bluuebunny/crossref_metadata_2025 huggingface dataset:
Recent Advances in Palladium‐Catalyzed Cross‐Coupling Reactions at ppm to ppb Molar Catalyst Loadings
Authors: Roy David , Uozumi Yasuhiro
Published: October 2017

We review here new developments in decreasing the catalyst loadings in palladium‐catalyzed C–C bond‐formation reactions to mol ppm or mol ppb levels. This decreases the cost of the catalyst and the toxicity of the reaction system, making the reaction more attractive to industry. The Heck reaction, Sonogashira reaction, Suzuki–Miyaura cross‐coupling reaction, other cross‐coupling reactions, and allylic arylation reactions are separately discussed to show clearly the progress made in each type of reaction. Apart from the catalyst loading, the other parameters of the reaction (temperature, solvent, etc.) are briefly discussed to illustrate the shift toward greener conditions. For most reactions, this shift is underway or well advanced, and catalyst loadings have been decreased to below 1 mol ppm. An abundance of catalytic systems are now available, and it is sometimes difficult to identify the best one, because the substrates examined can vary widely from publication to publication. In the future, emphasis should be placed on the studying the full scope of the reaction at mol ppm catalyst loadings, rather than examining a few examples at these levels during the reaction‐optimization process.

magnified image
(2‐Pyridyl)sulfonyl Groups for ortho‐Directing Palladium‐ Catalyzed Carbon–Halogen Bond Formation at Functionalized Arenes
Authors: Guilbaud Johan , Labonde Marine , Cattey Hélène , Contal Sylvie , Montalbetti Christian , Pirio Nadine , Roger Julien , Hierso Jean‐Cyrille
Published: October 2017

We describe an efficient palladium‐catalyzed selective C–H ortho‐monohalogenation (X=I, Br, Cl, F) of various functionalized (2‐pyridyl)arylsulfones. ortho‐, meta‐ and para‐functionalization is tolerated at the arene group which undergoes C–H halogenation. Some modifications are also possible on the 2‐(arylsulfonyl)heteroaryl directing groups. A comparison of the halogenation efficiency suggests that bromination is the practical method of choice, while chlorination and fluorination are possible but more challenging. Under forcing conditions ortho‐dihalogenation can also be achieved.

magnified image
Direct Access to 2‐Thioxooxazolidin‐4‐ones and Oxazolidine‐2,4‐diones from α‐Keto Thioesters through Thiolate Transfer
Authors: Maity Rajib , Naskar Sandip , Mal Kanchan , Biswas Sandipa , Das Indrajit
Published: October 2017

We report a direct synthesis of 2‐thioxooxazolidin‐4‐ones and oxazolidine‐2,4‐diones from α‐keto thioesters with sodium thiocyanate or potassium cyanate, respectively. The reactions proceed through nucleophilic substitution of a thioester with thiocyanate/cyanate anion, thiolate anion addition to carbonyl carbon, and subsequent intramolecular C−O heterocyclization.

magnified image
Lactols in Asymmetric Sequential Organo‐ and Gold‐Catalysis: Synthesis of Densely Functionalized Epimeric Bicyclic O,O‐Acetals
Authors: You Zhi‐Hao , Chen Ying‐Han , Wu Xiao‐Na , Liu Yan‐Kai
Published: October 2017

Starting from substituted racemic lactols, the combination of organo/gold catalytic system works extremely well providing epimeric bicyclic O,O‐acetals as 5,6‐, and 6,6‐fused ring systems in good isolated yield with excellent enantioselectivities as pure diastereomers only after simple chromatographic purification. To highlight the synthetic potential, several oxygen‐containing heterocycles were prepared smoothly via a diversity‐oriented sequential process with high regio‐ and stereoselectivity, which are important structural units found in natural products and bioactive unnatural molecules.

magnified image
Distributive mixing in a corotating twin screw channel using Lagrangian particle calculations
Authors: Xu Baiping , Yu Huiwen , Turng Lih‐Sheng
Published: October 2017

This work is devoted to the development of a new mapping method for the numerical simulation of melt flow in the complicated forward conveying element of a corotating twin screw extruder under the assumption of periodic boundary conditions of inlet and outlet. The mesh superposition technique (MST) provided by the commercial computational fluid dynamics (CFD) software POLYFLOW was used to deal with the internal moving screw elements, and the flow field of polymer melt obeying the Bird–Carreau constitutive model on the fixed meshes of the flow domain was further solved. After inputting the exported data of the flow field from POLYFLOW, the self‐developed code was further used to characterize the mixing behavior at a finite time under different rotation speeds of the screw elements. A novel mapping method was proposed to convert the instantaneous flow field at the initial time point into the velocity field at any time point. Advection evolution of passive particle groups was simulated by a fourth‐order Runge–Kutta tracking method, and the corresponding variance index was also calculated. The effect of screw rotation speed on distributive mixing was examined. The results showed that the mixing was highly dependent on the initial position whether the particle groups were first placed close to or far away from the intermeshing zone.
Binary Blends of Polyimide and Benzothienobenzothiophene for High‐Performance Solution‐Processed Organic Phototransistors
Authors: Ljubic Darko , Liu Weifeng , González‐Espinoza Cristina E. , Hu Nan‐Xing , Wu Yiliang , Zhu Shiping
Published: October 2017

