bluuebunny/crossref_metadata_2025 huggingface dataset:
Development of a highly accurate and sensitive diagnostic tool for pyrethroid‐resistant chimeric P450 CYP337B3 of Helicoverpa armigera using loop‐mediated isothermal amplification
Authors: Choi Bo Hey , Hur Joon Haeng , Heckel David G. , Kim Juil , Koh Young Ho
Published: September 2018

Recent studies have shown that pyrethroid resistance in the cotton bollworm (CBW) Helicoverpa armigera is conferred by the generation of a chimeric CYP337B3 gene, which resulted from unequal crossing‐over between the CYP337B1 and CYP337B2 genes. In this study, we developed a diagnostic protocol based on the loop‐mediated isothermal amplification (LAMP) assay for the detection of chimeric CYP337B3. The CYP337B3 LAMP assay utilized six primers and generated strong fluorescence signals visible to the naked eye under normal or ultraviolet light. The primers were designed based on CYP337B3v1 (JQ995292), the major allele detected in Australia. The detection limit of this LAMP assay was 10 fg genomic DNA in a 25‐µl reaction mixture. Compared with CYP337B2v1, the Korean CYP337B3v2 allele had two nucleotide mismatches within the amplifying regions of this LAMP assay; therefore, we confirmed that polymerase chain reaction‐synthesized CYP337B3v2 was well amplified using this LAMP assay. In addition, we determined that the presence of CYP337B3 from H. armigera collected by pheromone traps from Korean fields could be confirmed using this LAMP assay. This assay could detect CYP337B3 even in heterozygotes, which is relevant because CYP337B3 is dominant, and heterozygotes are pyrethroid resistant. Therefore, the newly developed CYP337B3 LAMP assay could detect the presence of pyrethroid resistance in H. armigera that were captured by pheromone traps during the early season and provide information on whether pyrethroids could be used to control H. armigera.
Tunable Fluorescence from a Responsive Hyperbranched Polymer with Spatially Arranged Fluorophore Arrays
Authors: Cao Xiaosong , Gan Weiping , Shi Yi , Xu Hui , Gao Haifeng
Published: September 2018

In the present study, a water‐soluble hyperbranched polymer platform that contained a Förster resonance energy transfer (FRET) array and exhibited varied fluorescence in response to solvent, light, and CN− anion stimuli was constructed. The use of chain‐growth copper‐catalyzed azide–alkyne cycloaddition polymerization (CuAACP) enabled accurate control of the ratio and distance of three incorporated fluorophores, coumarin (Cou), nitrobenzoxadiazole (NBD), and photoswitchable spiropyran (SP), that could be reversibly transformed into the red‐emitting merocyanine (MC) state. Within the FRET system, the energy flow from Cou to MC was significantly enhanced by the introduction of NBD as a central fluorophore relay. Moreover, the energy‐transfer efficiency was increased by changing the solvent from tetrahydrofuran to more polar water; this was accompanied by a clear color change and fluorescence behavior. These correlations of polymer composition and solvent polarity to the FRET efficiency were finally applied to the effective detection of CN− anion; thus demonstrating a function of this polymer as a CN− sensor.
Deadlock and Blockage Control of Automated Manufacturing Systems with an Unreliable Resource
Authors: Luo JianChao , Xing KeYi , Zhou MengChu
Published: September 2018

This work studies the deadlock and blockage control problem of an automated manufacturing system (AMS) with a single unreliable resource. It aims to develop a robust control policy to ensure that AMS can produce all parts in the absence of resource failures, and when the unreliable resource fails, the system can continuously produce all parts that do not require the failed resource. To this end, we divide the system into two regions, continuous and non‐continuous, based on whether all parts in them can be produced continuously or not. For the non‐continuous region, dominating region constraints are established to ensure that all parts in it do not block the production of parts in the continuous region, and an optimal deadlock avoidance policy based on a Petri net model is introduced to guarantee its deadlock‐free operation. For the continuous region, we configure a resource order policy to ensure the smooth productions of AMS. By integrating the dominating region constraints and deadlock avoidance policy with the configured resource order policy, we propose a novel robust control policy. It is proven to be of polynomial complexity and more permissive than the existing one with the same resource order policy. Also, it is tested to be more permissive than other existing policies.
H∞ Filtering for Spatially Interconnected Time‐Delay Systems with Interconnected Chains in Finite Frequency Domains
Authors: Wang Guopeng , Xu Huiling , Zhang Guizhou , Yao Juan
Published: September 2018

This paper deals with the problem of delay‐dependent H∞ filtering for spatially interconnected time‐delay systems (SITSs) with interconnected chains in finite frequency domains. First, a multidimensional (N‐D) hybrid time‐delay Roesser model and a delay‐dependent finite frequency bounded ream lemma (BRL) for SITSs with interconnected chains are proposed. Then, using the obtained delay‐dependent finite frequency BRL, a finite frequency H∞ filter design method can be derived by solving a set of linear matrix inequalities (LMIs). Finally, a practical example is provided to clearly demonstrate the effectiveness of the proposed method.
Reduced distractor interference in neurotypical adults with high expression of autistic traits irrespective of stimulus type
Authors: Muller Spaniol Mayra , Shalev Lilach , Mevorach Carmel
Published: September 2018

Attention atypicality is evident in autism spectrum disorder (ASD) and its broader phenotype with previous studies suggesting that in some cases participants can be more efficient at ignoring distracting irrelevant information. However, it is not clear to what extent this improved filtering capacity is driven by perceptual atypicality, such as local bias or atypical face processing, which is also sometimes reported in these populations. For instance, better ability to ignore the global aspect of a display could stem from a local perceptual bias rather than from improved distractor inhibition. To test whether distractor suppression per se, is associated with high expression of autistic traits, in the present study a large cohort of neurotypical participants (n = 218), in whom expression of autistic traits was assessed, performed two nonspatial attention selection tasks with different categories of stimuli (global/local and face/scene). Importantly, both tasks involved a conflict with one aspect of the stimuli designated as the target and the other designated as the distractor. Across the two experiments adults with high autistic traits were overall, better able to ignore distractors than adults with low autistic traits, irrespective of the type of perceptual processing involved. These results support the notion that autistic tendencies are associated with increased attention filtering (at least when target and distractor remain constant) which is not dependent on perceptual biases. Thus, future work in the broader autism phenotype should explicitly consider the effect played by attention mechanisms in this population. Autism Res 2018, 11: 1345–1355. © 2018 International Society for Autism Research, Wiley Periodicals, Inc.

