bluuebunny/crossref_metadata_2025 huggingface dataset:
A Niccolite Structural Multiferroic Metal–Organic Framework Possessing Four Different Types of Bistability in Response to Dielectric and Magnetic Modulation
Authors: Zhao Jiong‐Peng , Xu Jian , Han Song‐De , Wang Qing‐Lun , Bu Xian‐He
Published: April 2017

Multiple switchable physical properties have been demonstrated in one single niccolite structural metal–organic framework, [(CH3CH2)2NH2][FeIIIFeII(HCOO)6] (1), including (i) a reversible ferroelastic phase transition triggered by freezing the disordered (CH3CH2)2NH2+ cations, (ii) a thermally switchable dielectric constant transition accompanied by phase transition, and (iii) thermal and positive magnetic field driven magnetic poles reversal at low temperatures, attributed to different responses of the magnetization of FeII and FeIII sublattices to external stimuli. More interestingly, the exchange anisotropy between the two sublattices can also give rise to tunable positive and negative exchange bias fields. Straightforwardly, such diverse demonstrations of bistability in one single material (depending on the specific tuning way) will provide extra freedom and flexibility for the design of switcher devices.
Dynamic Orthogonal Switching of a Thermoresponsive Self‐Organized Helical Superstructure
Authors: Zhang Lingli , Wang Ling , Hiremath Uma S. , Bisoyi Hari Krishna , Nair Geetha G. , Yelamaggad Channabasaveshwar V. , Urbas Augustine M. , Bunning Timothy J. , Li Quan
Published: April 2017

Controllable manipulation of self‐organized dynamic superstructures of functional molecular materials by external stimuli is an enabling enterprise. Herein, we have developed a thermally driven, self‐organized helical superstructure, i.e., thermoresponsive cholesteric liquid crystal (CLC), by integrating a judiciously chosen thermoresponsive chiral molecular switch into an achiral liquid crystalline medium. The CLC in lying state, in both planar and twisted nematic cells, exhibits reversible in‐plane orthogonal switching of its helical axis in response to the combined effect of temperature and electric field. Consequently, the direction of the cholesteric grating has been observed to undergo 90° switching in a single cell, enabling non‐mechanical beam steering along two orthogonal directions. The ability to reversibly switch the cholesteric gartings along perpendicular directions by appropriately adjusting temperature and electric field strength could facilitate their applications in 2D beam steering, spectrum scanning, optoelectronics and beyond.
Merging Photoredox Catalysis with Iron(III) Catalysis: C5‐H Bromination and Iodination of 8‐Aminoquinoline Amides in Water
Authors: Qiao Huijie , Sun Suyan , Yang Fan , Zhu Yu , Kang Jianxun , Wu Yusheng , Wu Yangjie
Published: April 2017

A simple and efficient protocol for the iron(III)‐catalyzed C5 halogenation of 8‐aminoquinoline with potassium halides via a photoredox process was developed, affording desired products in good to excellent yields. This reaction features its mild and green conditions (proceeding in water under air at room temperature). Electronic effect is not obvious in this reaction, and the desired products can be afforded in good to excellent yields regardless of the benzamides possessing electron‐donating groups or electron‐withdrawing groups; comparatively, substrates containing electron‐donating groups result in slightly higher yields of the coupling products than those of electron‐withdrawing groups. Moreover, a gram‐scale bromination reaction was also successfully fulfilled, demonstrating its potential applicable value in organic synthesis.

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Combining Copper‐Catalyzed Hydroboration with Palladium‐Catalyzed Suzuki Coupling for the One‐pot Synthesis of Arylallylamines under Micellar Conditions
Authors: Horn Pedro A. , Braun Roger K. , Isoppo Victória G. , Costa Jessie S. da , Lüdtke Diogo S. , Moro Angélica V.
Published: April 2017

Herein we report the one‐pot dual‐metal catalytic synthesis of arylallylamines, by combination of a Cu‐catalyzed hydroboration with a Pd‐catalyzed Suzuki arylation, using a broad range of aryl halides. Importantly, the reaction sequence was entirely performed in water, in the presence of small amounts of SPGS‐550M, without the need of solvent switch or addition of organic co‐solvents, rendering it operationally simple and environmentally benign. The usefulness of this methodology was highlighted in a short synthesis of the pharmaceutically important compound naftifine.

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Photoinduced Copper(I)‐Catalyzed Cyanation of Aromatic Halides at Room Temperature
Authors: Kim Kicheol , Hong Soon Hyeok
Published: April 2017

The first photoinduced copper(I)‐catalyzed cyanation of aromatic halides at room temperature has been developed. The sp2 cyanation reaction exhibits outstanding tolerance to functional groups including primary amines and carboxylic acids, and chemoselectivity to SN2‐reactive alkyl chlorides. Mechanistic investigations indicate that the reaction occurs via a single‐electron transfer (SET) between the aryl halide and an excited copper(I) cyanide catalytic intermediate.