A novel, soluble, and strong electron withdrawing polyimide (PI), and its first use to modulate photoelectrical characteristics of organic thin film phototransistors (OPTs), are reported. The PI with strong electron‐withdrawing repeating units is solution blended with UV‐responsive organic semiconductor 2,7‐dipentyl[1]benzothieno[3,2‐b][1]benzothiophene (C5‐BTBT). Photoelectrical properties of OPTs are affected by content but not molecular weight of PI in the blends, which is attributed to strong charge trapping at the interface. 10 wt% PI only in the blends can completely suppress the hysteresis under UV light and increase the drain photocurrent by more than six orders of magnitude in the subthreshold region. All the blend‐based OPTs show excellent operational stability in air and high sensitivity to UV light at a low intensity (0.12 mW cm−2). Iphc/ID and photosensitivity were 106 and 429 A W−1, respectively, for 70:30 PI1:C5‐BTBT blend. All the blend‐based OPTs have response times of ≈1 s and decay times (UV off) of 149 s, which are 16 times faster and 2 times slower than the control C5‐BTBT OPT. Density functional theory calculations is used to understand the mechanisms. This work demonstrates that the PI/C5‐BTBT blends represent a very promising system for high‐performance OPT devices.
A Redox‐Based Resistive Switching Memory Device Consisting of Organic–Inorganic Hybrid Perovskite/Polymer Composite Thin Film
Authors: Ercan Ender , Chen Jung‐Yao , Tsai Ping‐Chun , Lam Jeun‐Yan , Huang Sophia Chao‐Wei , Chueh Chu‐Chen , Chen Wen‐Chang
Published: October 2017

This study describes the first perovskite‐based redox resistive switching memory using CH3NH3PbBr3 nanoparticles (NPs) dispersed in an insulating solid polymer electrolyte, poly(ethylene oxide) (PEO), and scrutinizes it in detail. Herein, PEO is chosen not only to perform a matrix function due to its ionic conductivity but also to support a preservative material surrounding the CH3NH3PbBr3 NPs to improve their stability. Further, it is revealed that PEO can serve as the chelating agent to coordinate with PbBr2/CH3NH3PbBr3 NPs in consequence of the direct interaction between Pb2+ cations and electron pairs of ether oxygen on the PEO chain to provide a host medium for the Pb2+ cations on both amorphous and crystalline phases. Consequently, it facilitates the associated redox‐based reactions to result in the metallic filament formation in the derived device, leading to the write‐once‐read‐many times resistive switching behavior. The field‐effect scanning electron microscopy and X‐ray photoelectron spectroscopy analyses are conducted to ascertain the detailed mechanism. It is unveiled that a stable dendritic‐like filament is grown in the CH3NH3PbBr3 NPs:PEO hybrid film, which is thus proposed to be the origin of the stable low resistive state and recovery of the conductive path during the reverse bias scan. This study presents a new perspective on the perovskite‐based resistive memory devices.
Exploring the Stability of Novel Wide Bandgap Perovskites by a Robot Based High Throughput Approach
Authors: Chen Shi , Hou Yi , Chen Haiwei , Tang Xiaofeng , Langner Stefan , Li Ning , Stubhan Tobias , Levchuk Ievgen , Gu Ening , Osvet Andres , Brabec Christoph J.
Published: October 2017

Currently, lead‐based perovskites with mixed multiple cations and hybrid halides are attracting intense research interests due to their promising stability and high efficiency. A tremendous amount of 3D and 2D perovskite compositions and configurations are causing a strong demand for high throughput synthesis and characterization. Furthermore, wide bandgap (≈1.75 eV) perovskites as promising top‐cell materials for perovskite–silicon tandem configurations require the screening of different compositions to overcome photoinduced halide segregation and still yielding a high open‐circuit voltage (Voc). Herein, a home‐made high throughput robot setup is introduced performing automatic perovskite synthesis and characterization. Subsequently, four kinds of compositions (i.e., cation mixtures of Cs–methylammonium (MA), Cs– formamidinium (FA), MA–FA, and FA–MA) with an optical bandgap of ≈1.75 eV are identified as promising device candidates. For Cs–MA and Cs–FA films it is found that the Br–I phase segregation indeed can be overcome. Moreover, Cs–MA, MA–FA, and Cs–FA based devices exhibit an average Voc of 1.17, 1.17, 1.12 V, and their maximum values approached 1.18, 1.19, 1.14 V, respectively, which are among the highest Voc (≈1.2 V) values for ≈40% Br perovskite. These findings highlight that the high throughput approach can effectively and efficiently accelerate the invention of novel perovskites for advanced applications.
Short‐Range Order in Mesoporous Carbon Boosts Potassium‐Ion Battery Performance
Authors: Wang Wei , Zhou Jinhui , Wang Zhuopeng , Zhao Liyun , Li Peihao , Yang Yong , Yang Chao , Huang Hanxin , Guo Shaojun
Published: October 2017

The adequate potassium resource on the earth has driven the researchers to explore new‐concept potassium‐ion batteries (KIBs) with high energy density. Graphite is a common anode for KIBs; however, the main challenge faced by KIBs is that K ions have the larger size than Li and Na ions, hindering the intercalation of K ions into electrodes and thus leading to poor rate performance, low capacity, and cycle stability during the potassiation and depotassiation process. Herein, an amorphous ordered mesoporous carbon (OMC) is reported as a new anode material for high‐performance KIBs. Unlike the well‐crystallized graphite, in which the K ions are squeezed into the restricted interlayer spacing, it is found that the amorphous OMC possesses larger interlayer spacing in short range and fewer carbon atoms in one carbon‐layers cluster, making it more flexible to the deformation of carbon layers. The larger interlayer spacing and the unique layered structure in short range can intercalate more K ions into the carbon layer, accommodate the increase of the interlayer spacing, and tolerate the volume expansion, resulting in a battery behavior with high capacity, high rate capability, and long cycle life.
Enhancing Mo:BiVO4 Solar Water Splitting with Patterned Au Nanospheres by Plasmon‐Induced Energy Transfer
Authors: Kim Jung Kyu , Shi Xinjian , Jeong Myung Jin , Park Joonsuk , Han Hyun Soo , Kim Suk Hyun , Guo Yu , Heinz Tony F. , Fan Shanhui , Lee Chang‐Lyoul , Park Jong Hyeok , Zheng Xiaolin
Published: October 2017

