bluuebunny/crossref_metadata_2025 huggingface dataset:
Bridging Therapy or IV Thrombolysis in Minor Stroke with Large Vessel Occlusion
Authors: Seners Pierre , Perrin Claire , Lapergue Bertrand , Henon Hilde , Debiais Séverine , Sablot Denis , Girard Buttaz Isabelle , Tamazyan Ruben , Preterre Cécile , Laksiri Nadia , Mione Gioia , Arquizan Caroline , Lucas Ludovic , Baron Jean‐Claude , Turc Guillaume ,   MINOR‐STROKE Collaborators
Published: April 2020

Objective

Whether bridging therapy (intravenous thrombolysis [IVT] followed by endovascular treatment) is superior to IVT alone in minor stroke with large vessel occlusion (LVO) is unknown.

Methods

Multicentric retrospective observational study including, in intention‐to‐treat, consecutive IVT‐treated minor strokes (National Institutes of Health Stroke Scale [NIHSS] ≤ 5) with LVO, with or without additional mechanical thrombectomy. Propensity‐score (inverse probability of treatment weighting) was used to reduce baseline between‐groups differences. The primary outcome was excellent outcome, that is, modified Rankin score 0 to 1 at 3 months follow‐up.

Results

Overall, 598 patients were included (214 and 384 in the bridging therapy and IVT groups, respectively). Following propensity‐score weighting, the distribution of baseline clinical and radiological variables was similar across the two patient groups. Compared with IVT alone, bridging therapy was not associated with excellent outcome (odds ratio [OR] = 0.96; 95% confidence interval [CI] = 0.75–1.24; p = 0.76), but was associated with symptomatic intracranial hemorrhage (OR = 3.01; 95% CI = 1.77–5.11; p < 0.0001). Occlusion site was a strong modifier of the effect of bridging therapy on outcome (pinteraction < 0.0001), with bridging therapy associated with higher odds of excellent outcome in proximal M1 (OR = 3.26; 95% CI = 1.67–6.35; p = 0.0006) and distal M1 (OR = 1.69; 95% CI = 1.01–2.82; p = 0.04) occlusions, but with lower odds of excellent outcome for M2 (OR = 0.53; 95% CI = 0.38–0.75; p = 0.0003) occlusions. Bridging therapy was associated with higher rates of symptomatic intracranial hemorrhage in M2 occlusions only (OR = 4.40; 95% CI = 2.20–8.83; p < 0.0001).

Interpretation

Although overall outcomes were similar in intended bridging therapy as compared to intended IVT alone in minor strokes with LVO, our results suggest that intended bridging therapy may be beneficial in M1 occlusions, whereas the benefit–risk profile may favor IVT alone in M2 occlusions. ANN NEUROL 2020 ANN NEUROL 2020;88:160–169
On‐Surface Synthesis of Cumulene‐Containing Polymers via Two‐Step Dehalogenative Homocoupling of Dibromomethylene‐Functionalized Tribenzoazulene
Authors: Urgel José I. , Di Giovannantonio Marco , Eimre Kristjan , Lohr Thorsten G. , Liu Junzhi , Mishra Shantanu , Sun Qiang , Kinikar Amogh , Widmer Roland , Stolz Samuel , Bommert Max , Berger Reinhard , Ruffieux Pascal , Pignedoli Carlo A. , Müllen Klaus , Feng Xinliang , Fasel Roman
Published: April 2020

Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on‐surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well‐controlled ultrahigh‐vacuum conditions. Here we report the on‐surface synthesis of a polymer linked by cumulene‐like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene‐like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X‐ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on‐surface synthesis of cumulene‐containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces.
Reversible Ligand‐Gated Ion Channel via Interconversion between Hollow Single Helix and Intertwined Double Helix
Authors: Bai Dongya , Yan Tengfei , Wang Shi , Wang Yanbo , Fu Jiya , Fang Xiaomin , Zhu Junyan , Liu Junqiu
Published: April 2020

Ligand responsiveness is one of the typical mechanisms in biological organization to trigger sophisticated channel switching. Here, we report a new type of helical trimer which can undergo transition between a hollow single helix and an intertwined double helix with no cavity by complexation and decomplexation of Cu ions. In addition, the one dimensional (1D) hollow helical tubes spontaneously generated from single helices via π‐π interactions embedded into the lipid bilayers and displayed satisfactory channel stability and efficiency. With the addition of CuIions and further extraction with ammonia, the disassembly and reassembly of 1D hollow helical tubes gave rise to the reversible switching of channel activity in situ inside the bilayers. The synthetic helical system provides the first model of reversible ligand‐gated ion channel by means of dynamic transition between single and double helices, which will be available for developing intelligent artificial nanochannels for potential biological and medicinal applications.
Modular and Versatile Trans‐Encoded Genetic Switches
Authors: Paul Avishek , Warszawik Eliza M. , Loznik Mark , Boersma Arnold J. , Herrmann Andreas
Published: April 2020

Current bacterial RNA switches suffer from lack of versatile inputs and are difficult to engineer. We present versatile and modular RNA switches that are trans‐encoded and based on tRNA‐mimicking structures (TMSs). These switches provide a high degree of freedom for reengineering and can thus be designed to accept a wide range of inputs, including RNA, small molecules, and proteins. This powerful approach enables control of the translation of protein expression from plasmid and genome DNA.
Reply to the Comment on “Realization of Lewis Basic Sodium Anion in the NaBH3− Cluster”
Authors: Liu Gaoxiang , Fedik Nikita , Martinez‐Martinez Chalynette , Ciborowski Sandra M. , Zhang Xinxing , Boldyrev Alexander I. , Bowen Kit H.
Published: April 2020