Lay Summary

In the present study, we show that neurotypical adults with high autistic traits are better able to avoid distraction from conspicuous (but completely irrelevant) distractors when told in advance to do so. This ability is not affected by the type of visual input (for instance, whether the distractor is a face or whether small rather than large letters should be reported). This finding could be important in better understanding the way attention is utilized in Autism.
Hyperplastic Response Following Soft Tissue Augmentation in the Esthetic Zone
Authors: Gluckman Howard , Du Toit Jonathan , Pontes Carla Cruvinel , Hille Jos
Published: September 2018

Introduction

The indications for augmentation of gingival tissue by connective tissue graft (CTG) are numerous. The techniques are widely adopted with extensive literature reporting high success. Harvest techniques include the mid to anterior palate, versus the posterior palate and tuberosity. The latter comprises denser collagen, identified as a more suitable graft. Alas, rarely have hyperplastic responses been reported.

Case Presentation

Two adult, Caucasian patients presented with clinical need for soft tissue augmentation. Autogenous tissue was opted for, harvesting from the tuberosity gingiva. De‐epithelialized outside the mouth and inserted into envelope flaps, late healing resulted in hyperplastic gingival lesions. Neither lesion could be successfully removed, and biopsy for histopathological investigation was carried out.

Conclusion

Hyperplastic response resulting from soft tissue augmentation with tuberosity CTG is rare but may occur. Laser or scalpel might not ensure complete removal. Informing the patient of this rare adverse effect may be important.
The prevalence of computed tomography‐defined leaflet thrombosis in intra‐ versus supra‐annular transcatheter aortic valve prostheses
Authors: Rashid Hashrul N. , Nasis Arthur , Gooley Robert P. , Cameron James D. , Brown Adam J.
Published: September 2018

Introduction

Leaflet thrombosis (LT) defined by computed tomography (CT) following transcatheter aortic valve replacement (TAVR) has been shown to increase cerebrovascular events. The neo‐sinus plays an important role in the development of LT. Intra‐annular valves (IAV) have a larger neo‐sinus when compared to supra‐annular valves (SAV), and has been associated with larger thrombus burden. The prevalence of LT with IAV and SAV in a larger, diverse cohort is unknown.

Methods

We performed a systematic review to assess the prevalence of LT in IAV versus SAV TAVR prostheses. Inclusion criteria were (1) reported CT‐defined LT following TAVR, (2) comparison between LT and non‐LT cohort, (3) separate registry/database, and (4) fully published status. A total of 2,013 citations were reviewed and 7 studies were included.

Results

Overall, 1,644 patients were included from 7 observational studies and the prevalence of LT following TAVR was 12.8%. The Portico valve system (IAV) had the highest prevalence of LT with 35.2%, followed by Symetis Acurate Neo (SAV) at 15.4% and the Lotus valve system (IAV) at 14.5%. LT occurred more frequently in IAV than SAV (13.5% vs. 7%, P = 0.02). Subanalysis of IAV versus SAV with the exclusion of the Portico valve was performed to ensure results were not influenced by this valve system and revealed IAV still had higher rates of LT (12.1% vs. 7%, P = 0.05).

Conclusion

In summary, IAV prostheses appear to be associated with higher rates of LT when compared with SAV.
Retracted: Chemoenzymatic Method for Enantioselective Synthesis of (R)‐2‐Phenylglycine and (R)‐2‐Phenylglycine Amide from Benzaldehyde and KCN Using Difference of Enzyme Affinity to the Enantiomers
Authors: Kawahara Nobuhiro , Asano Yasuhisa
Published: September 2018

In general, enzymatic and chemoenzymatic methods for asymmetric synthesis of α‐amino acids are performed using highly enantioselective enzymes. The enzymatic reactions using α‐aminonitrile as a starting material have been performed using reaction conditions apart from the chemical Strecker synthesis. We developed a new chemoenzymatic method for the asymmetric synthesis of α‐amino acids from aldehydes and KCN by performing Strecker synthesis and nitrilase reaction in the same reaction mixture. Nitrilase AY487533 that showed rather low enantioselectivity in hydrolysis of 2‐phenylglycinonitrile (2PGN) to 2‐phenylglycine (2PG) was utilized in the hydrolysis of aminonitrile formed from benzaldehyde and KCN via 2PGN by Strecker synthesis, preferentially synthesizing (R)‐2PG with more than 95 % yield and enantiomeric excess (ee). The method was also utilized for the synthesis of (R)‐2‐phenylglycine amide ((R)‐2PGNH2) from benzaldehyde and KCN by the chemoenzymatic reaction in the presence of a mutated nitrilase AY487533W186A, which catalyzes the conversion of 2PGN to 2PGNH2.
Phosphorescent Cyclometalated Platinum(II) aNHC Complexes
Authors: Soellner Johannes , Strassner Thomas
Published: September 2018

The synthesis and characterization of the first bidentate C^C* cyclometalated platinum(II) complexes based on abnormal N‐heterocyclic carbenes (aNHC) is presented. The aNHC ligand precursors are prepared from benzonitriles and anilines to form 1,2,3‐trisubstituted imidazolium salts. The title compounds were synthesized by in situ generation of the silver carbene complex, followed by transmetalation to platinum and subsequent introduction of the β‐diketonate ligand. Structural characterization by 2D NMR experiments, as well as solid‐state structures unequivocally prove the abnormal binding mode of the aNHC ligands. Additionally, the photophysical properties of the platinum(II) complexes were examined and studied in detail by DFT calculations and cyclic voltammetry experiments. The title compounds proved to be strongly emissive at room temperature in the green to orange region of the visible spectrum, with emission efficiencies of up to 69 %.
On Jeff=0 Ground State Iridates(V): Tracking Residual Paramagnetism in New Bi2NaIrO6
Authors: Prasad Beluvalli E. , Doert Thomas , Felser Claudia , Jansen Martin
Published: September 2018

