bluuebunny/crossref_metadata_2025 huggingface dataset:
Redox‐Triggered Chirality Switching and Guest‐Capture/Release with a Pillar[6]arene‐Based Molecular Universal Joint
Authors: Xiao Chao , Wu Wanhua , Liang Wenting , Zhou Dayang , Kanagaraj Kuppusamy , Cheng Guo , Su Dan , Zhong Zhihui , Chruma Jason J. , Yang Cheng
Published: January 2020

A chiral electrochemically responsive molecular universal joint (EMUJ) was synthesized by fusing a macrocyclic pillar[6]arene (P[6]) to a ferrocene‐based side ring. A single crystal of an enantiopure EMUJ was successfully obtained, which allowed, for the first time, the definitive correlation between the absolute configuration and the circular dichroism spectrum of a P[6] derivative to be determined. The self‐inclusion and self‐exclusion conformational change of the EMUJ led to a chiroptical inversion of the P[6] moiety, which could be manipulated by both solvents and changes in temperature. The EMUJ also displayed a unique redox‐triggered reversible in/out conformational switching, corresponding to an occupation/voidance switching of the P[6] cavity, respectively. This phenomenon is an unprecedented electrochemical manipulation of the capture and release of guest molecules by supramolecular hosts.
Photoredox Catalysis of Aromatic β‐Ketoesters for in Situ Production of Transient and Persistent Radicals for Organic Transformation
Authors: Yang Xiu‐Long , Guo Jia‐Dong , Xiao Hongyan , Feng Ke , Chen Bin , Tung Chen‐Ho , Wu Li‐Zhu
Published: January 2020

Radical formation is the initial step for conventional radical chemistry. Reported herein is a unified strategy to generate radicals in situ from aromatic β‐ketoesters by using a photocatalyst. Under visible‐light irradiation, a small amount of photocatalyst fac‐Ir(ppy)3 generates a transient α‐carbonyl radical and persistent ketyl radical in situ. In contrast to the well‐established approaches, neither stoichiometric external oxidant nor reductant is required for this reaction. The synthetic utility is demonstrated by pinacol coupling of ketyl radicals and benzannulation of α‐carbonyl radicals with alkynes to give a series of highly substituted 1‐naphthols in good to excellent yields. The readily available photocatalyst, mild reaction conditions, broad substrate scope, and high functional‐group tolerance make this reaction a useful synthetic tool.
Tunable Surface Wrinkling by a Bio‐Inspired Polyamine Anion Coacervation Process that Mediates the Assembly of Polyoxometalate Nanoclusters
Authors: Chilivery Rakesh , Begum Gousia , Chaitanya Vahinipathi , Rana Rohit Kumar
Published: January 2020

A bio‐inspired method is used to render controlled wrinkling surface patterns on supramolecular architectures assembled from polyoxometalate (POM) clusters. It involves a polyamine‐multivalent anion interaction generating positively charged coacervates, which while dictating the assembly of POM into spherical structures further facilitate an interesting surface morphogenesis with wrinkling patterns. This spontaneous surface wrinkling depends on the type of multivalent anion and the pH. As the polyamine‐anion interaction becomes stronger, the wrinkles turn denser with lesser depth, which eventually undergoes post‐buckling to engender a complex surface pattern. Interestingly, the order of influence exerted by different anions on the morphology follows the Hofmeister series. Moreover, the mild synthesis conditions keep the functional POM units dispersed in the sphere with a structural transformability to their lacunary form.
Photoresponsive Propeller‐like Chiral AIE Copper(I) Clusters
Authors: Kong Yu‐Jin , Yan Zhi‐Ping , Li Si , Su Hui‐Fang , Li Kai , Zheng You‐Xuan , Zang Shuang‐Quan
Published: January 2020

A pair of propeller‐like chiral trinuclear CuI clusters (R/S‐Cu3) with unique photoinduced fluorescence enhancement were prepared. R/S‐Cu3 showed intense variable luminescence after UV light irradiation, which was attributed to the stepwise oxidation of ligand in the clusters. It exhibited typical aggregation‐induced emission (AIE) (αAIE=17.3). Mechanism studies showed that metal cluster‐centered (MCC) and triplet metal‐to‐ligand charge‐transfer (3MLCT) processes are the origin of the luminescence; the processes are regulated by a restriction of intramolecular motions mechanism in a different state. The chiral structure and AIE feature endow R/S‐Cu3 with remarkable circularly polarized luminescence (glum=2×10−2) in the aggregated state. It shows good capability for producing reactive oxygen species. This work enriches the kinds of atomically precise AIE clusters, gains insight into their luminescence mechanism, and offers the prospect of application in multifunctional materials.
Nickel‐Catalyzed Asymmetric Hydrogenation of 2‐Amidoacrylates
Authors: Hu Yawen , Chen Jianzhong , Li Bowen , Zhang Zhenfeng , Gridnev Ilya D. , Zhang Wanbin
Published: January 2020

Earth‐abundant nickel, coordinated with a suitable chiral bisphosphine ligand, was found to be an efficient catalyst for the asymmetric hydrogenation of 2‐amidoacrylates, affording the chiral α‐amino acid esters in quantitative yields and excellent enantioselectivity (up to 96 %ee). The active catalyst component was studied by NMR and HRMS, which helped us to realize high catalytic efficiency on a gram scale with a low catalyst loading (S/C=2000). The hydrogenated products could be simply converted into chiral α‐amino acids, β‐amino alcohols, and their bioactive derivatives. Furthermore, the catalytic mechanism was investigated using deuterium‐labeling experiments and computational calculations.
Rheological improvement in performance of low‐rank coal–water slurries using novel cost‐effective additives
Authors: Amin Naila , Tahir Muhammad Suleman , Saleem Mehmood , Khan Zakir , Aslam Muhammad , Bazmi Aqeel Ahmed , Ghauri Moinuddin , Sagir Muhammad
Published: January 2020

