchoscopy showed fresh bloody phlegm in his tracheae. No specific findings were detected with any tests. After treatment with several medications and support with extracorporeal membrane oxygenation, his condition improved, although the etiology of the disease remained unknown. Transthoracic and transesophageal echocardiogram revealed severe mitral valve regurgitation with ruptured mitral chordae tendineae. These suggested that the sudden onset of mitral valve regurgitation had caused severe alveolar hemorrhage.

Conclusion

Severe alveolar hemorrhage, especially with right‐sided infiltration on chest radiography, should be considered a symptom of acute mitral regurgitation.
Clinical and Magnetic Resonance Imaging Outcome Predictors in Pediatric Anti–N‐Methyl‐D‐Aspartate Receptor Encephalitis
Authors: Bartels Frederik , Krohn Stephan , Nikolaus Marc , Johannsen Jessika , Wickström Ronny , Schimmel Mareike , Häusler Martin , Berger Andrea , Breu Markus , Blankenburg Markus , Stoffels Johannes , Hendricks Oliver , Bernert Günther , Kurlemann Gerd , Knierim Ellen , Kaindl Angela , Rostásy Kevin , Finke Carsten
Published: April 2020

Objective

To evaluate disease symptoms, and clinical and magnetic resonance imaging (MRI) findings and to perform longitudinal volumetric MRI analyses in a European multicenter cohort of pediatric anti–N‐methyl‐D‐aspartate receptor encephalitis (NMDARE) patients.

Methods

We studied 38 children with NMDARE (median age = 12.9 years, range =1–18) and a total of 82 MRI scans for volumetric MRI analyses compared to matched healthy controls. Mixed‐effect models and brain volume z scores were applied to estimate longitudinal brain volume development. Ordinal logistic regression and ordinal mixed models were used to predict disease outcome and severity.

Results

Initial MRI scans showed abnormal findings in 15 of 38 (39.5%) patients, mostly white matter T2/fluid‐attenuated inversion recovery hyperintensities. Volumetric MRI analyses revealed reductions of whole brain and gray matter as well as hippocampal and basal ganglia volumes in NMDARE children. Longitudinal mixed‐effect models and z score transformation showed failure of age‐expected brain growth in patients. Importantly, patients with abnormal MRI findings at onset were more likely to have poor outcome (Pediatric Cerebral Performance Category score > 1, incidence rate ratio = 3.50, 95% confidence interval [CI] = 1.31–9.31, p = 0.012) compared to patients with normal MRI. Ordinal logistic regression models corrected for time from onset confirmed abnormal MRI at onset (odds ratio [OR] = 9.90, 95% CI = 2.51–17.28, p = 0.009), a presentation with sensorimotor deficits (OR = 13.71, 95% CI = 2.68–24.73, p = 0.015), and a treatment delay > 4 weeks (OR = 5.15, 95% CI = 0.47–9.82, p = 0.031) as independent predictors of poor clinical outcome.

Interpretation

Children with NMDARE exhibit significant brain volume loss and failure of age‐expected brain growth. Abnormal MRI findings, a clinical presentation with sensorimotor deficits, and a treatment delay > 4 weeks are associated with worse clinical outcome. These characteristics represent promising prognostic biomarkers in pediatric NMDARE. ANN NEUROL 2020 ANN NEUROL 2020;88:148–159
Reductively Caged, Photoactivatable DNA‐PAINT for High‐Throughput Super‐resolution Microscopy
Authors: Jang Soohyun , Kim Mingi , Shim Sang‐Hee
Published: April 2020

In DNA points accumulation in nanoscale topography (DNA‐PAINT), capable of single‐molecule localization microscopy with sub‐10‐nm resolution, the high background stemming from the unbound fluorescent probes in solution limits the imaging speed and throughput. Herein, we reductively cage the fluorescent DNA probes conjugated with a cyanine dye to hydrocyanine, acting as a photoactivatable dark state. The additional dark state from caging lowered the fluorescent background while enabling optically selective activation by total internal reflection (TIR) illumination at 405 nm. These benefits from “reductive caging” helped to increase the localization density or the imaging speed while preserving the image quality. With the aid of high‐density analysis, we could further increase the imaging speed of conventional DNA‐PAINT by two orders of magnitude, making DNA‐PAINT capable of high‐throughput super‐resolution imaging.
Tailoring the Morphology and Fractal Dimension of 2D Mesh‐like Gold Gels
Authors: Hiekel Karl , Jungblut Swetlana , Georgi Maximilian , Eychmüller Alexander
Published: April 2020

As there is a great demand of 2D metal networks, especially out of gold for a plethora of applications we show a universal synthetic method via phase boundary gelation which allows the fabrication of networks displaying areas of up to 2 cm2. They are transferred to many different substrates: glass, glassy carbon, silicon, or polymers such as PDMS. In addition to the standardly used web thickness, the networks are parametrized by their fractal dimension. By variation of experimental conditions, we produced web thicknesses between 4.1 nm and 14.7 nm and fractal dimensions in the span of 1.56 to 1.76 which allows to tailor the structures to fit for various applications. Furthermore, the morphology can be tailored by stacking sheets of the networks. For each different metal network, we determined its optical transmission and sheet resistance. The obtained values of up to 97 % transparency and sheet resistances as low as 55.9 Ω/sq highlight the great potential of the obtained materials.
A Vinyl Cyclopropane Ring Expansion and Iridium‐Catalyzed Hydrogen Borrowing Cascade
Authors: Wübbolt Simon , Cheong Choon Boon , Frost James R. , Christensen Kirsten E. , Donohoe Timothy J.
Published: April 2020