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Consensus algorithm‐based approach to fundamental modeling of water pipe networks
Authors: Lee Shin Je , Lee Jong Min , Wu Jingbo , Allgöwer Frank , Suh Jung Chul , Lee Gibaek
Published: April 2017

Modeling the flow dynamics of leaks in water pipe networks is an extremely difficult problem due to the complex entangled network structure and hydraulic phenomenon. A mathematical model for leak dynamics in water pipe networks based on consensus algorithm and water hammer theory is proposed. The resulting model is a simple and linearly interconnected system even though the dynamics of water pipe networks has considerable complexity. The model is then validated using experimental data obtained from real pipe network. A comparative study demonstrates the proposed model can describe the real system with high qualitative and quantitative accuracy and it can be used to develop model‐based leak detection and location algorithm based on state estimation. To show applicability of the proposed model, we apply cooperativeestimation to the developed model. The results demonstrate the consensus‐based pipe model can be potentially used for leak detection and location with state estimation. © 2017 American Institute of Chemical EngineersAIChE J, 63: 3860–3870, 2017
A promising technique of Aegle marmelos leaf extract mediated self‐assembly for silver nanoprism formation
Authors: Rao K. Jagajjanani. , Praneeth N. V. S. , Paria Santanu
Published: April 2017

The Aegle marmelos leaf extract (LE) mediated synthesis of prismatic and spherical Ag nanoparticles (NPs) has been studied. The formation of prismatic structures from spherical NPs was observed microscopically using scanning electron microscope, transmission electron microscope, and atomic force microscope. The shape transformation from spherical NPs to prismatic nanostructures was studied by simply changing LE concentration, keeping constant AgNO3 concentration (1 mM). The role of pH toward prism formation and the effect of sonication on the formed structures were also investigated. The antimicrobial activity of the synthesized Ag spherical/prismatic NPs was evaluated against gram negative bacteria (Escherichia coli, Pseudomonas aeruginosa) and on a phytopathogen Fusarium solani. This green synthesis approach for the synthesis of prismatic Ag nanostructures may be useful for surface‐enhanced Raman spectroscopy application for the detection of low concentration organic molecules, apart from the studied antimicrobial activity. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3670–3680, 2017
An Ion‐Responsive Pincer‐Crown Ether Catalyst System for Rapid and Switchable Olefin Isomerization
Authors: Kita Matthew R. , Miller Alexander J. M.
Published: April 2017

Rapid, selective, and highly controllable iridium‐catalyzed allylbenzene isomerization is described, enabled by tunable hemilability based on alkali metal cation binding with a macrocyclic “pincer‐crown ether” ligand. An inactive chloride‐ligated complex can be activated by halide abstraction with sodium salts, with the resulting catalyst [κ5‐(15c5NCOPiPr)Ir(H)]+ exhibiting modest activity. Addition of Li+ provides a further boost in activity, with up to 1000‐fold rate enhancement. Ethers and chloride salts dampen or turn off reactivity, leading to three distinct catalyst states with activity spanning several orders of magnitude. Mechanistic studies suggest that the large rate enhancement and high degree of tunability stem from control over substrate binding.
A Vicinal Electrophilic Diborylation Reaction Furnishes Doubly Boron‐Doped Polycyclic Aromatic Hydrocarbons
Authors: John Alexandra , Bolte Michael , Lerner Hans‐Wolfram , Wagner Matthias
Published: April 2017

Ten examples of unsymmetrically benzannulated, boron‐doped polycyclic aromatic hydrocarbons (B‐PAHs) were prepared by a one‐pot protocol using 4,5‐dichloro‐1,2‐bis(trimethylsilyl)benzene (1), BBr3, and selected PAHs—among them anthracene, benzo[a]pyrene, biphenylene, and fluoranthene. After mesitylation at the boron centers, the resulting air‐ and water‐stable products were investigated by 1H/11B{1H}/13C{1H} NMR spectroscopy, X‐ray crystallography, cyclic voltammetry, and UV/Vis absorption/emission spectroscopy. The experiments were augmented by DFT calculations. Most of the B‐PAHs are brightly luminescent (ΦPL up to 90 %) and undergo reversible reduction at moderate half‐wave potentials. The two chloro substituents of 1 are not only mandatory for accomplishing efficient diborylation, but can subsequently be used for Stille‐type coupling reactions to introduce 2‐thienyl moieties. Alternatively, Cl/H exchange is achievable with HSiEt3 in a quantitative, Pd‐catalyzed transformation.
The Reactivity of Benzyl Lithium Species is Regulated by Intermediate Structures
Authors: Kroesen Ulrike , Knauer Lena , Strohmann Carsten
Published: April 2017