Coal–water slurry (CWS) has been targeted as a promising fuel and an alternative to fuel oil. CWS has numerous advantages of low and convenient transportation and high solid content. Pakistan is going through a severe energy crisis and among the top 10 countries facing energy crises reported by the United Nations. Besides, Pakistan has become the top seventh country in coal reserves (i.e., 185 billion tones) after the discovery of huge lignite coal reserves in Thar, Sind province. Previous studies investigated the use of additives to enhance CWS properties at a low shear rate and its utilization accordingly. Particularly, the present work studied the high range of shear rate to improve the properties of CWS for transportation and combustion purposes. This study on the improvement in performance of rheology properties of CWS is conducted to improve the properties by cost‐effective additives. The coal concentration varies from 20% to 60%, whereas runs were carried out with and without the cost‐effective additives. The results demonstrated that the coal slurry showed shear‐thinning property when viscosity was increased at high concentrations in the absence of additives. The addition of additive changed the rheological behavior from pseudoplastic to dilatant region. The presence of a high fraction of coal increased the apparent viscosity of CWS. The static stability test of all coal samples was performed using rod drop method at concentrations of 40% to 60%. The study found that stability was achieved earlier with a lower concentration of 40% as compared with higher concentrations of 50–60%. It is expected that this research would be helpful for the country facing adverse energy crises that badly affect the economy and other social aspects of human life.
Design of a run‐to‐run controller based on discrete sliding‐mode observer
Authors: Wang Haiyan , Pan Tianhong , Ding Shihong , Chen Shan
Published: January 2020

In this study, a run‐to‐run controller based on a discrete sliding‐mode observer (DSMO) is presented for photolithography manufacturing processes. A second‐order DSMO is introduced to estimate the process disturbances caused by tool aging and preventive maintenance. The proposed controller is constructed by applying DSMO estimation to the deadbeat control law and the stable region is discussed. Numerical simulations and an industrial case demonstrated the performance of the proposed algorithm. It is observed that the proposed controller has a superior performance over the exponentially weighted moving average (EWMA) and double EWMA (dEWMA) controller under the first‐order integrated moving average disturbance with shift or drift. This superiority is maintained when the system contains a certain plant‐model mismatch. Moreover, the tolerance of the proposed controller for metrology delay is better than that of the dEWMA controller.
Future projections and uncertainty assessment of precipitation extremes in the Korean peninsula from the CMIP5 ensemble
Authors: Lee Youngsaeng , Shin Younggwan , Boo Kyung‐On , Park Jeong‐Soo
Published: January 2020

Projections of changes in extreme climate are sometimes predicted by multimodel ensemble methods that combine forecasts from individual simulation models using weighted averaging. One method to assign weight to each model is the Bayesian model averaging (BMA) in which posterior probability is used. For the cases of extreme climate, the generalized extreme value distribution (GEVD) is typically used. We applied the approach of GEV‐embedded BMA to a series of 35 years of the annual maximum daily precipitation data (both historical data and data gathered from simulation experiments for future periods) over the Korean peninsula as simulated by the models in the Coupled Model Intercomparison Project Phase 5 (CMIP5). Simulation data under two Representative Concentration Pathway (RCP) scenarios, namely RCP4.5 and RCP8.5, were used. Observed data and 17 CMIP5 models for 12 gird cells in Korea have been examined to predict future changes in precipitation extremes. A simple regional frequency analysis of pooling observations from three stations in each cell was employed to reduce the estimation variance and local fluctuations. A bias correction technique using the regression‐type transfer function was applied to these simulation data. Return levels spanning over 20 and 50 years, as well as the return periods relative to the reference years (1971–2005), were estimated for two future periods, namely Period 1 (2021–2050) and Period 2 (2066–2095). From these analyses, relative increase observed in the spatially averaged 20‐year (50‐year) return level was approximately 23% (16%) and 45% (36%) in the RCP4.5 and RCP8.5 experiments, respectively, by the end of the 21st century. We concluded that extreme rainfalls will likely occur two times and four times more frequently in the RCP4.5 and RCP8.5 scenarios, respectively, as compared to in the reference years by the end of the 21st century.
Autism Heterogeneity in a Densely Sampled U.S. Population: Results From the First 1,000 Participants in the RI‐CART Study
Authors: McCormick Carolyn E. B. , Kavanaugh Brian C. , Sipsock Danielle , Righi Giulia , Oberman Lindsay M. , Moreno De Luca Daniel , Gamsiz Uzun Ece D. , Best Carrie R. , Jerskey Beth A. , Quinn Joanne G. , Jewel Susan B. , Wu Pei‐Chi , McLean Rebecca L. , Levine Todd P. , Tokadjian Hasmik , Perkins Kayla A. , Clarke Elaine B. , Dunn Brittany , Gerber Alan H. , Tenenbaum Elena J. , Anders Thomas F. ,   Rhode Island Consortium for Autism Research and Treatment (RI‐CART), Sheinkopf Stephen J. , Morrow Eric M.
Published: January 2020