Open‐shell transition metal oxides are capable of developing a rich diversity of electronic phases. The specific features evolving crucially depend on an intricate interplay of various local and long‐range electronic interactions. Recently, the 5d transition elements have come into sharp focus because for these elements spin‐orbit coupling (SOC) and onsite Coulomb repulsion (U) are on a comparable energy scale. For Ir4+ the t2g level associated to an octahedral crystal field (CF) is split by SOC, giving rise to a Jeff=
spin state and rendering respective oxides like Sr2IrO4 as Mott insulators. Transferring this scenario to iridium(V) oxides would lead to a diamagnetic ground state, Jeff=0. However, reported experimental results do not lend unambiguous support for such an electronic state. Theoretical explanations for the breakdown of the J=0 magnetic state suffer from conspicuous discrepancies. In an attempt to empirically contribute to resolving the puzzle, Bi2NaIrO6 was synthesized in high purity by precipitation from homogeneous solution; it represents an iridium(V) oxide where long range band structure effects and magnetic superexchange are minimized, and the t2g degeneracy is lifted geometrically. We managed to reduce the strength of paramagnetic response, lending support to a Jeff=0 ground state of Bi2NaIrO6, exhibiting van Vleck type behavior.
Tabletop 700 MHz electron paramagnetic resonance imaging spectrometer
Authors: Buchanan Laura A. , Rinard George A. , Quine Richard W. , Eaton Sandra S. , Eaton Gareth R.
Published: September 2018

Low frequency electron paramagnetic resonance imaging is a powerful tool to noninvasively measure the physiological status of tumors. Here, we report on the design and functionality of a rapid scan and pulse tabletop imaging spectrometer based around an arbitrary waveform generator and 25 mm cross‐loop resonator operating at 700 MHz. Two and four‐dimensional rapid scan spectral‐spatial images are presented. This tabletop imager is a prototype for future preclinical imagers.
Oncologist volume and outcomes in older adults diagnosed with diffuse large B cell lymphoma
Authors: Huntington Scott F. , Hoag Jessica R. , Zhu Weiwei , Wang Rong , Zeidan Amer M. , Giri Smith , Podoltsev Nikolai A. , Gore Steven D. , Ma Xiaomei , Gross Cary P. , Davidoff Amy J.
Published: September 2018

Background

Although provider‐level volume is frequently associated with outcomes in cancers requiring complex surgeries, whether similar relations exist for cancers treated primarily with systemic therapy is unknown.

Methods

Using a population‐based cohort analysis of older adults diagnosed with diffuse large B cell lymphoma (DLBCL) during the years 2004‐2011, we evaluated the association between oncologist volume and 4 clinical outcomes (receipt of any chemotherapy, receipt of an anthracycline‐containing or equivalent regimen, early hospitalization, and overall survival). Our primary explanatory variable was lymphoma treatment volume, defined as the number of patients with newly diagnosed lymphoma for which an oncologist initiated therapy during a 12‐month look‐back period from each incident DLBCL case.

Results

We identified 8247 Medicare beneficiaries who were newly diagnosed with DLBCL. Chemotherapy was administered to 6202 (75.2%) beneficiaries, and 71.4% of cytotoxic regimens contained an anthracycline. Beneficiaries who were treated by higher‐volume oncologists had increased odds of receiving chemotherapy (adjusted odds ratio [aOR], 1.45; 95% confidence interval [CI], 1.24‐1.70; P <.001) and of receiving an anthracycline‐containing regimen (aOR, 1.26; 95% CI, 1.06‐1.50; P = .009). Receiving care from a higher‐volume provider was also associated with decreased hospitalization (aOR, 0.80; 95% CI, 0.69‐0.95; P = .007) and improved survival (adjusted hazard ratio, 0.85; 95% CI, 0.79‐0.92; P < .001).

Conclusion

In older adults diagnosed with DLBCL, receiving care from a provider with more experience treating lymphoma patients was associated with receipt of guideline‐adherent therapy, reduced hospitalizations, and improved survival. Clinical volume may be an important factor in providing high‐quality cancer care in the modern era.
An optimized procedure to develop a 3‐dimensional microfluidic hydrogel with parallel transport networks
Authors: Jafarkhani Mahboubeh , Salehi Zeinab , Shokrgozar Mohammad Ali , Mashayekhan Shohreh
Published: September 2018

The development of microfluidic hydrogels is an attractive method to generate continuous perfusion, induce vascularization, increase solute delivery, and ultimately improve cell viability. However, the transport processes in many in vitro studies still have not been realized completely. To address this problem, we have developed a microchanneled hydrogel with different collagen type I concentrations of 1, 2, and 3 wt% and assessed its physical properties and obtained diffusion coefficient of nutrient within the hydrogel. It is well known that microchannel geometry has critical role in maintaining stable perfusion rate. Therefore, in this study, a computational modeling was applied to simulate the 3D microfluidic hydrogel and study the effect of geometric parameters such as microchannel diameters and their distance on the nutrient diffusion. The simulation results showed that the sample with 3 channels with a diameter of 300 μm has adequate diffusion rates and efficiency (56%). Moreover, this system provides easy control and continuous perfusion rate during 5 days of cell culturing. The simulation results were compared with experimental data, and a good correlation was observed for nutrient profiles and cell viability across the hydrogel.
Retracted: Application of VR computer image technology in 3D virtualization of sports human science
Authors: Cheng Yuan
Published: September 2018