The reaction of benzyl lithiums is an important aspect in organic and organometallic synthesis. Reported herein are detailed insights into the reactivity of benzyl lithiums as regulated by intermediate structures. By discussing the carbometalation of allylamines and the reaction of the formed benzyl‐lithium compounds with electrophiles, the influence of the metal as well as the solvent on the electronic structure of the intermediate is described. This molecular structure strongly influences the reactivity of these intermediates. By choosing the appropriate reaction conditions, the regioselectivity of reactions with electrophiles can be regulated. With trimethylchlorosilane in n‐pentane a selective reaction at the para‐position takes place. In contrast, selective reaction at the benzylic position, with trimethylchlorostannane in tetrahydrofuran (THF) as a solvent, is accomplished.
A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation
Authors: Widegren Magnus B. , Harkness Gavin J. , Slawin Alexandra M. Z. , Cordes David B. , Clarke Matthew L.
Published: April 2017

A new hydrogenation catalyst based on a manganese complex of a chiral P,N,N ligand has been found to be especially active for the hydrogenation of esters down to 0.1 mol % catalyst loading, and gives up to 97 % ee in the hydrogenation of pro‐chiral deactivated ketones at 30–50 °C.
Highly reusable support‐free copper(II) complex of para‐hydroxy‐substituted salen: Novel, efficient and versatile catalyst for C─N bond forming reactions
Authors: Sharghi Hashem , Aberi Mahdi , Shiri Pezhman
Published: April 2017

An air‐stable, highly active and versatile method for C─N bond forming reactions is reported. Under mild conditions using a highly reusable support‐free Cu(II)–salen complex, structurally diverse N‐aryl‐substituted compounds were obtained via direct C─N bond forming reaction of HN‐heterocycles with aryl iodides or three‐component C─N bond forming reaction of 2‐bromobenzaldehyde, aniline derivatives and sodium azide in good to excellent yields. C─N bond forming reaction for benzimidazole derivatives was also performed in the presence of the catalyst under ambient conditions. A series of hybrid benzimidazoles bearing morpholine, tetrazole and quinoxaline backbones were produced using this method. All reactions were performed in short times under air. The Cu(II) catalyst could be reused up to eight times in the direct cross‐coupling reaction of 9H–carbazole with iodobenzene without any decrease in its catalytic activity.
Retracted: Chiral Jacobsen's catalyst immobilized on zinc poly(styrene‐phenylvinylphosphonate)‐phosphate functionalized by diamine as highly efficient and reusable catalyst for alkene epoxidation
Authors: Huang Jing , Luo Yan , Cai Jiali
Published: April 2017

Chiral Jacobsen's catalyst anchored on zinc poly(styrene‐phenylvinylphosphonate)‐phosphate (ZnPS‐PVPA) functionalized by diamines shows superior catalytic activities (conversion up to 99%; enantiomeric excess up to 99%) in the enantioselective epoxidations of unfunctional olefins with m‐chloroperoxybenzoic acid and NaIO4 as oxidants. The whole chiral salen Mn(III) catalyst, including the ZnPS‐PVPA support and the linker as well as chiral salen Mn ligand together contribute to the chirality of products. The heterogeneous catalyst has the potential for use in industry owing to superior stability (recycling nine times) and activity in large‐scale reactions (such as 200 times).
Influence of seasonality on cetacean diversity, abundance, distribution and habitat use in the western Mediterranean Sea: Implications for conservation
Authors: Arcangeli Antonella , Campana Ilaria , Bologna Marco A.
Published: April 2017

Cetaceans are key biological indicators of the status of marine waters and are protected under an extensive legislative framework. Research about these highly dynamic species is challenging, so seasonal cycles and patterns of distribution, especially in high sea areas, are still poorly understood.

This study contributes to improving knowledge about cetacean occurrence in largely unexplored areas of medium‐latitudes in the western Mediterranean Sea. Systematic surveys were conducted along a trans‐regional transect over 3 years (October 2012 to September 2015) allowing consistent data collection over almost 60 000 km of effort through all seasons.

Seasonal cetacean diversity was investigated using a 25 km2 grid cell as a statistical unit to explore patterns of abundance, distribution, and habitat use in three marine sectors (Sardinian–Balearic, Bonifacio Strait, Tyrrhenian). All cetacean species regularly present in the Mediterranean basin were detected, with highest occurrence in fin whale and striped dolphin, followed by bottlenose dolphin and sperm whale.

The Sardinian–Balearic sector generally showed higher species richness and diversity than the Tyrrhenian, where seasonal variations were more pronounced. The study suggested seasonal movements, especially for fin whale and striped dolphin, in the Sardinian–Balearic sector with peaks of occurrence during spring/summer and lower numbers during winter/autumn, and also delivered interesting insights to rarer pelagic species.