Plasmonic metal nanostructures have been extensively investigated to improve the performance of metal oxide photoanodes for photoelectrochemical (PEC) solar water splitting cells. Most of these studies have focused on the effects of those metal nanostructures on enhancing light absorption and enabling direct energy transfer via hot electrons. However, several recent studies have shown that plasmonic metal nanostructures can improve the PEC performance of metal oxide photoanodes via another mechanism known as plasmon‐induced resonant energy transfer (PIRET). However, this PIRET effect has not yet been tested for the molybdenum‐doped bismuth vanadium oxide (Mo:BiVO4), regarded as one of the best metal oxide photoanode candidates. Here, this study constructs a hybrid Au nanosphere/Mo:BiVO4 photoanode interwoven in a hexagonal pattern to investigate the PIRET effect on the PEC performance of Mo:BiVO4. This study finds that the Au nanosphere array not only increases light absorption of the photoanode as expected, but also improves both its charge transport and charge transfer efficiencies via PIRET, as confirmed by time‐correlated single photon counting and transient absorption studies. As a result, incorporating the Au nanosphere array increases the photocurrent density of Mo:BiVO4 at 1.23 V versus RHE by ≈2.2‐fold (2.83 mA cm−2).
Extrinsic Movable Ions in MAPbI3 Modulate Energy Band Alignment in Perovskite Solar Cells
Authors: Zhang Jing , Chen Renjie , Wu Yongzhen , Shang Minghui , Zeng Zhaobing , Zhang Ying , Zhu Yuejin , Han Liyuan
Published: October 2017

Ionic movement is considered awful in perovskite solar cells (PSCs) for relating with the hysteresis and long‐term instability. However, the positive role of ions to enhance the energy band bending for high performance PSC is always overlooked, let alone reducing the hysteresis. In this work, LiI is doped in CH3NH3PbI3. It is observed that the aggregation of Li+/I− tunes the energy level of the perovskite and induces n/p doping in CH3NH3PbI3, which makes charge extraction quite efficient from perovskite to both NiO and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) layer. Therefore, in NiO/LiI doped perovskite/PCBM solar cells, Li+ and I− modulate the interface energy band alignment to facilitate the electron/hole transport and reduce the interface energy loss. On the other hand, n/p doping enlarges Fermi energy level splitting of the PSCs to improve the photovoltage. The performance of LiI doped PSCs is much higher with reduced hysteresis compared to the undoped solar cells. This work highlights the positive effect of selective ionic doping, which is promisingly important to design the stable and efficient PSCs.
The View From the Top: Academic Emergency Department Chairs’ Perspectives on Education Scholarship
Authors: Clarke Samuel O. , Jordan Jaime , Yarris Lalena M. , Fowlkes Emilie , Kurth Jaqueline , Runde Daniel , Coates Wendy C.
Published: October 2017

Education scholarship continues to grow within emergency medicine (EM) and in academic medicine in general. Despite a growing interest, would‐be education scholars often struggle to find adequate mentorship, research training, funding, and protected time to produce rigorous scholarship. The ways in which individual academic EM departments can support this mission remains an area in need of description.

Objectives

We sought to describe academic EM department chairs’ perceptions of education scholarship and facilitators and barriers to producing high‐quality education scholarship.

Methods

We conducted a qualitative study using a grounded theory–derived approach. Participants were solicited directly, and semistructured interviews were conducted via telephone. Interviews were transcribed verbatim and were analyzed by three study investigators using a coding matrix. Discrepancies in coding were resolved via in depth discussion.

Results

We interviewed seven EM chairs from academic departments throughout North America (six in geographically diverse regions of the United States and one in western Canada). Chairs described education scholarship as lacking clearly defined and measurable outcomes, as well as methodologic rigor. They identified that education faculty within their departments need training and incentives to pursue scholarly work in a system that primarily expects teaching from educators. Chairs acknowledged a lack of access to education research expertise and mentorship within their own departments, but identified potential resources within their local medical schools and universities. They also voiced willingness to support career development opportunities and scholarly work among faculty seeking to perform education research.

Conclusions

Academic EM chairs endorse a need for methodologic training, mentorship, and access to expertise specific to education scholarship. While such resources are often rare within academic EM departments, they may exist within local universities and schools of medicine. Academic EM chairs described themselves as willing and able to support faculty who wish to pursue this type of work.
Positive effects of refugee presence on host community nutritional status in Turkana County, Kenya
Authors: Gengo Rieti G. , Oka Rahul C. , Vemuru Varalakshmi , Golitko Mark , Gettler Lee T.
Published: October 2017

Objectives

Refugee camps are often assumed to negatively impact local host communities through resource competition and conflict. We ask instead whether economic resources and trade networks associated with refugees have benefits for host community health and nutrition. To address this question we assess the impacts of Kakuma Refugee Camp in northwest Kenya, comparing anthropometric indicators of nutritional status between Turkana communities in the region.