We reply to the comment by S. Pan and G. Frenking who challenged our interpretation of the Na−:→BH3 dative bond in the recently synthesized NaBH3− cluster. Our conclusion remains the same as that in our original paper (https://doi.org/10.1002/anie.201907089 and https://doi.org/10.1002/ange.201907089). This conclusion is additionally supported by the energetic pathways and NBO charges calculated at UCCSD and CASMP2(4,4) levels of theory. We also discussed the suitability of the Laplacian of electron density (QTAIM) and Adaptive Natural Density Partitioning (AdNDP) method for bond type assignment. It seems that AdNDP yields more sensible results. This discussion reveals that the complex realm of bonding is full of semantic inconsistencies, and we invite experimentalists and theoreticians to elaborate this topic and find solutions incorporating different views on the dative bond.
Enantioselective S−H Insertion Reactions of α‐Carbonyl Sulfoxonium Ylides
Authors: Momo Patrícia B. , Leveille Alexandria N. , Farrar Elliot H. E. , Grayson Matthew N. , Mattson Anita E. , Burtoloso Antonio C. B.
Published: April 2020

The first example of enantioselective S−H insertion reactions of sulfoxonium ylides is reported. Under the influence of thiourea catalysis, excellent levels of enantiocontrol (up to 95 % ee) and yields (up to 97 %) are achieved for 31 examples in S−H insertion reactions of aryl thiols and α‐carbonyl sulfoxonium ylides.
Double‐stranded RNAs targeting inhibitor of apoptosis gene show no significant cross‐species activity
Authors: Chereddy Shankar C. R. R. , Gurusamy Dhandapani , Howell Jeffrey L. , Palli Subba R.
Published: April 2020

RNA interference (RNAi) has become an integral part of mainstream research due to its versatility and ease of use. However, the potential nontarget effects associated with double‐stranded RNAs (dsRNA) are poorly understood. To explore this, we used dsRNAs targeting the inhibitor of apoptosis (iap) gene from nine insect species and assayed their possible nontarget effects. For each assay, we used a control (dsRNA targeting the gene coding for green fluorescent protein, GFP) and a species‐specific dsRNA targeting nine iap genes in insect species to evaluate target gene knockdown efficiency, apoptosis phenotype in cells and mortality in insects. Our results revealed that dsIAP efficiently knocks down iap gene expression and induces apoptosis phenotype and mortality in target insect species. In contrast, no significant knockdown of the iap gene expression, apoptosis phenotypes, or mortality were detected in cell lines developed from nontarget insects or nontarget insects treated with dsIAPs. Interestingly, even among closely related insects such as stink bugs, Nezara viridula, Halyomorpha halys, and Murgantia histrionica, with substantial sequence similarity among iap genes from these insects, no significant nontarget effects of dsIAP were observed under the conditions tested. These data demonstrate no significant nontarget effects for dsIAPs and suggest that the threat of nontarget effects of RNAi technology may not be substantial.
Recent Advances in Noble‐Metal‐Free Catalysts for Electrocatalytic Synthesis of Ammonia under Ambient Conditions
Authors: Xiang Zhongyuan , Li Lihong , Wang Ying , Song Yanlin
Published: April 2020

Ammonia is an essential chemical for producing fertilizers and energy carriers. However, the industrial Haber–Bosch process causes huge CO2 emissions and energy waste. As a promising alternative for Haber‐Bosch process, electrochemical synthesis of ammonia has drawn much attention. Catalysts, as a vital part of electrochemical nitrogen reduction reaction (NRR), have developed rapidly in recent years. Compared to noble‐metal catalysts, noble‐metal‐free catalysts possess a low‐cost advantage. In this review, noble‐metal‐free catalysts, including metal‐based materials, metal organic frameworks (MOFs), MXenes, and metal‐free materials, are summarized. In addition, effective design strategies are discussed, along with the main problems and some potential directions of noble‐metal‐free NRR catalysts.
Effects of Mn‐doping on the Structural and Electrochemical Properties of Na3Ni2SbO6 for Sodium‐Ion Battery
Authors: Kee Yongho , Put Brecht , Dimov Nikolay , Staykov Aleksandar , Okada Shigeto
Published: April 2020

Invited for this month's cover picture is the group of Prof. Shigeto Okada. The cover picture shows 2 kinds of synthesized Mn‐doped Na3Ni2−xMnxSbO6 layered oxide cathode materials for Na‐ion batteries. The heavily doped (x=0.5) sample in the right side suffers from large polarization, corresponding to the reduced two‐phase reaction range and a large volume change of the unit cell upon sodium extraction. On the other hand, the lightly Mn‐doped (x=0.25) sample in the left side shows enhanced O’3–P’3 phase transition kinetics due to the smaller volume change of the unit cell. Read the full text of the Article at 10.1002/batt.201900166.
Fundamental review of organosolv pretreatment and its challenges in emerging consolidated bioprocessing
Authors: Wei Kit Chin Danny , Lim Steven , Pang Yean Ling , Lam Man Kee
Published: April 2020