Compared with traditional geometric modeling techniques, image‐based modeling technology has the advantages of simple operation, quick reconstruction, and strong sense of reality. Compared with the three‐dimensional scanning technology, it has the characteristics of low cost and simple algorithm. In a broad sense, the image‐based 3D modeling technique not only includes the geometric modeling of the entity but also includes visual restoration, ie, reconstruction of the geometric model of the entity using the image, and restoration of its corresponding surface texture, reflection properties, lighting conditions, and the like. This paper focuses on the application of geometric reconstruction methods to study the application of VR computer images in the three‐dimensional virtualization of sports human science. By combining the background difference method and the interframe difference method, the target region where the moving human body is located can be accurately extracted from the video, and then the idea of the human body can be divided along the virtual plane. Finally, the end‐point feature points of the human body are determined by the geodesic distance, and a three‐dimensional model skeleton is buried using a discrete penalty function, and an image‐based three‐dimensional reconstruction system is realized.
TMP778, a selective inhibitor of RORγt, suppresses experimental autoimmune uveitis development, but affects both Th17 and Th1 cell populations
Authors: Lyu Cancan , Bing So Jin , Wandu Wambui S. , Xu Biying , Shi Guangpu , Hinshaw Samuel J. , Lobera Mercedes , Caspi Rachel R. , Lu Lin , Yang Jianfei , Gery Igal
Published: September 2018

Experimental autoimmune uveitis (EAU), an animal model for severe intraocular inflammatory eye diseases, is mediated by both Th1 and Th17 cells. Here, we examined the capacity of TMP778, a selective inhibitor of RORγt, to inhibit the development of EAU, as well as the related immune responses. EAU was induced in B10.A mice by immunization with interphotoreceptor retinoid‐binding protein (IRBP). Treatment with TMP778 significantly inhibited the development of EAU, determined by histological examination. In addition, the treatment suppressed the cellular immune response to IRBP, determined by reduced production of IL‐17 and IFN‐γ, as well as lower percentages of lymphocytes expressing these cytokines, as compared to vehicle‐treated controls. The inhibition of IFN‐γ expression by TMP778 is unexpected in view of this compound being a selective inhibitor of RORγt. The observation was further confirmed by the finding of reduced expression of the T‐bet (Tbx21) gene, the transcription factor for IFN‐γ, by cells of TMP778‐treated mice. Thus, these data demonstrate the capacity of TMP778 to inhibit pathogenic autoimmunity in the eye and shed new light on its mode of action in vivo.
[(SeO)4P8W48O184]32–: a Tetraselenite‐Embedded Derivative of the Cyclic 48‐Tungsto‐8‐Phosphate
Authors: Wang Kai‐Yao , Zhang Shu , Ding Dong , Ma Tian , Kortz Ulrich , Wang Cheng
Published: September 2018

The tetraselenite‐incorporated 48‐tungsto‐8‐phosphate [(SeO)4P8W48O184]32– (Se4P8W48) has been synthesized by treating SeO2 with the superlacunary, macrocyclic polyanion precursor [P8W48O184]40– (P8W48) in aqueous solution. Single crystal X‐ray diffraction analysis was carried out on K26Li6[(SeO)4P8W48O184]·98H2O [KLi‐Se4P8W48, monoclinic space group C2/m, a = 35.3618(9) Å; b = 21.7869(6) Å; c = 24.6187(7) Å; β = 132.5822(15) °; V = 13965.4(7) Å3; Z = 2]. The polyanion Se4P8W48 contains four SeO32– groups, adopting a trigonal‐pyramidal coordination geometry, grafted on the rim of the central cavity of P8W48. These four Se atoms are arranged in a coplanar fashion that is perpendicular to the main plane of P8W48, resulting in an overall D2h point group symmetry for Se4P8W48. The KLi‐Se4P8W48 bulk material was characterized by X‐ray diffraction, infrared, UV/Uis, and NMR spectroscopy, as well as thermogravimetric and elemental analysis.
Homodinuclear Lanthanide Complexes with the Divergent Heterotopic 4,4′‐Bipyridine N‐Oxide (bipyMO) Ligand
Authors: Armelao Lidia , Belli Dell'Amico Daniela , Bellucci Luca , Bottaro Gregorio , Ciattini Samuele , Labella Luca , Manfroni Giacomo , Marchetti Fabio , Mattei Carlo Andrea , Samaritani Simona
Published: September 2018

The synthesis of dinuclear molecular complexes [Eu2(dbm)6(bipyMO)2], 1, [Tb2(dbm)6(bipyMO)2], 2, [Eu2(tta)6(bipyMO)2], 3 [Eu2(hfac)6(bipyMO)3], 4, [Tb2(hfac)6(bipyMO)3], 5 is here reported (bipyMO = 4,4′‐bipyridine N‐oxide, Hdbm = dibenzoylmethane, Htta = thenoyltrifluoroacetone, Hhfac = hexafluoroacetylacetone). The products were obtained in mild conditions and with high yields reacting anhydrous lanthanide β‐diketonates and bipyMO in 1:1 or 1.5 molar ratio in toluene. X‐ray single crystal studies on 2, 3, 4 showed that the heterotopic ligands are hypodentate, bridging the two lanthanide centres exclusively through the oxygen atom. Photoluminescence studies show bright red emissions from europium derivatives with absolute quantum yields up to 44 %.
Ferrocenyl‐Functionalized η5‐Thiophene Cr(CO)3 Half‐Sandwich Compounds
Authors: Speck J. Matthäus , Korb Marcus , Hildebrandt Alexander , Lang Heinrich
Published: September 2018