The objective of this study was to establish a large, densely sampled, U.S. population‐based cohort of people with autism spectrum disorder (ASD). The Rhode Island Consortium for Autism Research and Treatment (RI‐CART) represents a unique public‐private‐academic collaboration involving all major points of service for families in Rhode Island affected by ASD. Diagnosis was based on direct behavioral observation via the Autism Diagnostic Observation Schedule, Second Edition. For the first 1,000 participants, ages ranged from 21 months to 64 years. Using Geographic Information System and published prevalence rates, the overall cohort is estimated to represent between 20% and 49% of pediatric age persons in Rhode Island with ASD, with demographics representative of U.S. Census. We observed a high rate of co‐occurring medical and psychiatric conditions in affected individuals. Among the most prominent findings of immediate clinical importance, we found that females received a first diagnosis of ASD at a later age than males, potentially due to more advanced language abilities in females with ASD. In summary, this is the first analysis of a large, population‐based U.S. cohort with ASD. Given the depth of sampling, the RI‐CART study reflects an important new resource for studying ASD in a representative U.S. population. Psychiatric and medical comorbidities in ASD constitute a substantial burden and warrant adequate attention as part of overall treatment. Our study also suggests that new strategies for earlier diagnosis of ASD in females may be warranted. Autism Res 2020, 13: 474–488. © 2020 International Society for Autism Research, Wiley Periodicals, Inc.

Lay Summary

The Rhode Island Consortium for Autism Research and Treatment (RI‐CART) represents a unique public‐private‐academic collaboration involving all major points of service for families in Rhode Island affected by autism spectrum disorder (ASD). In this article, we provide results from the first 1,000 participants, estimated to represent >20% of affected families in the state. Importantly, we find a later age at first diagnosis of ASD in females, which potentially calls attention to the need for improved early diagnosis in girls. Also, we report a high rate of co‐occurring medical and psychiatric conditions in affected individuals.
Purification and characterization of chitinase from Paenibacillus sp.
Authors: Du Jinghe , Duan Shan , Miao Jianyin , Zhai Miaomiao , Cao Yong
Published: January 2020

The chitinase‐producing bacteria Paenibacillus sp. was isolated from soil samples. The chitinase was purified successively by ammonia sulfate fractional precipitation followed by chromatography on DEAE 52‐cellulose column and then on Sephadex G‐75 column. The chitinase has a molecular weight of ca. 30 kDa as measured by sodium dodecyl sulfate–polyacrylamide gel electrophoresis (SDS‐PAGE) electrophoresis. Its optimum pH is 4.5, and its optimum temperature is 50 °C with colloidal chitin as a substrate. The enzyme is stable below 45 °C and in pH ranges between 4.5 and 5.5. It is activated by glucosamine, glucose, N‐acetylglucosamine, and metal ions including Ca2+, Fe2+, Fe3+, and Ni2+. It is inhibited by SDS, H2O2, ascorbic acid, Cu2+, Mg2+, Ba2+, Sn2+, Cr3+, and K+. With colloidal chitin as substrate, the Km and the Vmax of the chitinase are 4.28 mg/mL and 14.29 μg/(Min·mL), respectively, whereas the end products of the enzymatic hydrolysis are 14.33% monomer and 85.67% dimer of N‐acetylglucosamine. The viscosity of carboxymethyl chitin decreased rapidly at the initial stages when subjected to chitinase hydrolysis, which indicates that the chitinase acts in an endosplitting pattern.
Generalized parametric cure models for relative survival
Authors: Jakobsen Lasse Hjort , Bøgsted Martin , Clements Mark
Published: January 2020

Cure models are used in time‐to‐event analysis when not all individuals are expected to experience the event of interest, or when the survival of the considered individuals reaches the same level as the general population. These scenarios correspond to a plateau in the survival and relative survival function, respectively. The main parameters of interest in cure models are the proportion of individuals who are cured, termed the cure proportion, and the survival function of the uncured individuals. Although numerous cure models have been proposed in the statistical literature, there is no consensus on how to formulate these. We introduce a general parametric formulation of mixture cure models and a new class of cure models, termed latent cure models, together with a general estimation framework and software, which enable fitting of a wide range of different models. Through simulations, we assess the statistical properties of the models with respect to the cure proportion and the survival of the uncured individuals. Finally, we illustrate the models using survival data on colon cancer, which typically display a plateau in the relative survival. As demonstrated in the simulations, mixture cure models which are not guaranteed to be constant after a finite time point, tend to produce accurate estimates of the cure proportion and the survival of the uncured. However, these models are very unstable in certain cases due to identifiability issues, whereas LC models generally provide stable results at the price of more biased estimates.
Smoothed empirical likelihood inference for ROC curve in the presence of missing biomarker values
Authors: Cheng Weili , Tang Niansheng
Published: January 2020

This paper considers statistical inference for the receiver operating characteristic (ROC) curve in the presence of missing biomarker values by utilizing estimating equations (EEs) together with smoothed empirical likelihood (SEL). Three approaches are developed to estimate ROC curve and construct its SEL‐based confidence intervals based on the kernel‐assisted EE imputation, multiple imputation, and hybrid imputation combining the inverse probability weighted imputation and multiple imputation. Under some regularity conditions, we show asymptotic properties of the proposed maximum SEL estimators for ROC curve. Simulation studies are conducted to investigate the performance of the proposed SEL approaches. An example is illustrated by the proposed methodologies. Empirical results show that the hybrid imputation method behaves better than the kernel‐assisted and multiple imputation methods, and the proposed three SEL methods outperform existing nonparametric method.
Retracted: JMJD6‐STAT3Y705ph axis promotes autophagy in osteosarcoma cancer cells by regulating ATG
Authors: Wang Kun , Du Baoyin , Xu Bin , Lv Xin
Published: January 2020

Background

Osteosarcoma cancer is a malignant tumor with poor outcome. Activation of STAT3 is closely related with tumor development. We intended to study the effects of JMJD6 on phosphorylation of STAT3 at Y705 site.