The study identified areas/seasons in which the combined effect of high species diversity, abundance, significance of hot spots and presence of juveniles require increasing conservation effort. Results underline the important contribution of continuous monitoring in high sea areas to the implementation of adaptive protection measures.
The Therapeutic Efficacy of Botulinum Toxin in Treating Scleroderma‐Associated Raynaud's Phenomenon: A Randomized, Double‐Blind, Placebo‐Controlled Clinical Trial
Authors: Bello Ricardo J. , Cooney Carisa M. , Melamed Eitan , Follmar Keith , Yenokyan Gayane , Leatherman Gwendolyn , Shah Ami A. , Wigley Fredrick M. , Hummers Laura K. , Lifchez Scott D.
Published: April 2017

Objective

To assess the therapeutic efficacy of local injections of botulinum toxin type A (Btx‐A) in improving blood flow to the hands of patients with Raynaud's phenomenon (RP) secondary to scleroderma.

Methods

In this randomized, double‐blind, placebo‐controlled clinical trial, patients with scleroderma‐associated RP received Btx‐A (50 units in 2.5 ml sterile saline) in one randomly selected hand and sterile saline (2.5 ml) in the opposite hand. Follow‐up at 1 and 4 months postinjection included laser Doppler imaging of hands, patient‐reported outcomes, and physical examination. We compared outcomes using paired t‐tests and population‐average generalized models with generalized estimating equations.

Results

Of 40 patients enrolled, 25 had limited scleroderma and 15 had diffuse scleroderma. From baseline to 1‐month follow‐up, there was a greater reduction in average blood flow in Btx‐A–treated hands compared to placebo‐treated hands. The model estimated that this difference was statistically significant (average difference −30.08 flux units [95% confidence interval −56.19, −3.98], P for interaction = 0.024). This difference was mainly influenced by patients with longstanding RP and diffuse scleroderma. Change in blood flow at 4‐month follow‐up was not significantly different between groups. Clinical measures (QuickDASH, McCabe Cold Sensitivity Score, pain on a visual analog scale, and Raynaud's Condition Score) improved slightly for Btx‐A–treated hands.

Conclusion

Our laboratory‐based laser Doppler imaging flow data do not support using Btx‐A to treat RP in all scleroderma patients. The secondary clinical outcomes suggest some positive effect, but its clinical meaningfulness is questionable. The role of Btx‐A in treating RP should be further studied with more homogeneous patient populations and in unique clinical situations such as acute digital ischemia.
Stabilities and Biological Activities of Vanadium Drugs: What is the Nature of the Active Species?
Authors: Levina Aviva , Lay Peter A.
Published: April 2017

Diverse biological activities of vanadium(V) drugs mainly arise from their abilities to inhibit phosphatase enzymes and to alter cell signaling. Initial interest focused on anti‐diabetic activities but has shifted to anti‐cancer and anti‐parasitic drugs. V‐based anti‐diabetics are pro‐drugs that release active components (e.g., H2VO4−) in biological media. By contrast, V anti‐cancer drugs are generally assumed to enter cells intact; however, speciation studies indicate that nearly all drugs are likely to react in cell culture media during in vitro assays and the same would apply in vivo. The biological activities are due to VV and/or VIV reaction products with cell culture media, or the release of ligands (e.g., aromatic diimines, 8‐hydroxyquinolines or thiosemicarbazones) that bind to essential metal ions in the media. Careful consideration of the stability and speciation of V complexes in cell culture media and in biological fluids is essential to design targeted V‐based anti‐cancer therapies.
Placebo‐like response in absence of treatment in children with Autism
Authors: Jones Rebecca M. , Carberry Caroline , Hamo Amarelle , Lord Catherine
Published: April 2017

Caregiver report is the most common measure of change in pediatric psychiatry. Yet, placebo response rates pose significant challenges to reliably detect a treatment response. The present study simulated an eight‐week clinical trial protocol for Autism Spectrum Disorder (ASD) for the purpose of testing the feasibility and validity of several outcome measures. Twenty caregivers answered questions about their child's behavior on their smartphone each week and completed a battery of paper questionnaires during weeks one and eight. No treatment was administered. Caregivers reported a significant decrease in problem behaviors on the Aberrant Behavior Checklist (ABC) (29% decrease) and general ASD behaviors on the Social Responsiveness Scale (SRS) (7% decrease). There was also a trend of behavior improvement from smartphone questions but no significant changes in clinical ratings of core diagnostic features of ASD. Participation in a comprehensive protocol in the absence of a particular treatment significantly influenced how caregivers perceived the severity of their children's problem behaviors. These placebo‐like effects represent substantial challenges for randomized controlled trials (RCTs) that use treatment as usual and have implications for future behavioral and pharmacological treatment trial designs. Autism Res 2017, 10: 1567–1572. © 2017 International Society for Autism Research, Wiley Periodicals, Inc.
Seeing into the Future: Future Time Orientation as a Moderator of Temporal Distance Effects on Educators' Decisions
Authors: Kogut Tehila , Eyal Tal , Sharon Idit
Published: April 2017