Lignocellulosic biomass is the most abundant renewable source of bioenergy. However, its intertwined structures prevent the embedded cellulose and hemicellulose from undergoing further chemical transformations. Organosolv pretreatment has been known to be effective in reducing the recalcitrance of lignocellulosic biomass. It possesses advantages in the recovery of components and the recovered components such as cellulose can be converted into bioproducts through consolidated bioprocessing (CBP). The main objective of this paper is to review recent developments in organosolv pretreatment, including a comparison of different organic solvents and their optimum operation conditions in terms of pretreatment performance and efficiency. Conventional solvents were also compared with several emerging solvents to discover more potential utilization of organosolv pretreatment. This paper also reviewed fundamental knowledge regarding organosolv pretreatment such as its mechanism, and the chemical and physical properties of the solvents, which are still rarely discussed in the literature due to a lack of conclusive information. The challenges and way forward for organosolv pretreatment were also analyzed in depth to consider the synergistic advantages after the integration of organosolv pretreatment into CBP. It is believed that, through more fundamental exploration and optimization work, organosolv pretreatment can play a vital role in determining the sustainability of CBP, to pave the way for more efficient bioprocessing in the future. © 2020 Society of Chemical Industry and John Wiley & Sons, Ltd
A systematic review and meta‐analysis of the effect of Vitamin D‐fortified food on glycemic indices
Authors: Emadzadeh Maryam , Sahebi Reza , Khedmatgozar Hamed , Sadeghi Ramin , Farjami Mahsa , Sharifan Payam , Ravanshad Yalda , Ferns Gordon A. , Ghayour‐Mobarhan Majid
Published: April 2020

Some reports indicated that Vitamin D may improve glycaemia indices in diabetic patients. The aim of this systematic and meta‐analysis was to evaluate effects of Vitamin D fortification on indices of glycemic control. Six databases (PubMed/Medline, ISI Web of Knowledge, Cochrane Library, Science Direct, Scopus, and Google Scholar) were searched, for randomized controlled trials that were published up to September 2018 and that compared the effect of Vitamin D‐fortified food versus regular diet in relation to glycemic control. Of the 4,379 studies originally found, 11 articles remained to be assessed for meta‐analysis. Vitamin D fortification was associated with a significant improvement in fasting serum glucose (mean difference [MD]: −2.772; 95% confidence interval [CI]: −5.435 to −0.109) and fasting serum insulin (MD: −2.937; 95% CI: −4.695 to −1.178) in patients with Type 2 diabetes mellitus. A diet with food enriched with Vitamin D was associated with a significant improvement in homeostatic model assessment of insulin resistance (MD: −1.608; 95% CI: −3.138 to −0.079) but was not associated with a significant reduction in hemoglobin A1C (MD: 0.034; 95% CI: −0.655 to 0.069). This meta‐analysis indicates that Vitamin D fortification improves indices of glycemic control. Hence, food fortified with Vitamin D may be of potential therapeutic value in diabetic patients, as an adjuvant therapy.
Injectable and moldable hydrogels for use in sensitive and wide range strain sensing applications
Authors: Qiao Zhen , Mieles Matthew , Ji Hai‐Feng
Published: April 2020

Recently, the use of hybrid double network (DN) hydrogels has become prominent due to their enhanced mechanical properties, which has opened the door for new applications of these soft materials. Only a few of these gels have demonstrated both injectable and moldable capabilities. In this work, we report the mechanical properties, gauge factor (GF) values and demonstrate both the injectability and moldability of a gelatin/polyacrylamide DN hydrogel. We optimized several parameters, such as, gelatin to polyacrylamide ratio, reactant concentrations and metal ion concentration, to produce a gelatin/polyacrylamide hydrogel with superior mechanical properties. The highest water content gel was capable of withstanding strains of 5000% before failure. These gels were facilely injected into molds where they effectively changed shape and maintained similar properties prior to remolding. When 20 mM calcium was doped into a similar gel, a tensile strength of 1.71 MPa was achieved. Aside from improving the mechanical properties of the gels, both Ca2+ and Mg2+ also improved their conductivity, so they were tested for use as strain sensors. The sensitivity of the hydrogel strain sensors were measured using the GF. For the 20 mM Ca2+ hydrogel, these GF values ranged from 1.63 to 6.85 for strains of 100% to 2100% respectively. Additionally, the sensors showed good stability over continuous cyclic stretching, demonstrating their long term reliability for strain sensing.
Graphene Quantum Dots Enhanced Photocatalytic Activity of Sb2WO6 Under Ultraviolet‐ and Visible‐Light Irradiation
Authors: Li Shan , Chen Zhongping , Wu Datong , Qin Yong , Kong Yong
Published: April 2020

A novel composite of graphene quantum dots functionalized Sb2WO6 (GQDs/Sb2WO6) was prepared by an electrostatic self‐assembly method and used as a photocatalyst for the degradation of an organic pollutant. The resulting GQDs/Sb2WO6 was characterized by electron microscopy and optical measurements. The photocatalytic activity of GQDs/Sb2WO6 was investigated by degrading methyl orange (MO) under UV‐light and visible‐light irradiation. Compared with pure Sb2WO6, enhancement of the photocatalytic performance of GQDs/Sb2WO6 was achieved, and the degradation efficiency for MO was almost 100% within 3 h under UV‐light irradiation and 71.4% within 3 h under visible‐light irradiation. The photocatalytic degradation mechanism of GQDs/Sb2WO6 was illustrated by free radical and hole scavenging experiments, and the main active species were confirmed to be holes (h+) and superoxide anion radicals (O2·−). Moreover, the GQDs/Sb2WO6 composites exhibited high recyclability and stability and had potential application for decomposing other organic contaminants in water.
Barriers to the circular economy in European small and medium‐sized firms
Authors: García‐Quevedo Jose , Jové‐Llopis Elisenda , Martínez‐Ros Ester
Published: April 2020