Methods

Osteosarcoma cancer cell lines (Saos‐2, MG‐63, and HOS) and clinical specimens were obtained. Interference RNA or JMJD6 mimic was transfected into the cells to silence or mimic JMJD6. Immunoprecipitation assay and glutathione S‐transferase (GST) pull down was implemented to investigate whether JMJD6 is associated with STAT3. STAT3‐null HOS cells were simultaneously transfected with the plasmids bearing STAT3WT or STAT3Y705F and EGFP‐tagged LC3 plasmids. Recombinant full‐length JMJD6 protein was subjected to in vitro kinase activity assay for testing its ability to phosphorylate STAT3. The severity of autophagy was indicated by the number of autophagosomes, expression of EGFP‐LC3, ratio of LC3‐II to LC3‐I, degradation percentage of long‐lived proteins and expression of autophagy associated gene (ATG).

Results

JMJD6 modulated the phosphorylation of STAT3 at Y705 site in osteosarcoma cells. Results from immunoprecipitation and GST pull down assays showed that JMJD6 associated with STAT3 in osteosarcoma cells. JMJD6 silence impeded the formation of autophagosomes, inhibited the accumulation of EGFP‐LC3, decreased the ratio of LC3‐II to LC3‐I, blocked the degradation of long‐lived proteins, and repressed the expression of ATG. JMJD6‐induced autophagy was impaired by STAT3Y705F which was not phosphorylated by JMJD6. The JMJD6‐STAT3Y705ph axis was implicated in the transcriptional regulation of ATG.

Conclusion

JMJD6 was included in regulating the phosphorylation of STAT3Y705 and promoted autophagy of osteosarcoma cells through its kinase activity.
Three‐Dimensional (3D) cell culture monitoring: Opportunities and challenges for impedance spectroscopy
Authors: De León Sorel E. , Pupovac Aleta , McArthur Sally L.
Published: January 2020

Three‐dimensional (3D) cell culture has developed rapidly over the past 5–10 years with the goal of better replicating human physiology and tissue complexity in the laboratory. Quantifying cellular responses is fundamental in understanding how cells and tissues respond during their growth cycle and in response to external stimuli. There is a need to develop and validate tools that can give insight into cell number, viability, and distribution in real‐time, nondestructively and without the use of stains or other labelling processes. Impedance spectroscopy can address all of these challenges and is currently used both commercially and in academic laboratories to measure cellular processes in 2D cell culture systems. However, its use in 3D cultures is not straight forward due to the complexity of the electrical circuit model of 3D tissues. In addition, there are challenges in the design and integration of electrodes within 3D cell culture systems. Researchers have used a range of strategies to implement impedance spectroscopy in 3D systems. This review examines electrode design, integration, and outcomes of a range of impedance spectroscopy studies and multiparametric systems relevant to 3D cell cultures. While these systems provide whole culture data, impedance tomography approaches have shown how this technique can be used to achieve spatial resolution. This review demonstrates how impedance spectroscopy and tomography can be used to provide real‐time sensing in 3D cell cultures, but challenges remain in integrating electrodes without affecting cell culture functionality. If these challenges can be addressed and more realistic electrical models for 3D tissues developed, the implementation of impedance‐based systems will be able to provide real‐time, quantitative tracking of 3D cell culture systems.
Plant‐derived protein bodies as delivery vehicles for recombinant proteins into mammalian cells
Authors: Schwestka Jennifer , Tschofen Marc , Vogt Stefan , Marcel Sylvain , Grillari Johannes , Raith Marianne , Swoboda Ines , Stoger Eva
Published: January 2020

The encapsulation of biopharmaceuticals into micro‐ or nanoparticles is a strategy frequently used to prevent degradation or to achieve the slow release of therapeutics and vaccines. Protein bodies (PBs), which occur naturally as storage organelles in seeds, can be used as such carrier vehicles. The fusion of the N‐terminal sequence of the maize storage protein, γ‐zein, to other proteins is sufficient to induce the formation of PBs, which can be used to bioencapsulate recombinant proteins directly in the plant production host. In addition, the immunostimulatory effects of zein have been reported, which are advantageous for vaccine delivery. However, little is known about the interaction between zein PBs and mammalian cells. To better understand this interaction, fluorescent PBs, resulting from the fusion of the N‐terminal portion of zein to a green fluorescent protein, was produced in Nicotiana benthamiana leaves, recovered by a filtration‐based downstream procedure, and used to investigate their internalization efficiency into mammalian cells. We show that fluorescent PBs were efficiently internalized into intestinal epithelial cells and antigen‐presenting cells (APCs) at a higher rate than polystyrene beads of comparable size. Furthermore, we observed that PBs stimulated cytokine secretion by epithelial cells, a characteristic that may confer vaccine adjuvant activities through the recruitment of APCs. Taken together, these results support the use of zein fusion proteins in developing novel approaches for drug delivery based on controlled protein packaging into plant PBs.
Online control of cell culture redox potential prevents antibody interchain disulfide bond reduction
Authors: Handlogten Michael W. , Wang Jihong , Ahuja Sanjeev
Published: January 2020