Methods

Participants were recruited at four sites in Turkana County (N = 586): Kakuma Town, adjacent to Kakuma Refugee Camp; Lorugum, an area with sustained economic development; Lokichoggio, formerly host to international NGOs, and now underdeveloped; and Lorengo, an undeveloped, rural community. We evaluated nutritional status using summed skinfold thickness and body mass index (BMI). Structured interviews provided contextual data.

Results

Age‐controlled multiple regression models reveal two distinct skinfold thickness profiles for both sexes: comparatively elevated values in Kakuma and Lorugum, and significantly lower values in Lorengo and Lokichoggio. BMI did not vary significantly by location. Despite better nutritional status, a large proportion of Kakuma residents still report worries about basic needs, including hunger, health, and economic security.

Conclusions

Kakuma Refugee Camp is associated with better host community energetic status indicators, compared to other relevant, regional sites varying in development and resources. Based on global nutritional standards, observed differences likely represent meaningful disparities in overall health. We suggest that access to cereals via refugee trade networks and employment might mediate this relationship. However, perceptions of refugees as illegitimate interlopers maintain a high psychological burden.
Docosahexaenoic acid is a beneficial replacement treatment for spinocerebellar ataxia 38
Authors: Manes Marta , Alberici Antonella , Di Gregorio Eleonora , Boccone Loredana , Premi Enrico , Mitro Nico , Pasolini Maria Pia , Pani Claudia , Paghera Barbara , Perani Daniela , Orsi Laura , Costanzi Chiara , Ferrero Marta , Zoppo Adele , Tempia Filippo , Caruso Donatella , Grassi Mario , Padovani Alessandro , Brusco Alfredo , Borroni Barbara
Published: October 2017

Objective

Spinocerebellar ataxia 38 (SCA38) is caused by mutations in the ELOVL5 gene, which encodes an elongase involved in the synthesis of polyunsaturated fatty acids, including docosahexaenoic acid (DHA). As a consequence, DHA is significantly reduced in the serum of SCA38 subjects. In the present study, we evaluated the safety of DHA supplementation, its efficacy for clinical symptoms, and changes of brain functional imaging in SCA38 patients.

Methods

We enrolled 10 SCA38 patients, and carried out a double‐blind randomized placebo‐controlled study for 16 weeks, followed by an open‐label study with overall 40‐week DHA treatment. At baseline and at follow‐up visit, patients underwent standardized clinical assessment, brain 18‐fluorodeoxyglucose positron emission tomography, electroneurography, and ELOVL5 expression analysis.

Results

After 16 weeks, we showed a significant pre–post clinical improvement in the DHA group versus placebo, using the Scale for the Assessment and Rating of Ataxia (SARA; mean difference [MD] = +2.70, 95% confidence interval [CI] = +0.13 to + 5.27, p = 0.042). At 40‐week treatment, clinical improvement was found significant by both SARA (MD = +2.2, 95% CI = +0.93 to + 3.46, p = 0.008) and International Cooperative Ataxia Rating Scale (MD = +3.8, 95% CI = +1.39 to + 6.41, p = 0.02) scores; clinical data were corroborated by significant improvement of cerebellar hypometabolism (statistical parametric mapping analyses, false discovery rate corrected). We also showed a decreased expression of ELOVL5 in patients’ blood at 40 weeks as compared to baseline. No side effect was recorded.

Interpretation

DHA supplementation is a safe and effective treatment for SCA38, showing an improvement of clinical symptoms and cerebellar hypometabolism. Ann Neurol 2017;82:615–621
Rapid Guest Exchange and Ultra‐Low Surface Tension Solvents Optimize Metal–Organic Framework Activation
Authors: Ma Jialiu , Kalenak Andre P. , Wong‐Foy Antek G. , Matzger Adam J.
Published: October 2017

Exploratory research into the critical steps in metal–organic framework (MOF) activation involving solvent exchange and solvent evacuation are reported. It is discovered that solvent exchange kinetics are extremely fast, and minutes rather days are appropriate for solvent exchange in many MOFs. It is also demonstrated that choice of a very low surface tension solvent is critical in successfully activating challenging MOFs. MOFs that have failed to be activated previously can achieve predicted surface areas provided that lower surface tension solvents, such as n‐hexane and perfluoropentane, are applied. The insights herein aid in the efficient activation of MOFs in both laboratory and industrial settings and provide best practices for avoiding structural collapse.
Effects of Febuxostat in Early Gout
Authors: Dalbeth Nicola , Saag Kenneth G. , Palmer William E. , Choi Hyon K. , Hunt Barbara , MacDonald Patricia A. , Thienel Ulrich , Gunawardhana Lhanoo
Published: October 2017

Objective

To assess the effect of treatment with febuxostat versus placebo on joint damage in hyperuricemic subjects with early gout (1 or 2 gout flares).

Methods

In this double‐blind, placebo‐controlled study, 314 subjects with hyperuricemia (serum uric acid [UA] level of ≥7.0 mg/dl) and early gout were randomized 1:1 to receive once‐daily febuxostat 40 mg (increased to 80 mg if the serum UA level was ≥6.0 mg/dl on day 14) or placebo. The primary efficacy end point was the mean change from baseline to month 24 in the modified Sharp/van der Heijde erosion score for the single affected joint. Additional efficacy end points included change from baseline to month 24 in the Rheumatoid Arthritis Magnetic Resonance Imaging Scoring (RAMRIS) scores for synovitis, erosion, and edema in the single affected joint, the incidence of gout flares, and serum UA levels. Safety was assessed throughout the study.