The concept of the circular economy (CE) is currently gaining impetus as a way to move towards sustainable, low‐carbon, resource‐efficient, and competitive economies. However, despite the potential benefits of CE activities, their implementation remains relatively rare. We use a cross‐sectional survey of European small and medium‐sized firms (SMEs) to identify the main barriers firms face to promote the CE, focusing specifically on the following: those related to a lack of resources (human and financial) and capabilities (expertise) and those related to the regulatory framework (administrative procedures and the costs of meeting the regulations). Our results indicate that it is the complexity of administrative/legal procedures and the costs of meeting regulations/legal standards that constitute the most significant barriers, whereas the lack of human resources is also perceived to be an obstacle by firms engaged in CE activities. Those obstacles may be considered revealed barriers, and it is only when the firms become involved in these activities that they actually perceive them. Furthermore, when we consider the breadth of CE activities, administrative procedures and regulations once again emerge as the most significant obstacles. Finally, we stress the need to distinguish between different CE activities given that the perception of barriers differs substantially across these activities. Firms undertaking a disruptive innovation redesigning products and services to minimize the use of materials are more likely to perceive all barriers as important. However, firms implementing such activities as minimizing waste, replanning energy usage, and using renewable energy only perceive those obstacles related to administrative procedures and regulations.
Genome analysis of peeling archival cytology samples detects driver mutations in lung cancer
Authors: Kunimasa Kei , Hirotsu Yosuke , Amemiya Kenji , Nagakubo Yuki , Goto Taichiro , Miyashita Yoshihiro , Kakizaki Yumiko , Tsutsui Toshiharu , Otake Sotaro , Kobayashi Hiroaki , Higuchi Rumi , Inomata Kie , Kumagai Takashi , Mochizuki Hitoshi , Nakamura Harumi , Nakatsuka Shin‐ichi , Nishino Kazumi , Imamura Fumio , Kumagai Toru , Oyama Toshio , Omata Masao
Published: April 2020

Introductions

When tumor tissue samples are unavailable to search for actionable driver mutations, archival cytology samples can be useful. We investigate whether archival cytology samples can yield reliable genomic information compared to corresponding formalin‐fixed paraffin‐embedded (FFPE) tumor samples.

Patients and Methods

Pretreatment class V archival cytology samples with adequate tumor cells were selected from 172 lung cancer patients. The genomic profiles of the primary lung tumors have been analyzed through whole‐exome regions of 53 genes. We compared the genomic profiles based on the oncogenicity and variant allele frequency (VAF) between the archival cytology and the corresponding primary tumors. We also analyzed the genomic profiles of serial cytological samples during the treatment of EGFR‐TKI.

Results

A total of 43 patients were analyzed with the paired samples for DNA mutations and other three patients were analyzed for their fusion genes. A total of 672 mutations were detected. Of those, 106 mutations (15.8%) were shared with both samples. Sixty of seventy‐seven (77.9%) shared mutations were oncogenic or likely oncogenic mutations with VAF ≧10%. As high as 90% (9/10) actionable driver mutations and ALK and ROS1 fusion genes were successfully detected from archival cytology samples. Sequential analysis revealed the dynamic changes in EGFR‐TKI‐resistant mutation (EGFR p.T790M) during the course of treatment.

Conclusion

Archival cytology sample with adequate tumor cells can yield genetic information compared to the primary tumors. If tumor tissue samples are unavailable, we can use archival cytology samples to search for actionable driver mutations.
Production of the Inaccessible Sesquiterpene (−)‐5‐Epieremophilene by Metabolically Engineered Escherichia coli
Authors: Luo Liu‐Qiong , Chen Yue‐Gui , Li De‐Sen , Liu Yan , Li Sheng‐Hong
Published: April 2020

(−)‐5‐Epieremophilene, an epimer of the versatile sesquiterpene (+)‐valencene, is an inaccessible natural product catalyzed by three sesquiterpene synthases (SmSTPSs1‐3) of the Chinese medicinal herb Salvia miltiorrhiza, and its biological activity remains less explored. In this study, three metabolically engineered Escherichia coli strains were constructed for (−)‐5‐epieremophilene production with yields of 42.4–76.0 mg/L in shake‐flask culture. Introducing an additional copy of farnesyl diphosphate synthase (FDPS) gene through fusion expression of SmSTPS1‐FDPS or dividing the FDP synthetic pathway into two modules resulted in significantly improved production, and ultimately 250 mg of (−)‐5‐epieremophilene were achieved. Biological assay indicated that (−)‐5‐epieremophilene showed significant antifeedant activity against Helicoverpa armigera (EC50=1.25 μg/cm2), a common pest of S. miltiorrhiza, implying its potential defensive role in the plant. The results provided an ideal material supply for studying other potential biological activities of (−)‐5‐epieremophilene, and also a strategy for manipulating terpene production in engineered E. coli using synthetic biology.
Simultaneous occurrence of triple teeth and double teeth in primary dentition: A rare case report and review of the literature
Authors: Lagarde Marianne , Bonnet Anne‐Laure , Douangmala Nina , Traing Marina , Dursun Elisabeth
Published: April 2020

This paper reports the case of a 3‐year‐old male patient with triple teeth in the right maxillary incisor region and double teeth in the left mandibular incisor region. He had pre‐existing medical conditions. The triple teeth were extracted and examined using micro‐computed tomography. A literature review was performed to discuss this abnormality.
Coronary pseudoaneurysm 1 week after complex percutaneous coronary intervention with drug‐eluting stent
Authors: Namazi Mohammad Hasan , Khani Mohammad , Faghihi Langroudi Taraneh , Abedi Fatemeh , Tabary Mohammadreza , Khaheshi Isa
Published: April 2020