The phenomenon of monoclonal antibody (mAb) interchain disulfide bond reduction during manufacturing processes continues to be a focus of the biotechnology industry due to the potential for loss of product, increased complexity of purification processes, and reduced stability of the drug product. We hypothesized that antibody reduction can be mitigated by controlling the cell culture redox potential and subsequently established a threshold redox potential above which the mAb remained intact and below which there were significant and highly variable amounts of reduced mAb. Using this knowledge, we developed three control schemes to prevent mAb reduction in the bioreactor by controlling the cell culture redox potential via an online redox probe. These control methodologies functioned by increasing the concentration of dissolved oxygen (DO), copper (II) (Cu), or both DO and Cu to maintain the redox potential above the threshold value. Using these methods, we were able to demonstrate successful control of antibody reduction. Importantly, the redox control strategies did not significantly impact the cell growth, viability, mAb production, or product quality attributes including aggregates, C‐terminal lysine, high mannose, deamidation, and glycation. Our results demonstrate that controlling the cell culture redox potential is a simple and effective method to prevent mAb reduction.
Pressurized intraperitoneal aerosol chemotherapy: a review of the introduction of a new surgical technology using the IDEAL framework
Authors: Tate S J , Torkington J
Published: January 2020

Background

The IDEAL (Idea, Development, Evaluation, Assessment, Long-term study) framework is a scheme of investigation for innovative surgical therapeutic interventions. Pressurized intraperitoneal aerosol chemotherapy (PIPAC) is a procedure based on laparoscopy to deliver intraperitoneal chemotherapy for peritoneal metastases, introduced in 2011. The aim of this article was to review literature on PIPAC and assess whether development of the technique has followed the IDEAL framework.

Methods

A search of MEDLINE and Embase was carried out to identify scientific reports on PIPAC published between January 2000 and February 2019. The studies were categorized according to the IDEAL stages.

Results

Eighty-six original research papers on PIPAC were identified. There were 23 stage 0, 18 stage 1, 25 stage 2a and six stage 2b studies. Protocol papers for stage 1, 2b and 3 studies, and trial registrations for stage 2a studies, were also identified. The number of centres publishing reports and the number of publications has increased each year. Overall, there has been progression through the IDEAL stages; however, about 60 per cent of clinical reports published in 2018 were stage 1 Idea-type studies.

Conclusion

Since its introduction, studies investigating PIPAC have progressed in line with the IDEAL framework. However, the majority of studies reported recently were stage 0 and 1 studies.
A trip down memory lane: Antecedents and outcomes of ad‐evoked nostalgia on Facebook
Authors: Youn Seounmi
Published: January 2020

Integrating the theories of nostalgia and consumer‐brand relationships, this study developed and tested a theoretical model for understanding ad‐evoked nostalgia within the context of Facebook. Online survey data (n = 395) were collected using Amazon MTurk to disentangle the relationships between antecedents, ad‐evoked nostalgia, and outcomes. An analysis of the structural model revealed that the need to belong and nostalgia proneness had positive, direct effects on ad‐evoked nostalgia, which subsequently affected self‐brand connections and brand engagement behaviors on Facebook. Facebook use intensity was not found to influence ad‐evoked nostalgia. Theoretical and managerial implications, along with future research directions, were discussed.
Percutaneous closure of patent ductus arteriosus in premature infants: A French national survey: A Titanic movement in technology and technique— Beware the icebergs!
Authors: Wilson Neil
Published: January 2020

Key Points

First national multicenter report of interventional closure of patent ductus arteriosus in preterm infants.

Results describe commendable technical and procedural success of 99% with year‐on‐year tendency for intervention in smaller patients.

Reported complications (8.9%) and outcome (1‐year mortality 6.8%) are far superior to contemporary surgical intervention but indicate room for improvement.
Communication to cure cath chaos
Authors: Blankenship James C.
Published: January 2020

Key Points

Communication errors in the cath lab may lead to incorrect medication administration or dosing, or incorrect sizes of devices deployed in patients, with catastrophic results. Use of closed‐loop communication minimizes these errors.

In this study, two rounds of quality improvement projects improved, but did not completely close the communication gap.

Standard setting by professional societies and individual cath lab leaders may be necessary to improve the use of closed‐loop communication in cath labs—although a completely successful strategy remains to be identified.
Flexible fluoroscopes
Authors: Balter Stephen
Published: January 2020

Key Points

Different fluoroscopes have various controls that influence radiation output and clinical image quality.

“Standard” settings often result in relatively high radiation output as a way of producing image quality is high enough almost all procedures.