The synthesis of η5‐Cr(CO)3 complexed 2,5‐Fc2‐ (3a), 3,4‐Fc2‐ (3b), 2,3‐Fc2‐ (3c) and 2‐Fc‐3,4,5‐Me3‐thiophenes (3d) [Fc = Fe(η5‐C5H4)(η5‐C5H5)] is described. These half‐sandwich compounds are accessible by the reaction of Cr(CO)3(MeCN)3 with the appropriate substituted thiophenes. The compounds were analyzed by NMR spectroscopy, where a highfield shift for the ring‐carbons and substituted hydrogen atoms of the thiophene core occurred. The 2,5‐ and 3,4‐derivatives could be characterized structurally by single‐crystal X‐ray diffraction analysis, demonstrating that a low bending of the sulfur atom out of the thiophene plane of up to 9.95(17)° and an anti‐arrangement of the ferrocenyl and Cr(CO)3 fragments is characteristic. Electrochemical measurements showed that each ferrocenyl unit could be oxidized separately with higher redox separations for the ferrocenyls of Cr(CO)3 complexes 3b (372 mV) and 3c (334 mV), than for the non complexed species 1b (244 mV) and 1c (283 mV). The potentials of the oxidation processes are shifted anodically by up to 144 mV, indicating an electron‐withdrawing character of the Cr(CO)3 unit. The irreversible Cr/Cr+ oxidations occurred at 545–895 mV. Within the electrochemical studies it could be shown that upon oxidation of the ferrocenyls the Cr(CO)3 half‐sandwich compounds rapidly decompose giving their non complexed thiophenes 1a–d. Solely for the Cr(CO)3‐2,3,4,5‐Me4‐thiophene 3d a reversible redox behavior was observed.
Structure and Magnetism of Seven‐Coordinate FeIII, FeII, CoII and NiII Complexes Containing a Heptadentate 15‐Membered Pyridine‐Based Macrocyclic Ligand
Authors: Antal Peter , Drahoš Bohuslav , Herchel Radovan , Trávníček Zdeněk
Published: September 2018

A heptadentate macrocyclic ligand, H2L (3,12,18‐triaza‐6,9‐dioxabicyclo[12.3.1]octadeca‐1,14,16‐triene‐3,12‐diacetic acid) with two acetate pendant arms, and its complexes [FeIIIL]ClO4 (1), [FeIIL]·H2O (2), [CoIIL]·H2O (3), and [NiIIL]·H2O (4) were synthesized. The complexes possess an axially compressed pentagonal bipyramidal geometry with the coordination numbers of 7 for 2 and 3, and 6 + 1 for 4. The magnetic susceptibility measurements revealed magnetic anisotropy for compounds 1–4 expressed by axial zero‐field splitting (ZFS) parameters (D = –1.3 cm–1 for 1, –9.6 cm–1 for 2, 29.1 cm–1 for 3, and –8.5 cm–1 for 4), with a rhombic ZFS (E/D = 0, 0.006, 0, and 0.193, respectively). Field‐induced slow relaxation of magnetization was observed for the CoII complex 3 only. The structural and magnetic features of 1–4 were compared with those of similar complexes containing ligand with two 2‐pyridylmethyl pendant arms. Magnetic features of the complexes were also evaluated using theoretical calculations (DFT, CASSCF/NEVPT2).
Improving the Energetic Properties of Dinitropyrazoles by Utilization of Current Concepts
Authors: Bölter Marc F. , Klapötke Thomas M. , Kustermann Tessa , Lenz Tobias , Stierstorfer Jörg
Published: September 2018

The syntheses of two different isomeric dinitropyrazole N‐oxides are described and compared to each other. 3,4‐Dinitropyrazole‐1N‐oxide (2) and 3,5‐dinitropyrazole‐1N‐oxide (4) were used, and four different nitrogen‐rich salts were synthesized in order to enhance performance and sensitivity values. Furthermore, two methylene‐bridged isomeric dinitropyrazoles were synthesized by using diiodomethane. The obtained compounds were characterized by using low‐temperature single‐crystal X‐ray diffraction, IR spectroscopy, multinuclear NMR spectroscopy, mass spectrometry, elemental analysis and DSC measurements. The bridged compounds show a high thermal stability (Tdec.: 319 °C and 330 °C) whereas the ionic compounds display lower values (Tdec.: 131 °C–266 °C). Furthermore, the sensitivity values toward impact, friction and electrostatic discharge were determined according to standard methods. Their sensitivity values lie in the range of 5 to 40 J for impact and 216 to 360 N for friction. Adapted from recalculated X‐ray densities and calculated heat of formation values, the energetic performances were computed by using the EXPLO5 code. They support the high energetic character of the title compounds. The values (VD: 7909–8279 m s–1; pCJ: 242–282 kbar) of the salts and bridged pyrazoles (VD: 7966 and 8140 m s–1; pCJ: 263 and 280 kbar) were compared to RDX.
Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand
Authors: Kaniewska Kinga , Dragulescu‐Andrasi Alina , Ponikiewski Łukasz , Pikies Jerzy , Stoian Sebastian A. , Grubba Rafał
Published: September 2018

We report the synthesis of the first series of terminal phosphido iron complexes supported by a β‐diketiminato ligand (Dippnacnac) and their catalytic activity in dehydrocoupling of secondary phosphines. Anionic and neutral mono‐ or diphosphido complexes were obtained from the reaction of [(Dippnacnac)FeCl2Li(dme)2] with the R2PLi (R = iPr, tBu, Cy, Ph) phosphides by tuning the stoichiometric ratio, polarity of the solvent, and the bulkiness of the substituents at the P‐atom. The structures of the synthesized compounds were determined by single‐crystal X‐ray diffraction, which revealed that the iron sites of the anionic complexes are four‐coordinate, whereas those of the neutral complexes are three‐coordinate with almost planar geometry. These phosphido iron complexes were also characterized by 1H NMR and zero‐field Mössbauer spectroscopy. The thermal stability and reactivity of selected complexes were studied. The catalytic properties of the phosphido complexes were confirmed by investigating the conversion of diphenylphosphine to symmetrical 1,1,2,2‐teraphenyldiphosphane.
Zinc‐Doped Nickel Oxide Hollow Microspheres – Preparation Hydrothermal Synthesis and Electrochemical Properties
Authors: Jiang Xueliang , Wang Zhijie , Deng Qi , Zhang Fuqing , You Feng , Yao Chu
Published: September 2018