A vinyl cyclopropane rearrangement embedded in an iridium‐catalyzed hydrogen borrowing reaction enabled the formation of substituted stereo‐defined cyclopentanes from Ph* methyl ketone and cyclopropyl alcohols. Mechanistic studies provide evidence for the ring‐expansion reaction being the result of a cascade based on oxidation of the cyclopropyl alcohols, followed by aldol condensation with the pentamethyl phenyl‐substituted ketone to form an enone containing the vinyl cyclopropane. Subsequent single electron transfer (SET) to this system initiates a rearrangement, and the catalytic cycle is completed by reduction of the new enone. This process allows for the efficient formation of diversely substituted cyclopentanes as well as the construction of complex bicyclic carbon skeletons containing up to four contiguous stereocentres, all with high diastereoselectivity.
Sulfonium Acids Loaded onto an Unusual Thiotemplate Assembly Line Construct the Cyclopropanol Warhead of a Burkholderia Virulence Factor
Authors: Trottmann Felix , Ishida Keishi , Franke Jakob , Stanišić Aleksa , Ishida‐Ito Mie , Kries Hajo , Pohnert Georg , Hertweck Christian
Published: April 2020

Pathogenic bacteria of the Burkholderia pseudomallei group cause severe infectious diseases such as glanders and melioidosis. Malleicyprols were identified as important bacterial virulence factors, yet the biosynthetic origin of their cyclopropanol warhead has remained enigmatic. By a combination of mutational analysis and metabolomics we found that sulfonium acids, dimethylsulfoniumpropionate (DMSP) and gonyol, known as osmolytes and as crucial components in the global organosulfur cycle, are key intermediates en route to the cyclopropanol unit. Functional genetics and in vitro analyses uncover a specialized pathway to DMSP involving a rare prokaryotic SET‐domain methyltransferase for a cryptic methylation, and show that DMSP is loaded onto the NRPS‐PKS hybrid assembly line by an adenylation domain dedicated to zwitterionic starter units. Then, the megasynthase transforms DMSP into gonyol, as demonstrated by heterologous pathway reconstitution in E. coli.
A Titanium Metal–Organic Framework with Visible‐Light‐Responsive Photocatalytic Activity
Authors: Cadiau Amandine , Kolobov Nikita , Srinivasan Sivaranjani , Goesten Maarten G. , Haspel Henrik , Bavykina Anastasiya V. , Tchalala Mohamed R. , Maity Partha , Goryachev Andrey , Poryvaev Artem S. , Eddaoudi Mohamed , Fedin Matvey V. , Mohammed Omar F. , Gascon Jorge
Published: April 2020

The one‐step synthesis and characterization of a new and robust titanium‐based metal–organic framework, ACM‐1, is reported. In this structure, which is based on infinite Ti−O chains and 4,4′,4′′,4′′′‐(pyrene‐1,3,6,8‐tetrayl) tetrabenzoic acid as a photosensitizer ligand, the combination of highly mobile photogenerated electrons and a strong hole localization at the organic linker results in large charge‐separation lifetimes. The suitable energies for band gap and conduction band minimum (CBM) offer great potential for a wide range of photocatalytic reactions, from hydrogen evolution to the selective oxidation of organic substrates.
In Situ Formation of Liquid Metals via Galvanic Replacement Reaction to Build Dendrite‐Free Alkali‐Metal‐Ion Batteries
Authors: Ding Yu , Guo Xuelin , Qian Yumin , Gao Hongcai , Weber Daniel H. , Zhang Leyuan , Goodenough John B. , Yu Guihua
Published: April 2020

Galvanic replacement reactions have been studied as a versatile route to synthesize nanostructured alloys. However, the galvanic replacement chemistry of alkali metals has rarely been explored. A protective interphase layer will be formed outside templates when the redox potential exceeds the potential windows of nonaqueous solutions, and the complex interfacial chemistry remains elusive. Here, we demonstrate the formation of room‐temperature liquid metal alloys of Na and K via galvanic replacement reaction. The fundamentals of the reaction at such low potentials are investigated via a combined experimental and computational method, which uncovers the critical role of solid‐electrolyte interphase in regulating the migration of Na ions and thus the alloying reaction kinetics. With in situ formed NaK liquid alloys as an anode, the dendritic growth of alkali metals can be eliminated thanks to the deformable and self‐healing features of liquid metals. The proof‐of‐concept battery delivers reasonable electrochemical performance, confirming the generality of this in situ approach and design principle for next‐generation dendrite‐free batteries.
Effect of Chain Length for Dicarboxylic Monomeric Units of Polyester Polyols on the Morphology, Thermal and Mechanical Properties of Thermoplastic Urethanes
Authors: Tuan Ismail Tuan N. M. , Ibrahim Nor A. , Palam Kosheela D. P. , Sendijarevic Aisa , Sendijarevic Ibrahim , M. Schiffman Christi , Hoong Seng S. , Noor Mohd A. M. , Yeong Shoot K. , Idris Zainab , Malek Emilia A. , Zainuddin Norhazlin , Sendijarevic Vahid
Published: April 2020