Research suggests that the temporal distance from decision outcomes leads to divergent decisions for the near and the distal future. As such, high‐level idealistic concerns and values dominate decisions for the distant future, whereas low‐level pragmatic concerns play a greater role in decisions for the near future. We examined how individual differences in future time orientation are related to decisions vis‐à‐vis the near versus the distal future. The results of three studies, with participants with varying levels of expertise—students (Studies 2 and 3), teachers (Study 1), and school principals (Study 2)—show that principals tend to be overall more idealistic in their choices. Yet discrepancies between decisions for the near versus the distal future exist among all three levels of expertise. However, this dominance of idealistic over pragmatic concerns for more distant future decisions effect was smaller the higher the future time orientation was (whether measured or manipulated). Implications for educational and managerial decision making and training are discussed. Copyright © 2017 John Wiley & Sons, Ltd.
Congenital Lung Agenesis: Incidence and Outcome in the North of England
Authors: Thomas Matthew , Robertson Nic , Miller Nicola , Rankin Judith , McKean Michael , Brodlie Malcom
Published: April 2017

Background

Unilateral lung agenesis is an uncommon congenital abnormality, with a lack of reported accurate incidence estimates. Prognosis is also uncertain, with older literature reporting poor outcomes.

Methods

The North of England register of congenital anomalies (Northern Congenital Abnormality Survey) records cases of congenital anomalies to mothers' resident in the region. We used the register to identify all patients with congenital lung agenesis born between 2004 and 2013 to calculate an accurate incidence estimate and report clinical outcomes with contemporary management.

Results

Four patients with congenital lung agenesis were born during the study period, giving an estimated incidence in the North of England of 1.22 per 100,000 live births (95% confidence interval, 0.33–3.11). Two patients had associated congenital heart disease requiring corrective surgery, and one had musculoskeletal anomalies. All four patients are alive and well without a regular oxygen requirement.

Conclusion

Contrary to previous reports, the medium term outcomes in our patients have been good, even when lung agenesis is associated with other congenital anomalies. Long‐term prognosis with modern management remains unknown, and the potential for the development of pulmonary hypertension remains a concern. Birth Defects Research 109:857–859, 2017. © 2017 Wiley Periodicals, Inc.
Alcohol‐tolerant mutants of cyanobacterium Synechococcus elongatus PCC 7942 obtained by single‐cell mutant screening system
Authors: Arai Sayuri , Hayashihara Kayoko , Kanamoto Yuki , Shimizu Kazunori , Hirokawa Yasutaka , Hanai Taizo , Murakami Akio , Honda Hiroyuki
Published: April 2017

Enhancement of alcohol tolerance in microorganisms is an important strategy for improving bioalcohol productivity. Although cyanobacteria can be used as a promising biocatalyst to produce various alcohols directly from CO2, low productivity, and low tolerance against alcohols are the main issues to be resolved. Nevertheless, to date, a mutant with increasing alcohol tolerance has rarely been reported. In this study, we attempted to select isopropanol (IPA)‐tolerant mutants of Synechococcus elongatus PCC 7942 using UV‐C‐induced random mutagenesis, followed by enrichment of the tolerant candidates in medium containing 10 g/L IPA and screening of the cells with a high growth rate in the single cell culture system in liquid medium containing 10 g/L IPA. We successfully acquired the most tolerant strain, SY1043, which maintains the ability to grow in medium containing 30 g/L IPA. The photosynthetic oxygen‐evolving activities of SY1043 were almost same in cells after 72 h incubation under light with or without 10 g/L IPA, while the activity of the wild‐type was remarkably decreased after the incubation with IPA. SY1043 also showed higher tolerance to ethanol, 1‐butanol, isobutanol, and 1‐pentanol than the wild type. These results suggest that SY1043 would be a promising candidate to improve alcohol production using cyanobacteria. Biotechnol. Bioeng. 2017;114: 1771–1778. © 2017 Wiley Periodicals, Inc.
Autodisplay of glucose‐6‐phosphate dehydrogenase for redox cofactor regeneration at the cell surface
Authors: Schüürmann Jan , Quehl Paul , Lindhorst Fabian , Lang Kristina , Jose Joachim
Published: April 2017

Inherent cofactor regeneration is a pivotal feature of whole cell biocatalysis. For specific biotechnological applications, surface display of enzymes is emerging as a tool to circumvent mass transfer limitations or enzyme stability problems. Even complex reactions can be accomplished applying displayed enzymes. Yet, industrial utilization of the technique is still impeded by lacking cofactor regeneration at the cell surface. Here, we report on the surface display of a glucose‐6‐phoshate dehydrogenase (G6PDH) via Autodisplay to address this limitation and regenerate NADPH directly at the cell surface. The obtained whole cell biocatalyst demonstrated similar kinetic parameters compared to the purified enzyme, more precisely KM values of 0.2 mM for NADP+ and calculated total turnover numbers of 107. However, the KM for the substrate G6P increased by a factor of 7 to yield 1.5 mM. The whole cell biocatalyst was cheaper to produce, easy to separate from the reaction mixture and reusable in consecutive reaction cycles. Furthermore, lyophilization allowed storage at room temperature. The whole cell biocatalyst displaying G6PDH was applicable for NADPH regeneration in combination with soluble as well as surface displayed enzymes and model reactions in combination with bacterial CYP102A1 and human CYP1A2 were realized. Biotechnol. Bioeng. 2017;114: 1658–1669. © 2017 Wiley Periodicals, Inc.
A plug‐and‐play pathway refactoring workflow for natural product research in Escherichia coli and Saccharomyces cerevisiae
Authors: Ren Hengqian , Hu Pingfan , Zhao Huimin
Published: April 2017