Operator knowledge of the characteristics of individual fluoroscopes is an essential element of radiation reduction below “standard settings” without reducing clinical benefits.
Microfluidic System with Extended‐Gate‐Type Organic Transistor for Real‐Time Glucose Monitoring
Authors: Didier Pierre , Lobato‐Dauzier Nicolas , Clément Nicolas , Genot Anthony J. , Sasaki Yui , Leclerc Éric , Minamiki Tsukuru , Sakai Yasuyuki , Fujii Teruo , Minami Tsuyoshi
Published: January 2020

Organic field‐effect transistors (OFETs) can be potentially employed to monitor cell activities for healthcare and medical treatment because of their attractive properties such as ease of use, flexibility, and low‐cost manufacturing processes. Although current OFET‐based sensors are suitable for point‐of‐care testing, the establishment of real‐time monitoring methods is in high demand for continuous monitoring of health conditions and/or biological cell activities. In this regard, we herein propose a microfluidic platform integrated with an extended‐gate‐type OFET for real‐time glucose monitoring. The mechanism of glucose detection depends on the artificial receptor phenylboronic acid and its boronate esterification. After optimization of the microfluidics for the OFET‐based sensor, the sensor was used to monitor glucose consumption and release in a model of pseudo‐liver cells. Random increases or decreases in the glucose concentration were reproducibly monitored.
Electrochemical Reduction of CO2 into C1 and C2 Hydrocarbons Using Dendritic Cu and Cu2O Electrodes
Authors: Feroze Muhammad Tajmeel , Sami Syed Kamran , Doonyapisut Dulyawat , Kim Byeongkyu , Chung Chan‐Hwa
Published: January 2020

Electroreduction of carbon dioxide to C1 and C2 hydrocarbons has emerged as an efficient way to utilize carbon dioxide and maintain the broken carbon‐cycle in the environment. Copper is a promising catalyst for such a purpose. The selectivity and stability of hydrocarbon production is still a challenge. Here we propose a simple one‐step electro‐deposition of copper followed by annealing in air, in which the dendritic structures of Cu and Cu2O electrodes have been prepared, to enhance the copper‐electrode properties in terms of morphology, selectivity, stability, and electrochemical performance. The selectivity of ethylene using modified dendritic Cu2O electrodes remains stable (from 19.21 % to 18.01 %) after the course of over 10 hours by applying a constant potential of −1.4 V. Our finding suggests a promising lead for the design of practical catalytic electrodes for the fuel synthesis with electrochemical CO2 reduction.
Influence of Quantum Dot Surface on Electrochemical DNA Sensing Mechanism
Authors: Fuku Xolile , Baker Priscilla , Iwuoha Emmanuel
Published: January 2020

Owing to their high surface‐to‐volume ratio, electrocatalytic activity, biocompatibility and novel electron transport properties, quantum dots (QDs) are highly attractive materials for the ultrasensitive detection of biological macromolecules via bioelectronic devices. In this study, a QD‐based genosensor was developed, in which Ga2Te3‐based QDs were synthesized using an aqueous solution approach by mixing 3‐mercaptosuccinic acid (3MSA)‐capped gallium metal precursor with reduced tellurium metal. The results enabled us to reach an original understanding related to the active material involved in the probe DNA sensing mechanism. The morphological and structural characterization of the QDs was performed prior to their utilization in a DNA sensor construction. High‐resolution TEM (HR‐TEM) and atomic force microscopy (AFM) images confirmed the spherical and crystalline nature of the QDs, whereas X‐ray photoelectron spectroscopy (XPS) and X‐ray diffraction (XRD) analyses were able to confirm the oxidation states and formation of the prepared QDs. UV/Vis was capable of finding the optical band gap energy and the photostability of the QDs. The resultant Ga2Te3 QDs together with metal ions confirmed their use for DNA signal detection through their DNA binding mechanism in the genosensor construction. Genosensing in Cs+ and Li+ ions exhibited high sensitivity (2.74–3.69 μA ng−1 mL) and very low detection limits (0.4 pg mL−1) with a linear dynamic range of 0.1–1 ng mL−1.
Multi‐Spectroscopic Interrogation of the Spatial Linker Distribution in Defect‐Engineered Metal–Organic Framework Crystals: The [Cu3(btc)2−x(cydc)x] Showcase
Authors: Rivera‐Torrente Miguel , Filez Matthias , Meirer Florian , Weckhuysen Bert M.
Published: January 2020

In the past few years, defect‐engineered metal–organic frameworks (DEMOFs) have been studied due to the plethora of textural, catalytic, or magnetic properties that can be enhanced by carefully introducing defect sites into the crystal lattices of MOFs. In this work, the spatial distribution of two different non‐defective and defective linkers, namely 1,3,5‐benzenetricarboxylate (BTC) and 5‐cyano‐1,3‐benzenedicarboxylate (CYDC), respectively, has been studied in different DEMOF crystals of the HKUST‐1 topology. Raman micro‐spectroscopy revealed a nonhomogeneous distribution of defect sites within the [Cu3(btc)2−x(cydc)x] crystals, with the CYDC linker incorporated into defect‐rich or defect‐free areas of selected crystals. Additionally, advanced bulk techniques have shed light on the nature of the copper species, which is highly dynamic and directly affects the reactivity of the copper sites, as shown by probe molecule FTIR spectroscopy. Furthermore, electron microscopy revealed the effect of co‐crystallizing CYDC and BTC on the crystal size and the formation of mesopores, further corroborated by X‐ray scattering analysis. In this way we have demonstrated the necessity of utilizing micro‐spectroscopy along with a whole array of bulk spectroscopic techniques to fully describe multicomponent metal–organic frameworks.
Diphenylberyllium Reinvestigated: Structure, Properties, and Reactivity of BePh2, [(12‐crown‐4)BePh]+, and [BePh3]−
Authors: Müller Matthias , Buchner Magnus R.
Published: January 2020