Polyester polyols of 2000 g mol−1 M mass were synthesized via polyesterification reaction of butane‐1,4‐diol (1,4‐BDO) with linear dicarboxylic acids (DCAs) of odd and even carbon numbers, ranging from C4 to C10. Melt transition temperatures and crystallization enthalpies of polyester polyols demonstrated differing trends between odd and even chain lengths of their DCA monomeric units, with the latter possessing higher melt transition temperatures and melting enthalpies. The underlying cause of this difference may be attributable to the formation of a crystalline phase between the polyols' alkyl groups, which leads to proper alignment of ester bonds to allow for formation of dipoles that effectively cancel the local polarization. Thermoplastic urethanes (TPUs) were prepared by reacting the polyester polyols with 4,4′‐methylene bis(phenyl isocyanate) (4,4′‐MDI) and 1,4‐BDO chain extender at mole ratio of 1:2:1, respectively. Morphology, thermal and mechanical properties of TPUs were measured. Mechanical properties of TPUs also differ according to even vs. odd chain length of DCA monomeric units: higher hardness, tensile strength, hysteresis and tensile set for the former. The difference in properties is likely related to differences in phase segregation between hard and soft segments as a result of formation of hydrogen bonds as well as dipole–dipole interactions. Therefore, these findings have practical significance in the selection of polyester polyols to design TPUs for their specific applications.
Tensile deformation and morphology changes in segmented elastomer films and fibers including mechanical property modeling
Authors: Sauer Bryan B. , Kampert William G.
Published: April 2020

Segmented polyether soft segment (SS) elastomers with different hard segments (HS) in film and fiber form were studied by birefringence, DSC, and tensile tests. To understand the morphological contributions to property differences, high resolution tapping AFM resolved ribbon‐like highly anisotropic hard domain (HD) lamellae in low modulus Pebax (polyamide 12 HS) and polyetherester (PEE), films, while lower HS content high melting poly(urethane urea) (PUU) had much smaller less anisotropic but higher melting HDs, explaining its enhanced thermal and mechanical hysteresis properties. Stress–strain tensile data demonstrate the excellent strength and toughness of PUUs and some spun PEE fibers, and film and fiber birefringence data applied during strain cycling up to very high stresses provided the molecular basis for the varying properties. The parameters from non‐Gaussian fits of tensile data provide insight into network properties for these systems exhibiting very high strengths and a large degree of strain hardening. Modeling of PEE and Pebax films also shows the effects of substantial plastic yielding of the HD networks. Tensile data were obtained as a function of strain rate and temperature to help understand the contributions of network restructuring and other factors. For fibers, strain rate data spanning seven decades show and unusual drop in strengths at very high strain rates. Temperature‐dependent tensile data also show large differences between PUU materials versus lower melting PEEs.
Preparation of Cr(VI)‐imprinted polypropylene nonwoven fibers using plasma polymerization‐assisted grafting
Authors: Luo Zhengwei , Xu Yiyang , Chen Haonan , Jiang Hui , Geng Wenhua , Wei Wuji , Lian Zhouyang
Published: April 2020

Polypropylene (PP) fibers were grafted with glycidyl methacrylate (GMA) using plasma polymerization and then aminated, imprinted, and crosslinked to prepare Cr(VI)‐imprinted fibers. The plasma polymerization conditions were optimized by single factor experiment and response surface methodology, and various properties and adsorption mechanism of the fibers were analyzed. The results showed that at pH 3, the imprinted fibers had a maximum Cr(VI) adsorption capacity of 173.36 mg/g, and the adsorption equilibrium could be reached within 40 min. In the presence of competing ions (SO42−, NO3− and PO43−) each at a concentration of 5 times of that of Cr(VI), the Cr(VI) adsorption rate of the fibers could be maintained at around 50%, which indicates that the imprinted fibers have high selectivity towards Cr(VI). The results also showed that the imprinted fibers had good reusability and enrichment ability, thus can be a good candidate for treating actual Cr(VI)‐contaminated water.
Composite of medium‐chain‐length polyhydroxyalkanoates‐co‐methyl acrylate and carbon nanotubes as innovative electrodes modifier in microbial fuel cell
Authors: Sirajudeen Abdul Azeez Olayiwola , Annuar Mohamad Suffian Mohamad , Subramaniam Ramesh
Published: April 2020