Pathway refactoring serves as an invaluable synthetic biology tool for natural product discovery, characterization, and engineering. However, the complicated and laborious molecular biology techniques largely hinder its application in natural product research, especially in a high‐throughput manner. Here we report a plug‐and‐play pathway refactoring workflow for high‐throughput, flexible pathway construction, and expression in both Escherichia coli and Saccharomyces cerevisiae. Biosynthetic genes were firstly cloned into pre‐assembled helper plasmids with promoters and terminators, resulting in a series of expression cassettes. These expression cassettes were further assembled using Golden Gate reaction to generate fully refactored pathways. The inclusion of spacer plasmids in this system would not only increase the flexibility for refactoring pathways with different number of genes, but also facilitate gene deletion and replacement. As proof of concept, a total of 96 pathways for combinatorial carotenoid biosynthesis were built successfully. This workflow should be generally applicable to different classes of natural products produced by various organisms. Biotechnol. Bioeng. 2017;114: 1847–1854. © 2017 Wiley Periodicals, Inc.
Competing risks analysis of microsatellite instability as a prognostic factor in colorectal cancer
Authors: Toh J , Chapuis P H , Bokey L , Chan C , Spring K J , Dent O F
Published: April 2017

Background

Despite an extensive literature suggesting that high microsatellite instability (MSI-H) enhances survival and protects against recurrence after colorectal cancer resection, such effects remain controversial as many studies show only a weak bivariate association or no multivariable association with outcome. This study examined the relationship between MSI status and colorectal cancer outcomes with adjustment for death from other causes as a competing risk.

Methods

A hospital database of patients following colorectal cancer resection was interrogated for clinical, operative, pathology, adjuvant therapy and follow-up information. MSI-H status was determined by immunohistochemistry for mismatch repair protein deficiency. The cumulative incidence of recurrence and colorectal cancer-specific death was evaluated by competing risks methods.

Results

Among 1009 patients who had a resection between August 2002 and December 2008, and were followed to at least December 2013, there were 114 (11·3 per cent) with MSI-H (72·8 per cent aged at least 70 years; 63·2 per cent women). After potentially curative resection, with adjustment for non-colorectal cancer death as a competing risk and adjustment for 22 clinical, operative and pathological variables, there was no association between MSI-H and recurrence (hazard ratio (HR) 0·81, 95 per cent c.i. 0·42 to 1·57) or colorectal cancer-specific death (HR 0·73, 0·39 to 1·35) in this patient population. For palliative resections, there was no association between MSI-H and colorectal cancer-specific death (HR 0·65, 0·21 to 2·04). MSI-H was associated with non-colorectal cancer death after both curative (HR 1·55, 1·04 to 2·30) and palliative (HR 3·80, 1·32 to 11·00) resections.

Conclusion

Microsatellite instability status was not an independent prognostic variable in these patients.
Simultaneous determination of difenoconazole, trifloxystrobin and its metabolite trifloxystrobin acid residues in watermelon under field conditions by GC–MS/MS
Authors: Kang Di , Zhang Haizhen , Chen Yuling , Wang Fei , Shi Lihong , Hu Deyu , Zhang Kankan
Published: April 2017

An optimized quick, easy, cheap, effective, rugged and safe method for the simultaneous determination of difenoconazole, trifloxystrobin and its metabolite trifloxystrobin acid residues in watermelon and soil was developed and validated by gas chromatography with tandem mass spectrometry. The samples were extracted with acetonitrile (1% formic acid) and cleaned up by dispersive solid‐phase extraction with octadecylsilane sorbent. The limit of quantification of the method was 0.01 mg/kg, and the limit of detection was 0.003 mg/kg for all three analytes. The recoveries of the fungicides in watermelon, pulp and soil were 72.32–99.20% for difenoconazole, 74.68–87.72% for trifloxystrobin and 78.59–92.66% for trifloxystrobin acid with relative standard deviations of 1.34–14.04%. The dissipation dynamics of difenoconazole and trifloxystrobin in watermelon and soil followed the first‐order kinetics with half‐lives of 3.2–8.8 days in both locations. The final residue levels of difenoconazole and trifloxystrobin were below 0.1 mg/kg (maximum residue level [MRL] set by China) and 0.2 mg/kg (MRL set by European Union), respectively, in pulp samples collected 14 days after the last application. These results could help Chinese authorities to establish MRL of trifloxystrobin in watermelon and provide guidance for the safe and proper application of both fungicides on watermelon.
Simultaneous quantification and semi‐quantification of amentoflavone and its metabolites in human intestinal bacteria by liquid chromatography Orbitrap high‐resolution mass spectrometry
Authors: Qian Yiyun , Jiang Shu , Zhu Zhenhua , Wang Qi , Su Shulan , Tao Jinhua , Duan Jin‐ao
Published: April 2017