Pseudoaneurysm formation is a rare complication after complex PCI with drug‐eluting stents. Cardiologists and interventionist should be familiar with this rare complication after PCI and its management options.
Highly Graphitized Porous Carbon‐FeNi3 Fabricated from Oleic Acid for Advanced Lithium–Sulfur Batteries
Authors: Chen Lin , Huang Liwu , Chen Guojie , Zhang Xinlin , Chen Yungui
Published: April 2020

Improving the electrical conductivity of sulfur, suppressing shuttle/dissolution of polysulfide, and enhancing reaction kinetics in Li–S batteries are essential for practical applications. Here, for the first time, we have used inexpensive oleic acid as a single carbon source, and have added commercial SiO2 as a template to form a porous structure, whereas introducing Fe(NO3)3 and Ni(NO3)2 as catalysts to increase the degree of graphitization. Moreover, the dual metal salts Fe(NO3)3 and Ni(NO3)2 can also form FeNi3 alloy, and our results show that FeNi3 nanoparticles accelerate the kinetic conversion reactions of polysulfide. By virtue of the well‐developed porous structure and high degree of graphitization, the highly graphitized porous carbon‐FeNi3 (GPC‐FeNi3) has high conductivity to ensure fast charge transfer, and the hierarchically porous structure facilitates ion diffusion and traps polysulfide. Thus, a GPC‐FeNi3/S cathode displays excellent electrochemical performance. At current rates of 0.2 and 1 C, a cathode of the GPC‐FeNi3/S composite with a sulfur content of 70 % delivers high initial discharge capacities of 1108 and 880 mA h g−1, respectively, and retains reversible specific capacities of 850 mA h g−1 after 200 cycles at 0.2 C and 625 mA h g−1 after 400 cycles at 1 C.
Heterogeneous Olefin Hydrogenation Enabled by a Highly‐Reduced Nickel(−II) Catalyst Precursor
Authors: Maier Thomas M. , Sandl Sebastian , Melzl Peter , Zweck Josef , Jacobi von Wangelin Axel , Wolf Robert
Published: April 2020

Invited for the cover of this issue is the group of Robert Wolf at the University of Regensburg and colleagues at the University of Hamburg. The image depicts the hydrogenation of triphenylethylene. Read the full text of the article at 10.1002/chem.201905537.
Enantioselective Synthesis of Polycyclic Aromatic Hydrocarbon (PAH)‐Based Planar Chiral Bent Cyclophanes by Rhodium‐Catalyzed [2+2+2] Cycloaddition
Authors: Aida Yukimasa , Nogami Juntaro , Sugiyama Haruki , Uekusa Hidehiro , Tanaka Ken
Published: April 2020

The enantioselective synthesis of polycyclic aromatic hydrocarbon (PAH)‐based planar chiral cyclophanes was achieved for the first time by the rhodium‐catalyzed intramolecular regio‐ and enantioselective [2+2+2] cycloaddition of tethered diyne‐benzofulvenes followed by stepwise oxidative transformations. The thus synthesized planar chiral bent cyclophanes, that possess bentp‐terphenyl‐ and 9‐fluorenone‐cores, were converted to 9‐fluorenol‐based ones with excellenteevalues of >99 % by diastereoselective 1,2‐reduction. These 9‐fluorenol‐based cyclophanes exhibited high fluorescence quantum yields, which were significantly higher than that of an acyclic reference molecule (78–82 % vs. 48 %). The bending effect on the chiroptical property was also examined, which revealed that the anisotropy factors (gabsvalues) for electronic circular dichroism (ECD) of these 9‐fluorenol‐based planar chiral bent cyclophanes increase as the tether length becomes shorter.
Bismuth‐Oxide‐Decorated Graphene Oxide Hybrids for Catalytic and Electrocatalytic Reduction of CO2
Authors: Mulik Balaji B. , Bankar Balasaheb D. , Munde Ajay V. , Biradar Ankush V. , Sathe Bhaskar R.
Published: April 2020

Global warming challenges are fueling the demand to develop an efficient catalytic system for the reduction of CO2, which would contribute significantly to the control of climate change. Herein, as‐synthesized bismuthoxide‐decorated graphene oxide (Bi2O3@GO) was used as an electro/thermal catalyst for CO2 reduction. Bi2O3@GO is found to be distributed uniformly, as confirmed by scanning electron and transmission electron microscopic analysis. The X‐ray diffraction (XRD) pattern shows that the Bi2O3 has a β‐phase with 23.4 m2 g−1 BET surface area. Significantly, the D and G bands from Raman spectroscopic analysis and their intensity ratio (ID/IG) reveal the increment in defective sites on GO after surface decoration. X‐ray photoelectron spectroscopic (XPS) analysis shows clear signals for Bi, C, and O, along with their oxidation states. An ultra‐low onset potential (−0.534 V vs. RHE) for the reduction of CO2 on Bi2O3@GO is achieved. Furthermore, potential‐dependent (−0.534, −0.734, and −0.934 vs. RHE) bulk electrolysis of CO2 to formate provides Faradaic efficiencies (FE) of approximately 39.72, 61.48, and 83.00 %, respectively. Additionally, in time‐dependent electrolysis at a potential of −0.934 versus RHE for 3 and 5 h, the observed FEs are around 84.20 % and 87.17 % respectively. This catalyst is also used for the thermal reduction of CO2 to formate. It is shown that the thermal reduction provides a path for industrial applications, as this catalyst converts a large amount of CO2 to formate (10 mm).
Entwurf und Betrieb eines Rohrreaktors mit enger Verweilzeitverteilung
Authors: Kockmann Norbert
Published: April 2020