A microbial fuel cell is a sustainable and environmental‐friendly device that combines electricity generation and wastewater treatment through metabolic activities of microorganisms. However, low power output from inadequate electron transfer to the anode electrode hampers its practical implementation. Nanocomposites of oxidized carbon nanotubes and medium‐chain‐length polyhydroxyalkanoates (mcl‐PHA) grafted with methyl acrylate monomers enhance the electrochemical function of electrodes in microbial fuel cell. Extensive polymerization of methyl acrylate monomers within mcl‐PHA matrix, and homogenous dispersion of carbon nanotubes within the graft matrix are responsible for the enhancement. Modified electrodes exhibit high conductivities, better redox peak and reduction of cell internal resistance up to 76%. A stable voltage output at almost 700 mV running for 225 H generates maximum power and current density of 351 mW/m2 and 765 mA/m2, respectively. Superior biofilm growth on modified surface is responsible for improved electron transfer to the anode hence stable and elevated power output generation.
New approach for stability study and determination of fluvoxamine in raw materials and pharmaceuticals through condensation with 2,2‐dihydroxyindane‐1,3‐dione
Authors: Abu‐hassan Ahmed A. , Omar Mahmoud A. , Derayea Sayed M.
Published: April 2020

The present study describes the validation of a selective spectroscopic method for assay of fluvoxamine maleate (FXM). The validated method relies on condensation of FXM with 2,2‐dihydroxyindane‐1,3‐dione and phenylacetaldehyde using Teorell–Stenhagen buffer (pH 6.6) to give coloured fluorescent product measured at 482 nm using 386 nm as the excitation wavelength. The parameters influencing the reaction were studied precisely and adjusted accurately. The constructed calibration graph appeared rectilinear over the following range (0.8–14 μg ml−1) and the estimated limit of detection was 0.25 μg ml−1. Two pharmaceutical products from the Egyptian market were assayed using the suggested method and the final results agreed with measurements from other reported methods. Moreover, the drug was subjected to diverse stress conditions including acidic, alkaline, thermal, and photolytic degradation to examine the FXM stability. Directives from the International Conference on Harmonisation guidelines were applied to establish the validity of the work.
Benchmarking of abdominal surgery: a study evaluating the HARM score in a European national cohort
Authors: Helgeland J , Skyrud K , Lindahl A K , Keller D , Augestad K M
Published: April 2020

Background

Reliable, easily accessible metrics of surgical quality are currently lacking. The HARM (HospitAl length of stay, Readmission and Mortality) score is a composite measure that has been validated across diverse surgical cohorts. The aim of this study was to validate the HARM score in a national population of patients undergoing abdominal surgery.

Methods

Data on all abdominal surgery in Norwegian hospitals from 2011 to 2017 were obtained from the Norwegian Patient Registry. Readmissions and 30-day postoperative complications as well as deaths in and out of hospital were evaluated. The HARM scoring algorithm was tested after adjustment by establishing a newly proposed length of stay score. The correlation between the HARM score and complications, as well as the ability of aggregated HARM scores to discriminate between hospitals, were analysed. Risk adjustment models were developed for nationwide hospital comparisons.

Results

The data consisted of 407 113 primary operations on 295 999 patients in 85 hospitals. The HARM score was associated with complications and complication severity (Goodman–Kruskal γ value 0·59). Surgical specialty was the dominating variable for risk adjustment. Based on 1-year data, the risk-adjusted score classified 16 hospitals as low HARM score and 16 as high HARM score of the 53 hospitals that had at least 30 operations.

Conclusion

The HARM score correlates with major outcomes and is associated with the presence and severity of complications. After risk adjustment, the HARM score discriminated strongly between hospitals in a European population of abdominal surgery.
Environmental policies, national culture, and stock price crash risk: Evidence from renewable energy firms
Authors: Yildiz Yilmaz , Karan Mehmet Baha
Published: April 2020

This study investigates the impact of country‐level environmental performance and national culture on the stock price crash risk of renewable energy firms. Employing a large sample of 626 renewable energy firms across 31 countries, we find a significant nonlinear relationship between country‐level environmental performance and crash risk. National culture dimensions are found to strongly predict the crash risk of renewable energy firms, particularly after the global financial crisis. On the contrary, national culture dimensions and environmental policies are observed to not exert any significance in explaining the crash risk of fossil fuel firms. Our results are robust with respect to alternative measures of stock price crash risk and the endogeneity of national culture dimensions. Overall, the findings of this paper contribute to the environmental economics literature by providing new evidence regarding the role of societal and environmental factors in explaining the stock price crash risk of energy firms.
Iron‐Based Nanozymes in Disease Diagnosis and Treatment
Authors: Shi Chu , Li Yan , Gu Ning
Published: April 2020

Iron‐based nanozymes are currently one of the few clinical inorganic nanoparticles for disease diagnosis and treatment. Overcoming the shortcomings of natural enzymes, such as easy inactivation and low yield, combined with their special nanometer properties and magnetic functions, iron‐based nanozymes have broad prospects in biomedicine. This minireview summarizes their preparation, biological activity, catalytic mechanism, and applications in diagnosis and treatment of diseases. Finally, challenges to their future development and the trends of iron‐based nanozymes are discussed. The purpose of this minireview is to better understand and reasonably speculate on the rational design of iron‐based nanozymes as an increasingly important new paradigm for diagnostics.
Effect of proximal balloon edge dilation technique for opening a side branch ostium in repetitive‐proximal optimizing technique sequence
Authors: Kume Teruyoshi , Murasato Yoshinobu , Yamada Ryotaro , Koyama Terumasa , Tamada Tomoko , Imai Koichiro , Okamoto Hiroshi , Enzan Ayano , Neishi Yoji , Uemura Shiro
Published: April 2020

Objective

The purpose of this experimental bench test was to compare stent deformation, obstruction of stent struts at a jailed side branch (SB) ostium, and stent strut malapposition between SB inflation using proximal balloon edge dilation (PBED) technique and SB inflation using conventional balloon dilation in repetitive‐proximal optimizing technique (re‐POT) sequence.