A quick, easy, effective method followed by ultra‐high‐pressure liquid chromatography coupled with linear ion trap–Orbitrap tandem mass spectrometry (UHPLC‐LTQ‐Orbitrap MS) was developed for the simultaneous identification and quantification of the metabolites produced by amentoflavone (AMF) in human intestinal bacteria from human feces. The method validated for quantification of AMF concerning precision, accuracy, recovery, matrix effect, stability and limits showed acceptable results. Compared with blank human intestinal bacteria chromatography, three metabolites were identified based on high‐accuracy protonated precursors and multi‐stage mass spectrometry (MSn) using the proposed strategy. At the same time, a new method was developed for semi‐quantification of three metabolites. We describe the trend over 24 h of concentration–time curves for AMF and its metabolites. Moreover, the main metabolic pathway of AMF was clarified in human intestinal bacteria. The method was validated and successfully applied to the detection and quantification of AMF and its metabolites.
Advanced model‐based control strategies for the intensification of upstream and downstream processing in mAb production
Authors: Papathanasiou Maria M. , Quiroga‐Campano Ana L. , Steinebach Fabian , Elviro Montaña , Mantalaris Athanasios , Pistikopoulos Efstratios N.
Published: April 2017

Current industrial trends encourage the development of sustainable, environmentally friendly processes with minimal energy and material consumption. In particular, the increasing market demand in biopharmaceutical industry and the tight regulations in product quality necessitate efficient operating procedures that guarantee products of high purity. In this direction, process intensification via continuous operation paves the way for the development of novel, eco‐friendly processes, characterized by higher productivity and lower production costs. This work focuses on the development of advanced control strategies for (i) a cell culture system in a bioreactor and (ii) a semicontinuous purification process. More specifically, we consider a fed‐batch culture of GS‐NS0 cells and the semicontinuous Multicolumn Countercurrent Solvent Gradient Purification (MCSGP) for the purification process. The controllers are designed following the PAROC framework/software platform and their capabilities are assessed in silico, against the process models. It is demonstrated that the proposed controllers efficiently manage to increase the system productivity, returning strategies that can lead to continuous, stable process operation. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:966–988, 2017
Understand participation rights of student‐athletes with disabilities
Authors: O'Brien Timothy
Published: April 2017

Several years have passed since the Office for Civil Rights issued a “Dear Colleague Letter” discussing the participation rights of student‐athletes with disabilities at the interscholastic level and the corresponding obligations of schools. Although a similar letter hasn't been issued at the intercollegiate level, that DCL, a federal regulation that addresses intercollegiate athletics, and a number of court cases collectively provide a helpful framework and important reminders for how to address these issues in the college sports arena.
Psychological biases of individual investors and financial satisfaction
Authors: Sahi Shalini Kalra
Published: April 2017

Traditional finance theory is based on the principle of maximization of utility and explains how choices are made by rational people. Although the theory provides numerous insights, observation of actual behavior of people was seen to be different from what the theory predicted. The homo economicus is in reality a homo sapien who has emotions and beliefs that help to filter the content from his or her environment. These beliefs and preferences that arise due to cognitive limitations, presence of emotions, and various psychological motives guide or bias his or her decisions. Much literature states that the biases should be corrected as they negatively impact financial behaviour and individual's well‐being. However, evolutionary psychology considers biases as design features of human mind. Thus, biases are not always bad, as at times, these biases can help the individual investor to choose the best course of action from the multiple possibilities and enable committing the less costly mistakes, thereby helping the individual to achieve satisficing behaviour. This paper aims to explore the investor biases and see whether they are related to the financial satisfaction of the individuals. Financial satisfaction is the measure of satisfaction with one's financial situation. The results showed that overconfidence bias, reliance on expert bias, and self‐control bias have a positive and significant association with financial satisfaction levels. Association of a few other biases with financial satisfaction was also observed under certain control conditions. This study provides further insights on investor behavior and paves the way for various possibilities for future research.
Chemical Activation in Blood Serum and Human Cell Culture: Improved Ruthenium Complex for Catalytic Uncaging of Alloc‐Protected Amines
Authors: Völker Timo , Meggers Eric
Published: April 2017