The first synthesis of BePh2 was accomplished almost a century ago. However, its structure has remained unknown so far, while the corresponding aryls of the elements adjacent to beryllium in the periodic table are well investigated. Herein, we present an improved synthesis for diphenylberyllium and show by X‐ray diffraction that it forms a trinuclear complex in the solid state. NMR spectroscopy revealed that this structure is also retained in solution but exhibits dynamic behavior. Its stability against heat and coordinating solvents is discussed and the possible obstacles to the synthesis of BePh2 from BeCl2 are examined. In the process of this study two ether adducts, BePh2⋅Et2O and Be2Ph4⋅Et2O, have been characterized as well as the previously unknown triphenylberyllate anion. From the latter several single‐crystal structures were obtained under various conditions, in which [BePh3]− is either isolated or acts as a ligand for Li+. Furthermore, the crown ether induced selfionization of BePh2 is described and the resulting [(12‐crown‐4)BePh]+ cation was isolated, which shows an unusual 4+1 coordination around the Be atom.
6‐Triphenylphosphinehexanoic Acid Conjugated Near‐Infrared Persistent Luminescence Nanoprobe for Autofluorescence‐Free Targeted Imaging of Mitochondria in Cancer Cells
Authors: Su Yu‐Bin , Zhao Xu , Chen Li‐Jian , Qian Hai‐Long , Yan Xiu‐Ping
Published: January 2020

Mitochondria, as the energy provider for cells, play a key role in cell physiological processes. Mitochondrion‐targeted imaging is of great significance for understanding the physiological functions and pathology involved in various diseases. Herein, we report the fabrication of 6‐triphenylphosphinehexanoic acid (TPP) conjugated near‐infrared persistent luminescence nanoparticles (PLNP) (PLNP‐TPP) for mitochondria‐targeted imaging in cancer cells. The PLNP was prepared by doping Cr(III) into gallogermanate through a hydrothermal method. The as‐prepared PLNP showed small size, monodispersity, excellent near‐infrared (NIR) luminescence and visible light renewable NIR luminescence. The grafted TPP facilitated the transportation of PLNP‐TPP across the mitochondrial membrane and enabled staining of the mitochondrial region in live cancer cells. This work provides a promising strategy for fabricating PLNP nanoprobes to realize mitochondrial‐targeting bioimaging.
Synthetic Biology Enables Programmable Cell‐Based Biosensors
Authors: Hicks Maggie , Bachmann Till T. , Wang Baojun
Published: January 2020

The front cover artwork is provided by the group of Dr. Baojun Wang (The University of Edinburgh). The image shows an engineered bacterial cell containing a genetic amplifier circuit which transforms a weak input signal into a larger easily detectable output signal. The electronics symbols used to illustrate the genetic circuit highlight the programmability of the circuit components enabled by state‐of‐the‐art synthetic biology tools. Read the full text of the Review at 10.1002/cphc.201900739.
High‐Pressure Synthesis of the Acentric Borate DyB5O8(OH)2
Authors: Zoller Michael , Heymann Gunter , Saxer Andreas , Huppertz Hubert
Published: January 2020

The novel dysprosium borate DyB5O8(OH)2 was synthesized in a Walker‐type multianvil apparatus at a pressure of 2.5 GPa and a temperature of 673 K. Single‐crystal diffraction data provided the basis for the structure solution and refinement. The compound crystallizes in the acentric monoclinic space group C2 (no. 5) with the lattice parameters a = 7.9288(5), b = 4.4009(3), c = 9.3409(8) Å, and a monoclinic angle of 113.76(1)°. Generally, DyB5O8(OH)2 is comprised of a layer‐like structure consisting of corner sharing [BO4]5– tetrahedra forming dreier and sechser rings, and eightfold coordinated dysprosium cations. Further characterizations were performed by IR and luminescence spectroscopy as well as high‐temperature X‐ray diffraction.
Niacin as a Potent Organocatalyst towards the Synthesis of Quinazolines Using Nitriles as C–N Source
Authors: Gujjarappa Raghuram , Vodnala Nagaraju , Reddy Velma Ganga , Malakar Chandi C.
Published: January 2020

An efficient and cost‐effective Vitamin‐B3‐catalyzed protocol towards the synthesis of diversely substituted quinazolines is illustrated using 2‐aminobenzylamines and nitriles as substrates. An organocatalytic transformation has been investigated where nitrile plays a role of C–N bond donor. The developed approach is applicable on a wide range of 2‐aminobenzylamines and nitriles for the synthesis of substituted quinazolines in high yields with a broad functional group tolerance.
Electrosynthesis of C3 Alkoxylated Quinoxalin‐2(1H)‐ones through Dehydrogenative C–H/O–H Cross‐Coupling
Authors: Jiang Xinpeng , Yang Liechao , Ye Zenghui , Du Xiaofan , Fang Liyun , Zhu Yu , Chen Keda , Li Jianjun , Yu Chuanming
Published: January 2020

A highly efficient electrochemically dehydrogenative C–H/O–H cross‐coupling between quinoxalin‐2(1H)‐ones and alcohols was developed under mild conditions. Using different types of alcohols as solvent, various 3‐alkoxylated quinoxalin‐2(1H)‐ones were synthesized in a simple undivided cell at room temperature. This novel electrochemical cross‐dehydrogenative coupling approach features broad functional group tolerance, metal‐ and oxidant‐free conditions, and moderate to good yields.
Real‐time performance assessment using fast interrupt request on a standard Linux kernel
Authors: Souza Rayanne , Freitas Miguel , Jimenez Marcelo , Magalhães João , Kubrusly Alan C. , Rodriguez Noemi
Published: January 2020