By using NiSO4·6H2O and Zn(NO3)2 as raw materials, zinc‐doped nickel oxide hollow microspheres (Zn‐NiO‐HM) were prepared through a hydrothermal method. Scanning electron microscope (SEM), transmission electron microscope (TEM), X‐ray photoelectron spectra (XPS), cyclic voltammetry (CV), galvanostatic current charge–discharge (GCD) and electro‐chemical impedance spectroscopy (EIS) were used to characterize the structure and the electrochemical properties of the Zn‐NiO‐HM. The results show that the Zn‐NiO‐HM had an obvious hollow microsphere structure, regular morphology and uniform particle size. The results of XPS indicate zinc was doped in the nickel oxide and existed in the form of Zn2+. The electrochemical measurements show that the electrochemical properties of the Zn‐NiO‐HM were better than those of the NiO powders and of the NiO hollow microspheres.
Cobalt Corroles with Bis‐Ammonia or Mono‐DMSO Axial Ligands. Electrochemical, Spectroscopic Characterizations and Ligand Binding Properties
Authors: Quesneau Valentin , Shan Wenqian , Desbois Nicolas , Brandès Stéphane , Rousselin Yoann , Vanotti Meddy , Blondeau‐Patissier Virginie , Naitana Mario , Fleurat‐Lessard Paul , Van Caemelbecke Eric , Kadish Karl M. , Gros Claude P.
Published: September 2018

Four bis‐ammonia ligated cobalt corroles and four mono‐DMSO ligated cobalt corroles with different meso‐aryl substituents on the macrocycle (A2B‐ and A3‐corroles) were synthesized and investigated as to their electrochemical and spectroscopic properties under different solution conditions. The complexation energies of the investigated cobalt corroles were theoretically calculated to illustrate the propensity of the cobalt center for penta‐coordination or hexa‐coordination with various axial ligands (DMSO, CO, py and NH3). The structure of one hexacoordinate bis‐NH3 cobalt corrole complex was also determined by X‐ray diffraction.
Regiospecific Remote Pt–H Interactions in Oligomethylene‐Vaulted (N^C^N)‐Pincer PtII Complexes
Authors: Komiya Naruyoshi , Hosokawa Takashi , Adachi Junya , Inoue Ryo , Kawamorita Soichiro , Naota Takeshi
Published: September 2018

(N^C^N)‐Pincer type bis(iminomethyl)phenylPtII complexes 1 and 2 having a macrocyclic vaulting structure consisting of deca‐ undeca‐, and dodecamethylene bridges were synthesized and subsequently characterized by NMR, IR spectroscopy, mass spectrometry, and single‐crystal XRD. Unprecedented remote intramolecular Pt–H interactions were observed on the linker hydrogen atoms at β‐and ζ‐positions in a highly regiospecific manner both in the crystal and solution states. The hydrogen bonding nature, originating from overlap between Pt dz² and σ* of the specific C–H bonds, was revealed by NBO analysis of 1 on the basis of dispersion‐corrected DFT calculations.
Regioselective Alcoholysis and Hydrochlorination Reactions of Spiro‐Epoxy Oxindoles at the Spiro‐Centre: Synthesis of 3,3‐Disubstituted Oxindoles and Application for Anticancer Agents
Authors: Tak Raj Kumar , Gupta Naveen , Kumar Manish , Kureshy Rukhsana I. , Khan Noor‐ul H. , Suresh E.
Published: September 2018

An efficient and highly regioselective BiIII catalyzed alcoholysis and Hydrochlorination reaction of spiro‐epoxy oxindole is demonstrated with alcohols and chlorine for easy access to 3,3‐disubstituted oxindoles. This protocol furnished alkyloxy and chlorinated products at the C3 spiro center of the epoxy ring in high yields up to 98 % with excellent regioselectivity > 99 %. The synthetic protocol was further exploited for the synthesis of the anti‐cancer active molecule, 1‐benzyl‐3‐(hydroxymethyl)‐3‐(phenylamino)indolin‐2‐one.
Utilization of Chromone‐3‐Carboxylic Acids as Acceptors in the Michael‐Type Decarboxylative Addition
Authors: Albrecht Anna
Published: September 2018

Decarboxylative Michael–type addition of malonic acid half thioesters to chromone‐3‐carboxylic acids has been developed. The reaction has been realized under Brønsted‐base catalysis providing biologically relevant 2‐substituted chromanones in good or very good yields. Mechanistic studies confirmed that the methodology proceeds according to the doubly decarboxylative reaction pathway. The possibility to perform the reaction in an asymmetric fashion has been demonstrated.
The Hydroxylated, Tetracyclic Bisquinolizidine Alkaloids Baptifoline and Epibaptifoline: Enantioselective Synthesis and Unambiguous Assignment of their Configuration at C‐13
Authors: Goller Jessica , Hübschle Christian B. , Breuning Matthias
Published: September 2018

The epimeric bisquinolizidines baptifoline and epibaptifoline are C‐13 hydroxylated derivatives of the well‐known lupine alkaloid anagyrine. We synthesized both compounds from 11‐allylcytisine and determined their uncertain configuration at the C‐13 stereocenter by NMR, chemical transformation, and X‐ray. The alcohol function was found to be in endo (α) position in baptifoline (configuration: 7R, 9R, 11R, 13R) and in exo (β) position in epibaptifoline (configuration: 7R, 9R, 11R, 13S).
Synthesis of Functionalized Arenopyrans and Arenylsulfanes by Reacting Nitroallylic Acetates with Arenols and Arenethiols
Authors: Basu Pallabita , Sikdar Robi , Kumar Tarun , Namboothiri Irishi N. N.
Published: September 2018

Nitroallylic acetates react with naphthols and electron‐rich phenols under mild conditions (TEA, DCM, room temp.) to afford arenopyrans in moderate to excellent yields. Such (3+3) annulation of a 1,3‐bielectrophilic nitroallylic acetate and a 1,3‐binucleophilic arenol involving an SN2′ reaction and an intramolecular 6‐endo‐trig cyclization takes place in a regio‐ and stereoselective manner. Surprisingly, the reaction of arenethiols under the same conditions provided nitroallylic thioethers instead of the expected arenothiopyrans presumably through a direct SN2 reaction.
Tetracyanocorannulene – an Easily Accessible and Strongly Electron‐Deficient Compound
Authors: Haupt Axel , Walter Ruben , Loll Bernhard , Lentz Dieter
Published: September 2018