In der Verfahrenstechnik ist die Verweilzeit eine wichtige Auslegungsgröße und eine enge Verweilzeitverteilung ist vorteilhaft, um bei komplexen chemischen Reaktionen mögliche Nebenprodukte zu vermeiden Eine gute radiale Vermischung mit geringer axialer Dispersion sorgt für eine enge Verweilzeitverteilung in einem Rohrreaktor. Die axiale Dispersion in laminarer Strömung in einem geraden Rohr ist sehr hoch und erzeugt damit eine breite Verweilzeitverteilung. Jedoch verbessern Sekundärströmungen die radiale Vermischung, die in diesem Beitrag für gekrümmte Rohrreaktoren untersucht werden. Entwurfshinweise zur guten radialen Vermischung und geometrische Ausführungen von Rohreaktoren mit Umlenkungen werden vorgestellt.
A CFD‐DEM approach to study the breakup of fractal agglomerates in an internal mixer
Authors: Frungieri Graziano , Boccardo Gianluca , Buffo Antonio , Marchisio Daniele , Karimi‐Varzaneh Hossein Ali , Vanni Marco
Published: April 2020

In this work we present a method to investigate the breakup of filler agglomerates in an internal mixer during a compounding operation. The method employs computational fluid dynamics (CFD) simulations along with discrete element method (DEM) simulations. CFD simulations are performed to compute the flow field inside a 2D section of a typical batch internal mixer with two tangential rotors. During the CFD simulation, we assume the filler agglomerates to behave as tracer particles, carried passively by the flow. The trajectory of the tracers, together with the experienced velocity gradients, are fed to a DEM code, built in the framework of Stokesian dynamics. The code computes the mechanical response of the agglomerates along the trajectory, from which it is finally possible to ascertain the occurrence of breakup. Simulations are performed to evaluate the robustness of the method on two different rotor speed ratio conditions and varying agglomerate strength.
Combined effect of nutrient and flashing light frequency for a biochemical composition shift in Nannochloropsis gaditana grown in a quasi‐isoactinic reactor
Authors: Lima Serena , Villanova Valeria , Grisafi Franco , Brucato Alberto , Scargiali Francesca
Published: April 2020

Artificial lighting may be an interesting opportunity for the cultivation of microalgae as an alternative to natural sunlight. In particular, light emitting diodes (LEDs) can be employed to tailor the lighting to the microalgal culture in a controlled mode in order to create flashing light. In order to establish the effect of the flashing frequency on growth and biochemical composition of a model microalga, a quasi‐isoactinic reactor, in which the light distribution is almost homogeneous, was set up. In this work, it was employed for the cultivation of the heterokont Nannochloropsis gaditana in two growth media with limiting and nonlimiting nutrients. The combined effect of nutrient concentration and flashing frequency on the growth, lipid content, fatty acid content, and pigment content was assessed for the first time. The results indicate that both nutrient concentration and flashing frequency influence the above‐mentioned parameters. In particular, under flashing light conditions, an increase of lipid content and a decrease of polyunsaturated fatty acids (PUFAs) and chlorophyll are observed when nutrients are deficient, while the opposite effects are shown when nutrients are abundant.
Evolution of lung pathology in lymphangioleiomyomatosis: associations with disease course and treatment response
Authors: Miller Suzanne , Stewart Iain D , Clements Debbie , Soomro Irshad , Babaei‐Jadidi Roya , Johnson Simon R
Published: April 2020

Lymphangioleiomyomatosis (LAM) is a rare multisystem disease with a variable clinical course. The lungs are infiltrated by nodules of LAM cells, stromal cells and inflammatory cells, causing lung cysts and respiratory failure. We used immunohistochemical markers in lung biopsy and transplant samples from a national cohort of women with LAM with linked clinical data to understand how LAM nodule cell populations changed with disease progression. Marker distribution was examined qualitatively by dual immunohistochemistry, and markers for LAM cells, fibroblasts, lymphatics, mast cells, proliferation, cathepsin K and mTOR pathway activity were quantitated in LAM nodules and compared with clinical features and prospective lung function loss. The LAM cell marker PNL2 was more extensively expressed in those with higher forced expiratory volume in one second (FEV1), higher diffusion in the lung for carbon monoxide (DLCO) and less extensive disease involvement whilst the converse was true for the protease cathepsin K. Each percentage increase in cathepsin K reactivity was associated with a 0.65% decrease in FEV1 (95% CI −1.11 to −0.18) and a 0.50% decrease in DLCO (95% CI −0.96 to −0.05). Higher reactivity to the mTOR complex 1 activation marker, phospho‐ribosomal protein S6, was associated with a better lung function response to rapamycin (p = 0.0001). We conclude that LAM nodules evolve with disease progression, with LAM cells becoming outnumbered by fibroblasts. Increasing cathepsin K expression is associated with more severe disease and lung function loss. Markers of mTOR activation predict the response to rapamycin, suggesting that more advanced LAM may be less mTOR responsive and treatments specifically targeted towards LAM associated fibroblasts may have roles as adjuncts to mTOR inhibition.
Gender‐specific association between body mass index and all‐cause mortality in patients with atrial fibrillation
Authors: Lyu Si‐qi , Yang Yan‐min , Zhu Jun , Wang Juan , Wu Shuang , Zhang Han , Shao Xing‐hui , Ren Jia‐meng
Published: April 2020

Background

Elevated body mass index (BMI) is related with reduced mortality in various cardiovascular diseases.

Hypothesis

Gender‐specific association between BMI and mortality exists in atrial fibrillation (AF).