This article presents the use of ARM's fast interrupt request (FIQ) to accomplish better jitter performance on real‐time drivers without using patches for real‐time extensions on the native Linux kernel code. Writing an FIQ interrupt handler is challenging due to the lack of Linux kernel support and the need to avoid page faults exception during its execution. We investigate and evaluate a mechanism that employs static mapping for peripherals and changes on the Linux kernel code to allow the FIQ interrupt handler to be written in the C language. Furthermore, the FIQ performance was evaluated by comparing it with a timer Interrupt Request on Linux PREEMPT‐RT in full CONFIG_PREEMPT_RT mode. Both were applied on a Linux driver for data acquisition of a pipeline inspection gauge system. Results show that the FIQ approach was able to reduce in 97.49% the interrupt jitter and, as a result, allowed an increase in the data acquisition frequency from 1024 Hz to 2048 Hz, showing that the FIQ approach can be considered for real‐time applications without resorting to real‐time extensions.
Correcting the January optimism effect
Authors: Franses Philip Hans
Published: January 2020

Each month, various professional forecasters give forecasts for next year's real gross domestic product (GDP) growth and unemployment. January is a special month, when the forecast horizon moves to the following calendar year. Instead of deleting the January data when analyzing forecast updates, I propose a periodic version of a test regression for weak‐form efficiency. An application of this periodic model for many forecasts across a range of countries shows that in January GDP forecast updates are positive, whereas the forecast updates for unemployment are negative. I document that this January optimism about the new calendar year is detrimental to forecast accuracy. To empirically analyze Okun's law, I also propose a periodic test regression, and its application provides more support for this law.
Genetic effect estimates in case‐control studies when a continuous variable is omitted from the model
Authors: Sheng Ying , Huang Chiung‐Yu , Lobach Siarhei , Zablotska Lydia , Lobach Iryna
Published: January 2020

Large‐scale genome‐wide analyses scans on massive numbers of various cases and controls are archived in the genetic databases that are publically available, for example, the Database of Genotypes and Phenotypes (https://www.ncbi.nlm.nih.gov/gap/). These databases offer unprecscendented opportunity to study the genetic effects. Yet, the set of nongenetic variables in these databases is often brief. From the statistical literature, we know that omitting a continuous variable from a logistic regression model can result in biased estimates of odds ratios (OR), even when the omitted and the included variables are independent. We are interested in assessing what information is needed to recover the bias in the OR estimate of genotype due to omitting a continuous variable in settings when the actual values of the omitted variable are not available. We derive two estimating procedures that can recover the degree of bias based on a conditional density of the omitted variable given the disease status and the genotype or the known distribution of the omitted variable and frequency of the disease in the population. Importantly, our derivations show that omitting a continuous variable can result in either under‐ or over‐estimation of the genetic effects. We performed extensive simulation studies to examine bias, variability, false‐positive rate, and power in the model that omits a continuous variable. We show the application to two genome‐wide studies of Alzheimer's disease.
Right inferior frontal gyrus: An integrative hub in tonal bilinguals
Authors: Gao Zhao , Guo Xin , Liu Cirong , Mo Yin , Wang Jiaojian
Published: January 2020

Right hemispheric dominance in tonal bilingualism is still controversial. In this study, we investigated hemispheric dominance in 30 simultaneous Bai‐Mandarin tonal bilinguals and 28 Mandarin monolinguals using multimodal neuroimaging. Resting‐state functional connectivity (RSFC) analysis was first performed to reveal the changes of functional connections within the language‐related network. Voxel‐based morphology (VBM) and tract‐based spatial statistics (TBSS) analyses were then used to identify bilinguals' alterations in gray matter volume (GMV) and fractional anisotropy (FA) of white matter, respectively. RSFC analyses revealed significantly increased functional connections of the right pars‐orbital part of the inferior frontal gyrus (IFG) with right caudate, right pars‐opercular part of IFG, and left inferior temporal gyrus in Bai‐Mandarin bilinguals compared to monolinguals. VBM and TBSS analyses further identified significantly greater GMV in right pars‐triangular IFG and increased FA in right superior longitudinal fasciculus (SLF) in bilinguals than in monolinguals. Taken together, these results demonstrate the integrative role of the right IFG in tonal language processing of bilinguals. Our findings suggest that the intrinsic language network in simultaneous tonal bilinguals differs from that of monolinguals in terms of both function and structure.
Clinical application of near infrared fiber optic spectroscopy for noninvasive bone assessment
Authors: Shanas No'ad , Querido William , Dumont Alexander , Yonko Elizabeth , Carter Erin , Ok Jina , Karchner James P. , Barbe Mary F. , Ali Sayed , Patil Chetan , Raggio Cathleen , Pleshko Nancy
Published: January 2020

Approaches for noninvasive bone quality assessment are of great clinical need, particularly in individuals that require close monitoring of disease progression. X‐ray measurements are standard approaches to assess bone quality; however, they have several disadvantages. Here, a nonionizing approach for noninvasive assessment of the second metacarpal bone based on near infrared (NIR) spectroscopy was investigated. Transcutaneous bone signal detection was experimentally confirmed with cadaveric hand data, and Monte Carlo modeling further indicated that 50% of the measured signals arise from bone. Spectral data were collected via a NIR fiber optic from the bone of individuals with osteogenesis imperfecta, a disease marked by frequent bone fractures and fragility. Multiple significant correlations were found between spectral parameters related to water, protein and fat, and standard bone quality parameters obtained by X‐ray measurements. The results from this preliminary study highlight the potential application of NIR spectroscopy for the noninvasive assessment of bone quality.