Background

The second proximal optimizing technique (POT) procedure in the re‐POT sequence might increase obstruction of stent struts at a jailed SB ostium, because deformation of stent cells at the main branch (MB) occurred during SB inflation for opening the SB ostium.

Methods

A fractal coronary bifurcation bench model made of flexible urethane was used, and crossover single‐stent implantation (Xience Sierra, Abbott Vascular, Santa Clara, CA, n = 12) was performed from the MB with the re‐POT sequence. During the re‐POT sequence, the jailing rate at the SB ostium assessed by videoscopy was compared between SB inflation using PBED technique (PBED group, n = 6) and SB inflation using conventional balloon dilation (conventional group, n = 6).

Results

The jailing rate after the second POT procedure tended to be lower in the PBED group than in the conventional group (26 ± 12% vs. 34 ± 8%, p = .211), and the change in the jailing rate during the second POT procedure was significantly smaller in the PBED group than in the conventional group (4.8 ± 5.3% vs. 11.6 ± 3.5%, p = .026).

Conclusions

In the re‐POT sequence, the PBED technique with a short balloon for SB inflation might minimize worsening of the jailing rate at the SB ostium during the second POT procedure.
Carbon Nanotube‐Based Molecularly Imprinted Voltammetric Sensor for Selective Diuretic Analysis of Dialysate and Hemodialysis Wastewater
Authors: de Oliveira Gabriela F. , Hudari Felipe F. , Pereira Fabíola M. V. , Zanoni Maria V. B. , da Silva José L.
Published: April 2020

A molecularly imprinted polymer (MIP)‐based electrochemical sensor was developed for the monitoring of hydrochlorothiazide (HCT) in dialysate and hemodialysis wastewater. The MIP was constructed by the electropolymerization of ortho‐phenylenediamine on multi‐walled carbon nanotube modified glassy carbon electrode surface. The experimental optimization was carried out by Plackett‐Burman design screening and central composite design. Through square wave voltammetry (SWV) analysis, the sensor presented linear response in the range of 5.0×10−6 to 1.0×10−4 mol L−1 (R=0.9995) and detection limit of 3.2×10−6 mol L−1. The film morphology was investigated by SEM, EDX and AFM, and the electrochemical response was confirmed by EIS. The MIP film exhibited excellent selectivity for HCT, rapid response and good practicability. The sensor was successfully applied for direct and selective determination of HCT in dialysate and hemodialysis wastewater samples with recovery rates ranging from 97 % to 102 % based on the standard addition method.
Redox Mediator‐Based Microbial Biosensors for Acute Water Toxicity Assessment: A Critical Review
Authors: Fang Deyu , Gao Guanyue , Yang Yajie , Wang Yu , Gao Lijuan , Zhi Jinfang
Published: April 2020

Water toxicity assessment is of great importance for monitoring water quality and safeguarding ecological health. Microbial biosensors, which use microorganisms as the bioreceptor, offer a promising complementary method for water quality evaluation. The present Minireview has particular emphasis on microbial biosensors that use redox mediators as signal indicators and their performance for water acute toxicity assessment. The principles, fabrication methods, and recent developments of electrochemical microbial biosensors are systematically summarized. In addition, the application of microbial fuel cells in water biological oxygen demand and biotoxicity determination are also briefly introduced. The main hurdles that hinder the on‐site application of electrochemical microbial biosensors are discussed. With unceasing efforts on improvement of sensitivity and stability, electrochemical microbial biosensors are promising to play more crucial roles in water quality evaluation.
Remarkable Energy Barrier for Magnetization Reversal in 3D and 2D Dysprosium‐Chloranilate‐Based Coordination Polymers
Authors: Mondal Arpan , Roy Subhadip , Konar Sanjit
Published: April 2020