Methods

In this multicenter observational study with a mean follow‐up of 1 year, a total of 1991 AF patients were enrolled and divided into two groups based on the gender. The primary endpoint was all‐cause mortality while the secondary endpoints were defined as cardiovascular mortality, stroke, and major adverse events during 1‐year follow‐up. Cox regression was performed to identify the association between BMI and clinical outcomes according to gender.

Results

Female patients with AF tended to be older (P = .027) and thinner (P < .001) than male patients with AF. They were more likely to have heart failure, hyperthyroidism, and valvular AF (all P < .05), but less likely to have coronary artery disease and prior myocardial infarction (all P < .01). Multivariate analysis revealed that overweight (HR(95%CI): 0.55(0.41‐0.75), P < .001) and obese patients (HR(95%CI): 0.56(0.34‐0.94), P = .028) were associated with significant lower all‐cause mortality compared with normal weight patients for the entire cohort. Similar association between elevated BMI and reduced all‐cause mortality were only identified in female patients with AF (overweight vs normal weight: HR(95%CI): 0.43(0.27‐0.70); obesity vs normal weight: HR(95%CI): 0.46(0.22‐0.97)), but not in male patients with AF.

Conclusion

This study indicates that overweight and obesity were related with improved survival in patients with AF. The association between elevated BMI and reduced mortality was dependent on gender, which was only significant in female patients, rather than male patients.
The Influence of Nozzle Type and Application Speed on Sicklepod Control with Cadre and Butyrac
Authors: de Moraes Jesaelen Gizotti , Prostko Eric P. , Kruger Greg R. , Rodrigues Camila Chiaranda
Published: April 2020

Sicklepod, also colloquially known as coffeeweed, is one of the most common and troublesome weeds in Georgia peanut production systems. Spray chamber/greenhouse studies were conducted to evaluate the effects of application speed (8 and 12 MPH), nozzle type (XR, TTI, and AIXR), and herbicide treatment on sicklepod control. Earn 0.5 CEUs in Integrated Pest Management by reading the article and taking the quiz at www.certifiedcropadviser.org/education/classroom/classes/804.
Crystal‐to‐Crystal Synthesis of Photocatalytic Metal–Organic Frameworks for Visible‐Light Reductive Coupling and Mechanistic Investigations
Authors: Gutiérrez Luis , Mondal Suvendu Sekhar , Bucci Alberto , Kandoth Noufal , Escudero‐Adán Eduardo C. , Shafir Alexandr , Lloret‐Fillol Julio
Published: April 2020

Postmodification of reticular materials with well‐defined catalysts is an appealing approach to produce new catalytic functional materials with improved stability and recyclability, but also to study catalysis in confined spaces. A promising strategy to this end is the postfunctionalization of crystalline and robust metal–organic frameworks (MOFs) to exploit the potential of crystal‐to‐crystal transformations for further characterization of the catalysts. In this regard, two new photocatalytic materials, MOF‐520‐PC1 and MOF‐520‐PC2, are straightforwardly obtained by the postfunctionalization of MOF‐520 with perylene‐3‐carboxylic acid (PC1) and perylene‐3‐butyric acid (PC2). The single crystal‐to‐crystal transformation yielded the X‐ray diffraction structure of catalytic MOF‐520‐PC2. The well‐defined disposition of the perylenes inside the MOF served as suitable model systems to gain insights into the photophysical properties and mechanism by combining steady‐state, time‐resolved, and transient absorption spectroscopy. The resulting materials are active organophotoredox catalysts in the reductive dimerization of aromatic aldehydes, benzophenones, and imines under mild reaction conditions. Moreover, MOF‐520‐PC2 can be applied for synthesizing gram‐scale quantities of products in continuous‐flow conditions under steady‐state light irradiation. This work provides an alternative approach for the construction of well‐defined, metal‐free, MOF‐based catalysts.
Self‐Supported Vanadium Carbide by an Electropolymerization‐Assisted Method for Efficient Hydrogen Production
Authors: Guo Lixia , Liu Yangyang , Teng Xue , Niu Yanli , Gong Shuaiqi , Chen Zuofeng
Published: April 2020

Exploring efficient electrodes toward the hydrogen evolution reaction (HER) remains a great challenge for large‐scale hydrogen production. Owing to its high earth abundance, low electrical resistivity, and small density, vanadium carbide (VC) is a promising HER electrode candidate but has been rarely explored. In this work, VC nanoparticles encased in nitrogen‐doped carbon matrix on carbon cloth (VC@NC/CC) were prepared as a binder‐free HER cathode through electropolymerization followed by carbothermal reduction under argon. In the first step of pyrrole electropolymerization, the VO43− anions, serving as both vanadium source and supporting electrolyte, were homogeneously incorporated in the positively charged polypyrrole (PPy) framework through coulombic interaction. The electropolymerization was effective for preparation of binder‐free metal carbide materials with various polymer monomers as carbon source, which was favorable for the high performance of metal carbide electrodes. During the pyrolysis process, the polymeric hybrids were converted to VC nanoparticles and entrapped in the PPy‐derived N‐doped carbon matrix. The optimized VC@NC/CC electrode exhibited high catalytic activity and durability in both acidic and alkaline media. The use of VC for efficient HER is remarkable, and such a convenient and versatile electropolymerization‐assisted method is appealing for the fabrication of industrially scalable large‐area VC electrodes for efficient hydrogen production.
RhoA/Rho‐kinases in asthma: from pathogenesis to therapeutic targets
Authors: Zhang Yan , Saradna Arjun , Ratan Rhea , Ke Xia , Tu Wei , Do Danh C , Hu Chengping , Gao Peisong
Published: April 2020