Herein we report the synthesis of tetracyanocorannulene by a simple and clean reaction that in principle can be performed on a multigram scale. The tetranitrile can be transformed into corannulene‐fused imides with fluorinated substituents. The cyano compound as well as the imides were investigated structurally by X‐ray diffraction and electrochemically by cyclic voltammetry. Tetracyanocorannulene as well as the derived bis[(pentafluorophenyl)imide] proved to be corannulene compounds with a large electron affinity.
A Stereoselective Synthesis of an Imino Glycal: Application in the Synthesis of (–)‐1‐epi‐Adenophorine and a Homoimindosugar
Authors: Chennaiah Ande , Dahiya Amit , Dubbu Sateesh , Vankar Yashwant D.
Published: September 2018

A concise stereoselective synthesis of an imino glycal is described in 8 steps starting from 1,2‐anhydro‐3,4,6‐tri‐O‐benzyl‐d‐glucopyranose. The utility of the imino glycal has been demonstrated in synthesis of (–)‐1‐epi‐adenophorine and a homoiminosugar as a glycosidase inhibitor. The important features of the developed route include high yields, high stereoselectivity, and application in the synthesis of other iminosugars. Additionally, a new synthon 2‐nitro‐imino glycal has also been synthesized which could act as valuable synthon in carbohydrate chemistry.
Stereoselective Synthesis of 1,2‐Annulated Sugars Having Substituted Tetrahydropyran/(‐furan) Scaffolds Using the Prins‐Reaction
Authors: Chennaiah Ande , Dubbu Sateesh , Parasuraman Kadigachalam , Vankar Yashwant D.
Published: September 2018

Lewis acid catalyzed silyl‐Prins/alkyne‐Prins reactions are utilized for the stereoselective synthesis of 1,2‐annulated sugars having substituted tetrahydropyran (or tetrahydrofuran) scaffolds from appropriately substituted sugar derived alkenyl (or alkynyl) alcohols. These annulated molecules having stereochemical/substitution dispositions similar to those of marine toxins such as maitotoxin could act as useful building blocks for the synthesis of these natural products. Further, the utility of the silyl‐Prins reaction is extended to the synthesis of cis‐sugar fused 4H‐naptho[1,2‐b]pyran and cis‐sugar fused pyrano[3,2‐c][1]benzopyran derivatives.
Rapid Access to Bi‐ and Tri‐Functionalized Dibenzofurans and their Application in Selective Suzuki–Miyaura Cross Coupling Reactions
Authors: Wern Caroline , Ehrenreich Christian , Joosten Dominik , Stein Thorsten vom , Buchholz Herwig , König Burkhard
Published: September 2018

Syntheses of 1,2‐, 1,3‐, 1,4‐, 1,8‐, 2,4‐, 3,4‐, 4,8‐, 1,2,4‐, 1,2,8‐ and 1,3,4‐functionalized dibenzofurans in few steps with good to excellent yields starting from dibenzofuran‐1‐ol or ‐4‐ol are presented. These rapidly accessible bi‐ or tri‐functionalized building blocks are of great interest for the synthesis of bioactive substances or functional material development. Furthermore, for intermediates containing both a bromine and a triflate moiety, a selective mono‐substitution by means of Suzuki–Miyaura reaction (SMR) is described.
Visible‐Light‐Mediated α‐Oxygenation of 3‐(N,N‐Dimethylaminomethyl)‐Indoles to Aldehydes
Authors: Stanek Filip , Pawłowski Robert , Mlynarski Jacek , Stodulski Maciej
Published: September 2018

The visible‐light‐mediated oxygenation of 3‐N,N‐(dimethylaminomethyl)‐indoles bearing various substituents afforded a series of 3‐carbaindole derivatives. Herein we describe the reaction scope, a plausible mechanism and a practical application of this transformation in the formal synthesis of (–)‐vincorine is described as well.
A Review on the Effects of Introducing CNTs in the Modification Process of Electrochemical Sensors
Authors: Beitollahi Hadi , Movahedifar Fahimeh , Tajik Somayeh , Jahani Shohreh
Published: September 2018

This review summarizes some developments in the fabrication of modified sensors and biosensors through the incorporating the carbon nanotubes (CNTs) in their modification ingredients. A large number of papers have paid attention towards the application of carbon nanotubes (CNTs) as electrode constituents and studied its electrochemical behavior. Here, we survey the achievements in the detection of various substances with high selectivity and sensitivity provided using CNTs based electrodes. Moreover, modified electrodes by CNTs have demonstrated the electrocatalytic features and higher sensitivity in detection of analytes. The improved characteristics arises from the large surface area and good conductivity of CNTs. However, it should be considered that the use of single walled carbon nanotubes (SWCNTs) or multi‐walled carbon nanotubes (MWCNTs), the presence of impurities, and the chemical procedures adopted are effective on the performance of the modified sensors.
Novel Flow‐through Potentiometric System for Dimethyamine Assessment Using New Ion Exchangers Doped‐polymeric Membrane Sensors
Authors: Hassan Saad S. M. , Kamel Ayman H. , Abd El‐Naby Heba
Published: September 2018