Results

Treatment with febuxostat did not lead to any notable changes in joint erosion over 2 years. In both treatment groups, the mean change from baseline to month 24 in the modified Sharp/van der Heijde erosion score for the single affected joint was minimal, with no between‐group differences. However, treatment with febuxostat significantly improved the RAMRIS synovitis score at month 24 compared with placebo treatment (change from baseline −0.43 versus −0.07; P <0.001), decreased the overall incidence of gout flares (29.3% versus 41.4%; P < 0.05), and improved serum UA control (62.8% versus 5.7%; P < 0.001). No major safety concerns were reported.

Conclusion

Urate‐lowering therapy with febuxostat improved magnetic resonance imaging–determined synovitis and reduced the incidence of gout flares in subjects with early gout.
Functional Classification of the Gut Microbiota: The Key to Cracking the Microbiota Composition Code
Authors: Rosen Connor E. , Palm Noah W.
Published: October 2017

The last decade has seen an explosion of research on the gut microbiota—the trillions of microorganisms that colonize the human gut. It is now clear that interindividual diversity in microbiota composition plays an important role in determining susceptibility to a wide variety of diseases. However, identifying the precise changes in microbiota composition that play causal roles has remained a largely unrealized goal. Here, we propose that functional classifications of microbes based on their interactions with and effects on the host—particularly the host immune system—will illuminate the role of the microbiota in shaping human physiology. We outline the benefits of “functional” classification compared to phylogenetic classifications, and review current efforts at functional classification of the microbiota. Finally, we outline a theoretical framework for classifying host‐microbiota interactions. Future advances enabling broader functional classifications of the microbiota promise to revolutionize our understanding of the role of gut microbes in health and disease.
RubisCO Early Oxygenase Activity: A Kinetic and Evolutionary Perspective
Authors: Ślesak Ireneusz , Ślesak Halina , Kruk Jerzy
Published: October 2017

RubisCO (D‐ribulose 1,5‐bisphosphate carboxylase/oxygenase) is Earth's main enzyme responsible for CO2fixation via carboxylation of ribulose‐1,5‐bisphosphate (RuBP) into organic matter. Besides the carboxylation reaction, RubisCO also catalyzes the oxygenation of RuBP by O2, which is probably as old as its carboxylation properties. Based on molecular phylogeny, the occurrence of the reactive oxygen species (ROS)‐removing system and kinetic properties of different RubisCO forms, we postulated that RubisCO oxygenase activity appeared in local microoxic areas, yet before the appearance of oxygenic photosynthesis. Here, in reviewing the literature, we present a novel hypothesis: the RubisCO early oxygenase activity hypothesis. This hypothesis may be compared with the exaptation hypothesis, according to which latent RubisCO oxygenase properties emerged later during the oxygenation of the Earth's atmosphere. The reconstruction of ancestral RubisCO forms using ancestral sequence reconstruction (ASR) techniques, as a promising way for testing of RubisCO early oxygenase activity hypothesis, is presented.
Phosphoinositide Diversity, Distribution, and Effector Function: Stepping Out of the Box
Authors: Choy Christopher H. , Han Bong‐Kwan , Botelho Roberto J.
Published: October 2017

Phosphoinositides (PtdInsPs) modulate a plethora of functions including signal transduction and membrane trafficking. PtdInsPs are thought to consist of seven interconvertible species that localize to a specific organelle, to which they recruit a set of cognate effector proteins. Here, in reviewing the literature, we argue that this model needs revision. First, PtdInsPs can carry a variety of acyl chains, greatly boosting their molecular diversity. Second, PtdInsPs are more promiscuous in their localization than is usually acknowledged. Third, PtdInsP interconversion is likely achieved through kinase‐phosphatase enzyme complexes that coordinate their activities and channel substrates without affecting bulk substrate population. Additionally, we contend that despite hundreds of PtdInsP effectors, our attention is biased toward few proteins. Lastly, we recognize that PtdInsPs can act to nucleate coincidence detection at the effector level, as in PDK1 and Akt. Overall, better integrated models of PtdInsP regulation and function are not only possible but needed.
Applications of Microfluidics in Quantitative Biology
Authors: Bai Yang , Gao Meng , Wen Lingling , He Caiyun , Chen Yuan , Liu Chenli , Fu Xiongfei , Huang Shuqiang
Published: October 2017

Quantitative biology is dedicated to taking advantage of quantitative reasoning and advanced engineering technologies to make biology more predictable. Microfluidics, as an emerging technique, provides new approaches to precisely control fluidic conditions on small scales and collect data in high‐throughput and quantitative manners. In this review, the authors present the relevant applications of microfluidics to quantitative biology based on two major categories (channel‐based microfluidics and droplet‐based microfluidics), and their typical features. We also envision some other microfluidic techniques that may not be employed in quantitative biology right now, but have great potential in the near future.
Enhanced Genome Editing Tools For Multi‐Gene Deletion Knock‐Out Approaches Using Paired CRISPR sgRNAs in CHO Cells
Authors: Schmieder Valerie , Bydlinski Nina , Strasser Richard , Baumann Martina , Kildegaard Helene Faustrup , Jadhav Vaibhav , Borth Nicole
Published: October 2017