Herein, two coordination polymers (CPs) [{Dy(Cl2An)1.5(CH3OH)}⋅4.5 H2O]n (1) and [Dy(Cl2An)1.5(DMF)2]n (2), in which Cl2An is chloranilate (2,5‐dihydroxy‐1,4‐benzoquinone dianion), exhibiting field‐induced single‐molecule magnet behavior with moderate barrier of magnetization reversal are reported. Detailed structural and topological analysis disclosed that 1 has a 3D network, whereas 2 has a 2D layered‐type structure. In both CPs, magnetic measurements showed weak antiferromagnetic exchange interaction between the dysprosium centers and field‐induced slow magnetic relaxation with barriers of 175(9)K and 145(7)K for 1 and 2, respectively. Notably, the energy barriers of magnetization reversal of 1 and 2 are remarkable for metal–chloranilate‐based 3D (1) and 2D (2) CPs. The temperature and field dependence of relaxation time indicate the presence of multiple relaxation pathways, such as direct, quantum tunneling of magnetization, Raman, and Orbach processes, in both CPs. Ab initio theoretical calculations reinforced the experimentally observed higher energy barrier in 1 as compared with 2 due to the presence of large transverse anisotropy in the ground state in the latter. The average transition magnetic moment between the computed low‐lying spin–orbit states also rationalized the relaxation as Orbach and Raman processes through the first excited state. BS‐DFT calculations were carried out for both CPs to provide more insight into the exchange interaction.
Nanostructures for Electrocatalytic CO2 Reduction
Authors: Ouyang Ting , Huang Sheng , Wang Xiao‐Tong , Liu Zhao‐Qing
Published: April 2020

One of the most effective ways to cope with the problems of global warming and the energy shortage crisis is to develop renewable and clean energy sources. To achieve a carbon‐neutral energy cycle, advanced carbon sequestration technologies are urgently needed, but because CO2 is a thermodynamically stable molecule with the highest carbon valence state of +4, this process faces many challenges. In recent years, electrochemical CO2 reduction has become a promising approach to fix and convert CO2 into high‐value‐added fuels and chemical feedstock. However, the large‐scale commercial use of electrochemical CO2 reduction systems is hindered by poor electrocatalyst activity, large overpotential, low energy conversion efficiency, and product selectivity in reducing CO2. Therefore, there is an urgent need to rationally design highly efficient, stable, and scalable electrocatalysts to alleviate these problems. This minireview also aims to classify heterogeneous nanostructured electrocatalysts for the CO2 reduction reaction (CDRR).
Discovery and Biomimetic Synthesis of a Phloroglucinol‐Terpene Adduct Collection from Baeckea frutescens and Its Biogenetic Origin Insight
Authors: Luo Shi‐Lin , Hu Li‐Jun , Huang Xiao‐Jun , Su Jun‐Cheng , Shao Xue‐Hua , Wang Lei , Xu Han‐Hong , Li Chuang‐Chuang , Wang Ying , Ye Wen‐Cai
Published: April 2020

A phloroglucinol‐terpene adduct (PTA) collection consisting of twenty‐four molecules featuring three skeletons was discovered from Baeckea frutescens. Inspired by its biosynthetic hypothesis, we synthesized this PTA collection by reductive activation of stable phloroglucinol precursors into highly reactive ortho‐quinone methide (o‐QM) intermediates and subsequently Diels–Alder cycloaddition. We also demonstrated, for the first time, the generation process of the active o‐QM by performing dynamic NMR and HPLC‐MS monitoring experiments. Moreover, the PTA collection showed significant antifeedant effect toward the Plutella xylostella larvae.
2,7,11,16‐Tetra‐tert‐Butyl Tetraindenopyrene Revisited by an “Inverse” Synthetic Approach
Authors: Elbert Sven M. , Haidisch Anika , Kirschbaum Tobias , Rominger Frank , Zschieschang Ute , Klauk Hagen , Mastalerz Michael
Published: April 2020

A new synthetic route to tetraindenopyrene (TIP)—a bowl‐shaped cut‐out structure of C70—is reported. The key step in this approach is a fourfold palladium‐catalyzed C−H activation that increases the yield more than 50 times in comparison to the approach originally described by Scott and co‐workers. Besides examination of its optoelectronic properties and study of its aggregation in solution, TIP was also re‐investigated by dispersion‐corrected DFT methods, which showed that dispersion interactions significantly increase the bowl‐to‐bowl inversion barrier. Furthermore, TIP was used as a semiconductor in p‐channel thin‐film transistors (TFTs).
Synthesis of Diverse Aromatic Ketones through C−F Cleavage of Trifluoromethyl Group
Authors: Ikeda Mai , Matsuzawa Tsubasa , Morita Takamoto , Hosoya Takamitsu , Yoshida Suguru
Published: April 2020

An efficient synthetic method of aromatic ketones through C−F cleavage of trifluoromethyl group is disclosed. The high functional group tolerance of the transformation and the remarkable stability of trifluoromethyl group in various reactions enabled multi‐substituted aromatic ketone synthesis in an efficient route involving useful transformations such as ortho‐lithiation, aryne chemistry, and cross‐couplings.
Thiourea‐Catalyzed C−F Bond Activation: Amination of Benzylic Fluorides
Authors: Houle Camille , Savoie Paul R. , Davies Clotilde , Jardel Damien , Champagne Pier Alexandre , Bibal Brigitte , Paquin Jean‐François
Published: April 2020

We describe the first thiourea‐catalyzed C−F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S‐ and O‐based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.
Linking population‐based registries to identify familial cancer risk in childhood cancer
Authors: Madanat‐Harjuoja Laura‐Maria , Pitkäniemi Janne , Hirvonen Elli , Malila Nea , Diller Lisa R.
Published: April 2020

Background

Linked population‐based registries provide a unique source for identification of new family cancer syndromes and for elucidating risk of early‐onset cancer in close relatives of cancer patients.