New simple potentiometric sensing systems are described for the sensitive and selective monitoring of dimethylamine (DMA). These systems are based on using polymeric membranes doped in some ion exchangers such as dimethylamine/phosphomolybdate [(CH3)2NH3]22+[MP]2− (Sensor I), dimethylamine/tetraphenylborate [(CH3)2NH3]+[TPB]− (Sensor II) and dimethylamine/phosphotungstate [(CH3)2NH3]+[TP]− (sensor III). All the sensing systems are incorporated in poly(vinyl chloride) matrix plasticized with o‐NPOE. In a Trizma buffer solution of pH 7.1, the sensors exhibit a stable, fast and linear response for 5.0×10−6–1.0×10−2, 2.5×10−5–1.0×10−2, and 5.0×10−6–1.0×10−2 mol L−1 DMA+ with slopes of 53.2±0.4, 49.4±0.6, and 53.8±0.3 mV decade−1, and detection limits of 2.0×10−6 (0.16 μg mL−1), 1.6×10−5(1.3 μg mL−1), and 1.4×10−6 (0.11 μg mL−1) mol L−1 for sensors (I), (II), and (III), respectively. Potentiometric selectivity measurements of these sensors reveal negligible interferences from most common aliphatic and aromatic amines. Satisfactory results are obtained with an average accuracy of 99.5 % and a mean precision of ±0.5 %. Validation of the proposed assay methods are examined by measuring the limit of detection, linearity range, accuracy, precision, within‐day repeatability, between‐days reproducibility and method ruggedness. Good performance characteristics and applicability of these sensors for DMA assessment in different matrices under static and hydrodynamic modes of measurements are demonstrated. The proposed sensors are also prepared in a tubular form and used as DMA detector in a two‐channel flow injection setup for continuous monitoring. The frequency rate is 27–53 samples h−1. The sensors are satisfactory applied for DMA quantification in both biological matrices and environmental samples with recoveries ranging between 95.0 and 104.0 %.
Impedance Detection of 3‐Phenoxybenzoic Acid with a Noncompetitive Two‐site Phage Anti‐immunocomplex Assay
Authors: Pali Madhavi , Bever Candace R. S. , Vasylieva Natalia , Hammock Bruce D. , Suni Ian I.
Published: September 2018

Both direct and non‐competitive two‐site (sandwich) immunoassays are reported for 3‐phenoxybenzoic acid (3‐PBA) utilizing signal transduction by electrochemical impedance spectroscopy (EIS), and the sandwich immunoassay reduces the detection limit for this small molecule analyte by ∼70×. The direct EIS immunoassay utilizes a polyclonal antibody to 3PBA for biomolecular recognition, while the sandwich EIS immunoassay utilizes in addition a previously reported antiimmunocomplex M13 bacteriophage clone. For both immunoassays, the polyclonal antibody film is immobilized atop an Au electrode by amide bond formation. The direct EIS immunoassay exhibits a 3‐PBA sensitivity of 5.4×104 kΩ cm2 M1, and a detection limit of 2.5×10−4 M (54 μg/ml), while the sandwich EIS immunoassay exhibits a 3PBA sensitivity of 4.2×106 kΩ cm2 M−1, and a detection limit of 3.4×10−6 M (0.74 μg/ml). For the sandwich EIS immunoassay, a constant excess (80×109 PFU/ml) of bacteriophage is maintained during all experiments. This is the first report of a bacteriophage‐assisted sandwich EIS assay.
Recent Advances in the Construction of Biofuel Cells Based Self‐powered Electrochemical Biosensors: A Review
Authors: Fu Liangying , Liu Jingju , Hu Zongqian , Zhou Ming
Published: September 2018

The application of biofuel cells (BFCs) for the construction of self‐powered electrochemical biosensors has recently received enormous attention with exciting advancements. The principle of BFCs for electrochemical biosensing is that the BFCs’ power output which is directly extracted by the biological reactions with the help of biocatalysts is closely related to the analyte's concentration. Such unique feature makes BFCs based electrochemical biosensors with two‐electrode system to be operated without the need of any external power source, which provides a more effective way for the miniaturization and convenient construction of electrochemical biosensors than the traditional electrochemical biosensors with three‐electrode system. Following our previous reviews (Electroanalysis 2012, 24, 197–209; Electroanalysis 2015, 27, 1786–1801), the current review is focused on the recent development and advances in the construction of BFCs based self‐powered electrochemical biosensors which are reported in the years between 2015 and 2018, with a particular emphasis on their possible practical applications in the fields of medical diagnosis, environmental monitoring, food analysis and wearable devices. For these reported BFCs‐based self‐powered electrochemical biosensors, the design approaches are still within the scope of effects (i.e., substrate, inhibition, blocking, gene regulation, enzyme, co‐stabilization, competition, and hybrid effects) summarized by our previous reviews. The outlook, challenges and developing tendency of the future research for the construction of BFCs based self‐powered electrochemical biosensor are discussed in the end. We expect that the advanced electrochemical biosensors based on BFCs with the unique self‐powered capability will continue attracting increasing research interest and lead to new opportunities in various attractive applications related to analytical chemistry.
Streamlined microfluidic analysis of phosphopeptides using stable isotope‐labeled synthetic peptides and MRM‐MS detection
Authors: Deng Jingren , Ikenishi Fumio , Smith Nicole , Lazar Iulia M.
Published: September 2018

Modern high‐throughput and high‐content biological research is performed with advanced instrumentation and complex and time‐consuming protocols, which, as a whole, pose a challenge for routine implementation in a research laboratory. In support of a “bioanalytical toolbox” with potential utility for exploring cellular functions mediated via protein phosphorylation‐a post‐translational modification (PTM) with essential regulatory roles in a variety of cellular processes‐in this work, we describe the development of a simple, integrated microfluidic chip that can perform targeted, quantitative analysis of phosphopeptides involved in cancer‐relevant signaling pathways. The microfluidic device comprises microreactors packed with C18 and TiO2 particles for on‐chip solid phase extraction (SPE) and phosphopeptide enrichment, and an ESI interface for facilitating multiple reaction monitoring (MRM)‐mass spectrometry (MS) detection. The chips are demonstrated for the detection of three phosphopeptides involved in ERBB2/MAPK signaling pathways, selected from the outcome of a proteomic study involving EGF stimulation of SKBR3/HER2+ breast cancer cells. The data demonstrate that the proposed microfluidic strategy can be used for the MS quantification of phosphopeptides in the low nM range from cell lysates without any prior sample pretreatment, fractionation or bioaffinity enrichment, and is generally applicable to the analysis of any phosphopeptide targets.