Since the establishment of clustered regularly interspaced short palindromic repeat (CRISPR)/Cas9, powerful strategies for engineering of CHO cell lines have emerged. Nevertheless, there is still room to expand the scope of the CRISPR tool box for further applications to improve CHO cell factories. Here, the authors demonstrate activity of the alternative CRISPR endonuclease Cpf1 in CHO‐K1 for the first time and that it can be used in parallel to CRISPR/Cas9 without any interference. Both, Cas9 and Cpf1, can be effectively used for multi‐gene engineering with a strategy based on paired single guide RNAs (sgRNAs) for full gene deletions. This strategy also enables the targeting of regulatory regions, which would not respond to the conventional frameshift mutations, as shown by removing the α‐1,6‐Fucosyltransferase 8 (FUT8) promoter resulting in a functional knock‐out. FUT8 also served as model to verify that deletion efficiency is size‐independent (2–150 kb). To test the suitability for multi‐gene approaches in combination with gene deletion, clones harboring triple deletions in β‐1,4‐Galactosyltransferase (B4GALT) isozymes are identified using solely conventional PCR/qPCR. In addition, two bicistronic transcription strategies are implemented to enable unequivocal pairing of sgRNAs: a CHO‐derived tRNA linker that works for both, Cas9 and Cpf1, as well as paired sgRNAs in an array format, which can be used with Cpf1 due to its RNA processing ability. These strategies broaden the range of application of CRISPR for novel gene editing approaches in CHO cells and also enable the efficient realization of a genome‐wide deletion library.
Enhancement of biomass and lipid productivity by overexpression of a bZIP transcription factor in Nannochloropsis salina
Authors: Kwon Sohee , Kang Nam Kyu , Koh Hyun Gi , Shin Sung‐Eun , Lee Bongsoo , Jeong Byeong‐ryool , Chang Yong Keun
Published: October 2017

Microalgae are considered as excellent platforms for biomaterial production that can replace conventional fossil fuel‐based fuels and chemicals. Genetic engineering of microalgae is prerequisite to maximize production of materials and to reduce costs for the production. Transcription factors (TFs) are emerging as key regulators of metabolic pathways to enhance production of molecules for biofuels and other materials. TFs with the basic leucine zipper (bZIP) domain have been known as stress regulators and are associated with lipid metabolism in plants. We overexpressed a bZIP TF, NsbZIP1, in Nannochloropsis salina, and found that transformants showed enhanced growth with concomitant increase in lipid contents. The improved phenotypes were also notable under stress conditions including N limitation and high salt. To understand the mechanism underlying improved phenotypes, we analyzed expression patterns of predicted target genes involved in lipid metabolism via quantitative RT‐PCR, confirming increases transcript levels. NsbZIP1 appeared to be one of type C bZIPs in plants that has been known to regulate lipid metabolism under stress. Taken together, we demonstrated that NsbZIP1 could improve both growth and lipid production, and TF engineering can serve as an excellent genetic engineering tool for production of biofuels and biomaterials in microalgae.
Randomized clinical trial of immersive virtual reality tour of the operating theatre in children before anaesthesia
Authors: Ryu J-H , Park S-J , Park J-W , Kim J-W , Yoo H-J , Kim T-W , Hong J S , Han S-H
Published: October 2017

Background

A virtual reality (VR) tour of the operating theatre before anaesthesia could provide a realistic experience for children. This study was designed to determine whether a preoperative VR tour could reduce preoperative anxiety in children.

Methods

Children scheduled for elective surgery under general anaesthesia were randomized into a control or VR group. The control group received conventional information regarding anaesthesia and surgery. The VR group watched a 4-min video showing Pororo, the famous little penguin, visiting the operating theatre and explaining what is in it. The main outcome was preoperative anxiety, assessed using the modified Yale Preoperative Anxiety Scale (m-YPAS) before entering the operating theatre. Secondary outcomes included induction compliance checklist (ICC) and procedural behaviour rating scale (PBRS) scores during anaesthesia.

Results

A total of 69 children were included in the analysis, 35 in the control group and 34 in the VR group. Demographic data and induction time were similar in the two groups. Children in the VR group had a significantly lower m-YPAS score than those in the control group (median 31·7 (i.q.r. 23·3–37·9) and 51·7 (28·3–63·3) respectively; P < 0·001). During anaesthesia, the VR group had lower ICC and PBRS scores than the control group.

Conclusion

This preoperative VR tour of the operating theatre was effective in alleviating preoperative anxiety and increasing compliance during induction of anaesthesia in children undergoing elective surgery. Registration number: UMIN000025232 (http://www.umin.ac.jp/ctr).
Chromatographic determination, decline dynamic and risk assessment of sulfoxaflor in Asian pear and oriental melon
Authors: Kabir Md. Humayun , Abd El‐Aty A. M. , Rahman Md. Musfiqur , Chung Hyung Suk , Lee Han Sol , Kim Sung Woo , Chang Hee‐Ra , Shin Ho‐Chul , Shin Sung Shik , Shim Jae‐Han
Published: October 2017

The dissipation pattern of sulfoxaflor in Asian pear cultivated in an open field conditions and in oriental melon grown under plastic house conditions was each studied in two different locations. Residues in field‐treated samples were determined using liquid chromatography coupled with an ultraviolet detector and confirmed by liquid chromatography–tandem mass spectrometry. A calibration curve for sulfoxaflor was linear over the concentration range 0.1–5.0 mg/L, with a coefficient of determination of 0.9999. The limits of detection and quantification (LOQ) were 0.007 and 0.02 mg/kg, respectively. Recoveries at three fortification levels (LOQ, 10 × LOQ and maximum residue limit) ranged from 70.5 to 86.2%, with a relative standard deviation ≤5.8%. The dissipation half‐lives were 10.8 and 7.9 days in pear and 5.4 and 5.9 days in oriental melon, at sites 1 and 2, respectively. Based on a pre‐harvest residue limit curve, it was predicted that, if the residues at 10 days before harvest in Asian pear are <0.54/0.61 mg/kg and those in oriental melon are <1.43/1.26 mg/kg, then the residue level will be below the maximum residue limit at harvest. Risk assessment at zero days showed a percentage acceptable daily intake of 10.80% in Asian pear and 1.77 and 1.55% in oriental melon, for sites 1 and 2, respectively. These values indicate that the fruits are safe for consumption.
Is the Profile of Fatty Acids, Tocopherols, and Amino Acids Suitable to Differentiate Pinus armandii Suspicious to Be Responsible for the Pine Nut Syndrome from Other Pinus Species?
Authors: Matthäus Bertrand , Li Peiwu , Ma Fei , Zhou Haiyan , Jiang Jun , Özcan Mehmet Musa
Published: October 2017