Methods

Using the Finnish Cancer Registry, we identified 9078 probands who had been diagnosed with cancer at <21 years of age between 1970 and 2012. Siblings, offspring, parents, nephews, and nieces of probands were identified from the Population Registry. Childhood and young adult (ChYA) cancer diagnoses (age 0‐39 years) in relatives were identified by linking to the Finnish Cancer Registry. The relative risk of ChYA cancer in family members of probands was estimated using standardized incidence ratios (SIRs).

Results

Among 58,010 family members of the 9078 probands, 363 ChYA cancers were diagnosed, 324 of which were expected (SIR, 1.12; 95% CI, 1.01‐1.24). The risk of ChYA cancer was elevated both in offspring (SIR, 2.25; 95% CI, 1.51‐3.24) and in siblings (SIR, 1.17; 95% CI, 1.01‐1.36). Offspring of probands with retinoblastoma were at highest risk (SIR, 75.85; 95% CI, 32.75‐149.45); risks were also elevated for siblings of probands with lymphoma (SIR, 1.62; 95% CI, 1.14‐2.25). Known cancer predisposition syndromes were observed in 29 (66%) of 44 sibling pairs with cancers diagnosed at <21 years of age and in 20% of the 135 families with a childhood cancer proband whose sibling was diagnosed with a young adult malignancy.

Conclusion

Linked population‐based registry data indicate a modestly increased risk of ChYA in relatives of children with cancer. Some of the observed cancer clusters in the cohort suggest novel patterns and familial cancer syndromes.
Prognostic significance of an invasive leader cell–derived mutation cluster on chromosome 16q
Authors: Pedro Brian , Rupji Manali , Dwivedi Bhakti , Kowalski Jeanne , Konen Jessica M. , Owonikoko Taofeek K. , Ramalingam Suresh S. , Vertino Paula M. , Marcus Adam I.
Published: April 2020

Background

Intratumoral heterogeneity is defined by subpopulations with varying genotypes and phenotypes. Specialized, highly invasive leader cells and less invasive follower cells are phenotypically distinct subpopulations that cooperate during collective cancer invasion. Because leader cells are a rare subpopulation that would be missed by bulk sequencing, a novel image‐guided genomics platform was used to precisely select this subpopulation. This study identified a novel leader cell mutation signature and tested its ability to predict prognosis in non–small cell lung cancer (NSCLC) patient cohorts.

Methods

Spatiotemporal genomic and cellular analysis was used to isolate and perform RNA sequencing on leader and follower populations from the H1299 NSCLC cell line, and it revealed a leader‐specific mutation cluster on chromosome 16q. Genomic data from patients with lung squamous cell carcinoma (LUSC; n = 475) and lung adenocarcinoma (LUAD; n = 501) from The Cancer Genome Atlas were stratified by 16q mutation cluster (16qMC) status (16qMC+ vs 16qMC−) and compared for overall survival (OS), progression‐free survival (PFS), and gene set enrichment analysis (GSEA).

Results

Poorer OS, poorer PFS, or both were found across all stages and among early‐stage patients with 16qMC+ tumors within the LUSC and LUAD cohorts. GSEA revealed 16qMC+ tumors to be enriched for the expression of metastasis‐ and survival‐associated gene sets.

Conclusions

This represents the first leader cell mutation signature identified in patients and has the potential to better stratify high‐risk NSCLC and ultimately improve patient outcomes.
Listwise learning to rank with extreme order sensitive constraint via cross‐correntropy
Authors: Liu Dezheng , Li Zhongyu , Ma Yuanyuan , Zhang Yulong
Published: April 2020

In information retrieval, learning to rank was originally proposed for ranking retrieved documents according to their relevance by machine learning techniques. In general, it can effectively improve the performance of critical ranking tasks, where the listwise approach is one of the most popular approaches adopted for ranking. However, considering that documents with more relevance receive greater attention, current ranking function based listwise approaches discriminate correctly ranked sequences with incorrect sequences; however, they are incapable of recognizing which incorrect sequences are relatively more satisfied. In this study, we propose a listwise approach based on an extreme order sensitive constraint to overcome the aforementioned drawback. We first define this constraint and then design a novel listwise loss function, ListXOS, based on the constraint via cross‐correntropy to improve the performance of ranking tasks. Experimental results on three public datasets present improved performance of learning to rank by 6% compared with conventional methods, which demonstrate the superiority of the proposed approach over related state‐of‐the‐art approaches.
Transformation of Metallic Ti to TiH2 Phase in the Ti/MgH2 Composite and Its Influence on the Hydrogen Storage Behavior of MgH2
Authors: Pukazhselvan D. , Sandhya Karakkadparambil Sankaran , Ramasamy Devaraj , Shaula Aliaksandr , Fagg Duncan Paul
Published: April 2020