Asthma is a chronic and heterogeneous disease characterised by airway inflammation and intermittent airway narrowing. The key obstacle in the prevention and treatment of asthma has been our incomplete understanding of its aetiology and biological mechanisms. The ras homolog family member A (RhoA) of the Rho family GTPases has been considered to be one of the most promising and novel therapeutic targets for asthma. It is well known that RhoA/Rho‐kinases play an important role in the pathophysiology of asthma, including airway smooth muscle contraction, airway hyper‐responsiveness, β‐adrenergic desensitisation and airway remodelling. However, recent advances have suggested novel roles for RhoA in regulating allergic airway inflammation. Specifically, RhoA has been shown to regulate allergic airway inflammation through controlling Th2 or Th17 cell differentiation and to regulate airway remodelling through regulating mesenchymal stem cell (MSC) differentiation. In this review, we evaluate the literature regarding the recent advances in the activation of RhoA/Rho‐kinase, cytokine and epigenetic regulation of RhoA/Rho‐kinase, and the role of RhoA/Rho‐kinase in regulating major features of asthma, such as airway hyper‐responsiveness, remodelling and inflammation. We also discuss the importance of the newly identified role of RhoA/Rho‐kinase signalling in MSC differentiation and bronchial epithelial barrier dysfunction. These findings indicate the functional significance of the RhoA/Rho‐kinase pathway in the pathophysiology of asthma and suggest that RhoA/Rho‐kinase signalling may be a promising therapeutic target for the treatment of asthma.
New directions in chimeric antigen receptor T cell [CAR‐T] therapy and related flow cytometry
Authors: Maryamchik Elena , Gallagher Kathleen Mary Ellen , Preffer Frederic I. , Kadauke Stephan , Maus Marcela V.
Published: April 2020

Chimeric antigen receptor (CAR) T cells provide a promising approach to the treatment of hematologic malignancies and solid tumors. Flow cytometry is a powerful analytical modality, which plays an expanding role in all stages of CAR T therapy, from lymphocyte collection, to CAR T cell manufacturing, to in vivo monitoring of the infused cells and evaluation of their function in the tumor environment. Therefore, a thorough understanding of the new directions is important for designing and implementing CAR T‐related flow cytometry assays in the clinical and investigational settings. However, the speed of new discoveries and the multitude of clinical and preclinical trials make it challenging to keep up to date in this complex field. In this review, we summarize the current state of CAR T therapy, highlight the areas of emergent research, discuss applications of flow cytometry in modern cell therapy, and touch upon several considerations particular to CAR detection and assessing the effectiveness of CAR T therapy.
An enhanced flower pollination algorithm‐based chaff point generation method with hardware implementation in WBAN
Authors: M. V. Karthikeyan , J. Martin Leo Manickam
Published: April 2020

In wireless body area networks (WBAN), device authentication and key agreement are the critical issues. In any real‐world cryptographic system, issues like these can be handled by one of the most practical bio‐cryptosystem schemes popularly known as fuzzy vault (FV). The secret key is encoded in a polynomial equation merged with physiological value and then combined with chaff (noise) points forming the FV. The most critical and computational intensive task in the FV is the chaff point generation, that is used to hide the valid point inside the vault pattern. In this paper, we propose an Enhanced Flower Pollination Algorithm based Chaff Point generation method with Hardware (EFPCH) implementation and have been proved to be a computationally fast and feasible algorithm for hardware implementation. The security of the FV depends on the infeasibility of the polynomial reconstruction and also in large number of chaff point. The existing methods for chaff point generation had taken less number of valid points and generate a maximum of 200 chaff points. But in our experimental result, we generated large number of chaff point (1:12) with a considerable amount of valid points over the existing algorithm. This work describes the key agreement model and implementation step required for identifying External programmer attached to the patient pacemaker. However, existing key agreement schemes have too many computational intensive tasks, making it unsuitable for system‐on‐chip (SoC) implementation. In the result of the described work, a practical SoC implementation of the wireless environment in WBAN is experimented. The results show that our proposed model has a more efficient implementation in generating larger chaff points and performs better than other current methods.
Role of fine‐needle aspiration cytology in early diagnosis of fungal infections
Authors: George Bistees , Rivera Rolon Maria Del Mar , Clement Cecilia G.
Published: April 2020

Background

Fine‐needle aspiration (FNA) is an important tool for the diagnosis of infectious diseases. In this study, we assessed the efficacy of FNA cytology in early diagnosis of fungal infections.

Methods

This was a retrospective study from January 2016 to August 2018. Electronic archives were searched for FNAs from superficial and deep lesions obtained from various sites with the diagnosis of fungal infection. Each case was evaluated for underlying predisposing conditions, FNA source, radiologic findings, culture, and serology results.

Results

A total of 15 cases were identified from the following sites: lung (eight), cervical lymph nodes (four), soft tissue (two), and retroperitoneal lymph node (one). Predisposing conditions were found in 11 patients: HIV (five), malignancy (three), and post‐transplant (three). Imaging impression was mostly malignancy vs infection. In all 15 cases, the diagnosis of fungal infection was done by FNA cytology. The presumptive genus specific diagnoses based on yeast morphology was given in 12 cases (five Histoplasma, four Cryptococcus, and three Coccidioides). The diagnosis of fungal infection was provided within 24 h in nine cases, four during onsite evaluation. Microbial cultures were confirmatory in seven cases, and five cases exhibited negative cultures with positive serology. Out of the 15 patients, 14 were discharged in fair condition, and one died with complications of heart graft failure.

Conclusion

FNA is a rapid and reliable method for early diagnosis of fungal infections, allowing a prompt and appropriate management, especially in immunocompromised patients. When onsite evaluation indicates infectious process, cultures can be timely done.