Pinus armandii is suspicious to be responsible for the Pine Nut Syndrome, a long lasting bitter and metallic taste after the consumption of pine nuts. To find chemical characteristic features for the differentiation of P. armandii from other Pinus species, 41 seed samples of the genus Pinus from 22 plant species were investigated regarding the content and the composition of fatty acids, tocopherols, and amino acids. The predominant fatty acids in the seed oils were linoleic acid (35.2 – 58.2 g/100 g), oleic acid (14.6 – 48.5 g/100 g), and pinolenic acid (0.2 – 22.4 g/100 g), while the vitamin‐E‐active compounds were dominated by γ‐tocopherol. The amino acid composition was mainly characterized by arginine and glutamic acid with amounts between 0.9 and 8.9 g/100 g as well as 2.1 g/100 g and 8.3 g/100 mg. On the basis of this investigation, a Principle Component Analysis has been used to identify the most important components for the differentiation of P. armandii from other Pinus species. Using the data for glutamic acid, 20:2Δ5,11, 18:3Δ5,9,12, 18:1Δ9, and oil content, a classification of the 41 samples into four different groups by cluster analysis was possible, but the characteristic features of P. armandii were too close to some other members of the genus Pinus, making a clear differentiation of this species difficult. Nevertheless, the investigation showed the similarities of different members of the genus Pinus with regard to fatty acids, vitamin‐E‐active compounds, and amino acids.
Hollow Structure and Electron Promotion Effect of Mesoporous Pd/CeO2 Catalyst for Enhanced Catalytic Hydrogenation
Authors: Wei Qinhong , Ma Qingxiang , Zuo Pingping , Fan Huailin , Qu Shijie , Shen Wenzhong
Published: October 2017

A hollow structured CeO2 spheres supported metallic Pd catalyst (Pd/CeO2‐H) was designed and prepared by a glucose hydrothermal method and impregnation method. The CeO2‐H consisted of an inner hollow cavity and an outer shell on which a large number of mesopores were formed. The Pd/CeO2‐H hollow sphere catalyst, which presented abundant surface oxygen vacancies, was investigated for catalytic hydrogenations of styrene and nitrobenzene to produce ethylbenzene and aniline. Activity tests indicated that the mesoporous Pd/CeO2‐H hollow sphere catalyst exhibited striking catalytic activity, which was attributed to the spatial core–shell structure that provided more active sites and facilitated reactant diffusion as well as surface defects (oxygen vacancies), which were capable of transferring electrons to metallic Pd. All of these advances are beneficial to give a higher catalytic hydrogenation performance.
Cake Filtration of Multicomponent Suspensions
Authors: Kühne Sophie , Peuker Urs A.
Published: October 2017

To investigate the separation behavior of multicomponent suspensions (emulsion slurries) consisting of oil droplets and solid particles suspended in water, cake filtration experiments were conducted. Results indicated that up to a certain volumetric content of oil droplets all oil was held back by the filter cake. Due to the deposition of the oil droplets inside the filter cakes, low porosities were obtained, which led to high specific cake resistances. The relationship between resistance and porosity could be well described using an established power law approach. Consequently, the results show an extended range of validity to lower filter cake porosities.
Porous Carbon/rGO Composite: An Ideal Support Material of Highly Efficient Palladium Electrocatalysts for the Formic Acid Oxidation Reaction
Authors: Ali Hassan , Zaman Shahid , Majeed Imran , Kanodarwala Fehmida K. , Nadeem Muhammad Amtiaz , Stride John Arron , Nadeem Muhammad Arif
Published: October 2017

Catalyst support materials play an important role in the electrochemical performance of the catalyst in fuel cells. Herein, we present a synergistic effect of surface area and electronic conductivity on the efficiency of a carbon support material towards its application in direct formic acid fuel cells. A composite of reduced graphene oxide (rGO) and metal organic framework (MOF‐5) derived porous carbon (PC) was used as a novel support material for a high dispersion of palladium nanoparticles. The rGO1‐C1 electrocatalyst, which consists of an equal ratio of PC and rGO, was found to be the most effective for the formic acid electro‐oxidation reaction. The obtained mass specific activity for Pd/rGO1‐C1 (969.76 mA mg−1) is 1.52 times higher than for Pd/rGO (639.5 mA mg−1) and 2.63 times higher than Pd/C (368.73 mA mg−1) synthesized under the same conditions and at given onset peak potentials. The Pd/rGO1‐C1 electrocatalyst was also found to be much more stable than other catalysts as evidenced by chronoamperometric measurements for up to 3000 s. The high activity and stability of the catalyst fabricated over the composite carbon support is due to a synergism between the Pd metal and the composite support toward charge transfer, where highly porous carbon provides a high surface area and the rGO is highly conductive, thereby boosting the electrical properties of the catalyst.
Influence of the Composition and Preparation of the Rotating Disk Electrode on the Performance of Mesoporous Electrocatalysts in the Alkaline Oxygen Reduction Reaction
Authors: Daems Nick , Breugelmans Tom , Vankelecom Ivo F. J. , Pescarmona Paolo P.
Published: October 2017