The current work explores the in‐situ formation of TiH2 additive in a Ti/MgH2 nanocomposite system. Mild mechanical milling leaves Ti chemically unchanged, while formation of stable TiH2–x occurs upon strong mechanical milling. TiH2–x further transforms to TiH2 upon recycling the powder (dehydrogenation and subsequent hydrogenation) and lowers the activation energy of MgH2 to 89.4 kJ (mol H2)−1 [Ea of as‐received MgH2 is 153 kJ (mol H2)−1]. This work also reiterates that metallic Ti additive mixed MgH2 requires strong mechanical milling for better H2 ab/de‐sorption performance. The current observations support the view that lattice strain may be an important factor in the catalysis of additives incorporated MgH2 hydrogen storage systems.
A typology of nonsuicidal self‐injury in a clinical sample: A latent class analysis
Authors: Shahwan Shazana , Lau Jue Hua , Abdin Edimansyah , Zhang Yunjue , Sambasivam Rajeswari , Teh Wen Lin , Gupta Bhanu , Ong Say How , Chong Siow Ann , Subramaniam Mythily
Published: April 2020

Nonsuicidal self‐injury(NSSI) is a behavioural concern and can present in diverse ways, varying by method, frequency, severity, function and so forth. The possible combinations of these features of NSSI produce an array of profiles that makes evaluation and management of this behaviour challenging. The aim of this study was to build upon previous work that reduces the heterogeneity of NSSI patterns by using latent class analysis (LCA) to identify a typology of NSSI. Participants consisted of 235 outpatients aged 14–35 years attending a tertiary psychiatric hospital in Singapore who had reported at least one NSSI behaviour within the last year. Eight indicators captured using the Functional Assessment of Self‐Mutilation were used in the LCA: frequency of NSSI, length of contemplation before engaging in NSSI, usage of more than three NSSI methods, suicidal ideation and four psychological functions of NSSI, that is, social‐positive, social‐negative, automatic‐positive and automatic‐negative. The LCA revealed three distinct groups: Class 1—Experimental/Mild NSSI, Class 2—Multiple functions NSSI/Low Suicide Ideation and Class 3—Multiplefunctions NSSI/Possible Suicide Ideation. Multinomial logistic regression analyses were conducted to examine the associations between class membership and sociodemographic variables as well as measures of emotion dysregulation, childhood trauma, depression and quality of life. Females were overrepresented in Class 3. In general, Class 3 had the poorest scores followed by Class 2. Our analyses suggest that different NSSI subtypes require different treatment indications. Profiling patterns of NSSI may be a potentially useful step in guiding treatment plans and strategies.
Recurrent selection for improved seed germination results in greater seedling growth potential
Authors: Dhakal Kundan , Springer Tim L.
Published: April 2020

Rapid seedling development increases the probability of stand establishment. This research investigated the seedling growth of three little bluestem [Schizachyrium scoparium (Michx.) Nash] populations (NU‐1, UC‐2, and UO‐2), three selection generations (Recurrent Selection Cycles 0 [C0], 1 [C1], and 2 [C2]), and four seedling ages (3‐, 4‐, 5‐, and 6‐wk‐old seedlings). Lines NU‐1 C1 and NU‐1 C2 were developed from NU‐1 C0 using two cycles of recurrent selection for increased seed germination at a low water potential. Other lines were created similarly from UC‐2 C0 and UO‐2 C0. The greenhouse experiment was a three‐by‐three‐by‐four factorial of population, generation, and age in a randomized complete block design replicated nine times and repeated twice. Root length, shoot height, and root and shoot biomass varied with population and generation, and shoot/root ratio varied with population (P ≤ .01). Root length averaged 17.6 cm among populations and ranged from 16.4 cm for generation C0 to 18.3 cm for C2. Shoot height averaged 7.0 cm among populations and ranged from 6.5 cm for generation C0 to 8.3 cm for C2. Root biomass averaged 13.5 mg among populations and ranged from 11.3 mg for generation C0 to 16.5 mg for C2. Shoot biomass averaged 13.0 mg among populations and ranged from 11.1 mg for generation C0 to 15.8 mg for C2. Shoot/root ratio varied from 0.87 for population UC‐2 to 1.06 for NU‐1. Plant materials with rapid seedling growth should lead to better establishment and persistence.
The Synthesis of Primary Amines through Reductive Amination Employing an Iron Catalyst
Authors: Bäumler Christoph , Bauer Christof , Kempe Rhett
Published: April 2020

The reductive amination of ketones and aldehydes by ammonia is a highly attractive method for the synthesis of primary amines. The use of catalysts, especially reusable catalysts, based on earth‐abundant metals is similarly appealing. Here, the iron‐catalyzed synthesis of primary amines through reductive amination was realized. A broad scope and a very good tolerance of functional groups were observed. Ketones, including purely aliphatic ones, aryl–alkyl, dialkyl, and heterocyclic, as well as aldehydes could be converted smoothly into their corresponding primary amines. In addition, the amination of pharmaceuticals, bioactive compounds, and natural products was demonstrated. Many functional groups, such as hydroxy, methoxy, dioxol, sulfonyl, and boronate ester substituents, were tolerated. The catalyst is easy to handle, selective, and reusable and ammonia dissolved in water could be employed as the nitrogen source. The key is the use of a specific Fe complex for the catalyst synthesis and an N‐doped SiC material as catalyst support.