We report a systematic study of the influence of the composition and preparation method of the electrocatalyst layer deposited on the rotating (ring) disk electrodes (RDE/RRDE) employed in the alkaline oxygen reduction reaction (ORR). To investigate and rationalize the generally underestimated role of these factors on the ORR performance of mesoporous electrocatalysts, we studied the activity and selectivity of nitrogen‐doped ordered mesoporous carbon as a function of the loading of electrocatalyst and of binder, of the type of binder, and of the addition order of the components onto the electrode. The use of an anion‐exchange polymer (Fumion FAA‐3®) as the binder instead of the commonly employed Nafion® increased the selectivity towards H2O2 and led to a lower kinetic current density. In addition, higher selectivity towards H2O was observed when increasing the loading of the catalyst and of the binder, although the latter resulted in a decreased kinetic current density. These results prove the crucial effect of the composition and preparation method of the layer deposited on the electrode on the ORR performance of the mesoporous electrocatalyst and can provide useful guidelines in view of the translation of the results of RDE studies to an alkaline fuel‐cell setup.
Synergistic Doping for Pseudocapacitance Sites in Alkaline Carbon Supercapacitors
Authors: Ni Mei , Huang Zhenghong , Lian Yimeng , Chen Renjie , Zhang Xiaoling , Nie Hailiang , Yang Wen
Published: October 2017

Pseudocapacitance sites emanating from co‐doping with nitrogen and phosphorous in hiearchical carbon are identified by using near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy. Associated space charge capacitance, characterized by using ultraviolet photoelectron spectroscopy (UPS), is induced by charging and enhances interfacial capacitance. Electrodes with high mass loading (8 mg cm−2) provide high energy density, and high stability is obtained (91.4 % retention after 10,000 cycles). We describe a two‐step synthetic procedure, relying on hard templating with nanosilica and pyrolyzing polyaniline in the presence of triphenylphosphine followed by silica etching and annealing in the presence of ammonia gas. This method yields hierarchical porous N−P co‐doped carbon (HP‐NPC).
Direct Arylation of Dipyrrolonaphthyridinediones Leads to Red‐Emitting Dyes with Conformational Freedom
Authors: Sadowski Bartłomiej , Rode Michał F. , Gryko Daniel T.
Published: October 2017

A series of bis‐aryl dipyrrolonaphthyridinediones (DPNDs) with various substitution patterns have been designed and synthesized by direct arylation. This reaction occurs regioselectively at positions 3 and 9, which gives a straightforward entry to unique dyes that absorb in the red/far‐red region and emit in the far‐red/NIR region. The photophysical properties (absorption and fluorescence wavelength) can be controlled by altering the steric hindrance and electronic character of the peripheral aryl group. The fluorescence quantum yields are moderate in the majority of cases and almost independent of changes in the solvent polarity. DPNDs bearing substituents at the ortho position that prevent free rotation of the phenyl ring emit stronger fluorescence relative to the unhindered para analogues and, at the same time their absorption and emission bands are blueshifted. We have used computational methods to explain why electron‐donating substituents have significantly stronger effects than electron‐withdrawing substituents on the optical properties by invoking the electron‐accepting character of the DPND. Electrochemical measurements revealed that the HOMO and LUMO, as well as the electrochemical band gap, also depend strongly on the electronic character of the peripheral group.
Highly Strained Organogold Complexes and Their Gold‐ or Rhodium‐Catalyzed Isomerizations
Authors: Mulks Florian F. , Faraji Shirin , Rominger Frank , Dreuw Andreas , Hashmi A. Stephen K.
Published: October 2017

The synthesis and characterization of (NHC)(tricyclo[4.1.0.02,7]hept‐1‐yl)gold(I) compounds is reported. Several of these organometallic compounds could be obtained by transmetalation from the organolithium precursor to the corresponding (NHC)gold(I) chlorides. These are by far the most strained stable organogold compounds reported so far. With these new compounds we were able to efficiently and selectively accomplish the first gold‐catalyzed rearrangement of organogold compounds, even better yields were obtained by the first rhodium‐catalyzed rearrangement of these organogold species. (E/Z)‐Mixtures of (NHC)(cyclohex‐2‐en‐1‐ylidenemethyl)gold(I) were obtained, none of the other known rearrangement products of tricycloheptanes. Additional insight into the chemical and physical properties of the strained compounds was obtained by spectroscopic and computational studies.
Multi‐block principal component analysis based on variable weight information and its application to multivariate process monitoring
Authors: Wang Lei , Deng Xiaogang
Published: October 2017

The traditional principal component analysis (PCA)‐based process monitoring method builds a global statistical model and omits the mining of the local variable behaviours, which may degrade the fault detection performance. Considering this problem, this paper proposes a variable weight information‐based multi‐block PCA (VWI‐MBPCA) method. Firstly, a sequence hierarchical clustering algorithm is proposed to divide the full PCA component space into several sub‐blocks, where the components sharing similar variable weight information are gathered together and then the sub‐block T2 statistic is constructed for monitoring sub‐block components. Further, the variables with small weight information on each component sub‐block are extracted to build an additional sub‐PCA model, where the statistic is developed to compensate the sub‐block T2 statistic. In order to integrate the monitoring results of each sub‐block, Bayesian inference is applied to construct an overall T2 statistic. To identify the faulty variables, a multi‐block PCA contribution plot is designed by choosing some specific blocks to highlight fault information. Finally, simulations on a numerical example and the benchmark Tennessee Eastman (TE) process are used to demonstrate the strengths of the proposed method.