Chemical (as opposed to light‐induced) activation of caged molecules is a rapidly advancing approach to trigger biological processes. We previously introduced the ruthenium‐catalyzed release of allyloxycarbonyl (alloc)‐protected amines in human cells. A restriction of this and all other methods is the limited lifetime of the catalyst, thus hampering meaningful applications. In this study, we addressed this problem with the development of a new generation of ruthenium complexes for the uncaging of alloc‐protected amines with superior catalytic activity. Under biologically relevant conditions, we achieved a turnover number >300, a reaction rate of 580 m−1 s−1, and we observed high activity in blood serum. Furthermore, alloc‐protected doxorubicin, as an anticancer prodrug, could be activated in human cell culture and induced apoptosis with a single low dose (1 μm) of the new catalyst.
Guanosine‐5′‐Monophosphate Polyamine Hybrid Hydrogels: Enhanced Gel Strength Probed by z‐Spectroscopy
Authors: Belda Raquel , García‐España Enrique , Morris Gareth A. , Steed Jonathan W. , Aguilar Juan A.
Published: April 2017

The self‐assembling tendencies of guanosine‐5′‐monophosphate (GMP) can be drastically increased using polyamines, with potential applications in the production of biocompatible smart materials, as well as for the design of antitumor drugs based on G‐quadruplex stabilization. Results from scanning electron microscopy (SEM), wide angle X‐ray scattering (WAXS), rheology, and nuclear magnetic resonance (NMR) z‐spectroscopy studies are presented.
N‐Methyl‐4‐pyridinium Tetrazolate Zwitterion‐Based Photochromic Materials
Authors: Chen Xiang‐Yi , Zhang Ning‐Ning , Cai Li‐Zhen , Li Pei‐Xin , Wang Ming‐Sheng , Guo Guo‐Cong
Published: April 2017

N,N′‐Disubstituted bipyridinium (viologen) and N‐monosubstituted bipyridinium compounds are well known for their electron‐transfer (ET) photochromic behavior. Their modification has exclusively focused on the N‐substituents to date. For the first time, we have studied the photochromic behavior when one pyridyl ring of the bipyridinium is substituted with a multifunctional azole group, and have found that two new coordination compounds based on N‐methyl‐4‐pyridinium tetrazolate (mptz) zwitterion, [Zn(mptz)2Br2] (1) and [Cd3(mptz)2Cl6]n⋅4n H2O (2), exhibit typical ET photochromic behavior owing to photoinduced ET from halogen anion to the mptz ligand. This work demonstrates a new simple, neutral photoactive molecule with electron‐accepting ability, which may act as a photoactive component for materials with potential photoswitching and photocatalysis applications.
Supramolecular Amino Acid Based Hydrogels: Probing the Contribution of Additive Molecules using NMR Spectroscopy
Authors: Ramalhete Susana M. , Nartowski Karol P. , Sarathchandra Nichola , Foster Jamie S. , Round Andrew N. , Angulo Jesús , Lloyd Gareth O. , Khimyak Yaroslav Z.
Published: April 2017

Supramolecular hydrogels are composed of self‐assembled solid networks that restrict the flow of water. l‐Phenylalanine is the smallest molecule reported to date to form gel networks in water, and it is of particular interest due to its crystalline gel state. Single and multi‐component hydrogels of l‐phenylalanine are used herein as model materials to develop an NMR‐based analytical approach to gain insight into the mechanisms of supramolecular gelation. Structure and composition of the gel fibres were probed using PXRD, solid‐state NMR experiments and microscopic techniques. Solution‐state NMR studies probed the properties of free gelator molecules in an equilibrium with bound molecules. The dynamics of exchange at the gel/solution interfaces was investigated further using high‐resolution magic angle spinning (HR‐MAS) and saturation transfer difference (STD) NMR experiments. This approach allowed the identification of which additive molecules contributed in modifying the material properties.
Near‐Infrared Circularly Polarized Light Triggered Enantioselective Photopolymerization by Using Upconversion Nanophosphors
Authors: Yang Guang , Zhu Liangfu , Hu Jingang , Xia Hongyan , Qiu Dong , Zhang Qijin , Zhang Douguo , Zou Gang
Published: April 2017

Circularly polarized light (CPL) is considered to be a true chiral entity and has been suggested as an explanation for the introduction of initial chiral biases into key biomolecular building blocks. CPL used recently asymmetric photochemical reactions is of wavelengths mainly in the UV and visible regions, whereas natural CPL observed in star‐forming regions of the Orion constellation falls in the IR region. Whether CPL in the IR or near‐IR region could be utilized to trigger asymmetric photochemical reactions remains to be determined. Herein, it is demonstrated that enantioselective photopolymerization can be realized by using λ=980 nm CPL as the only chiral source. By incorporating NaYF4 nanophosphors as the antenna species, the enantioselective photopolymerization of achiral benzaldehyde‐substituted diacetylene monomer can be realized based on an upconversion mechanism upon exposure to λ=980 nm CPL. The screw direction of the helical PDA chains can be completely controlled by the handedness of incident λ=980 nm CPL.
Discrimination of Saccharides by a Simple Array
Authors: Bojanowski N. Maximilian , Bender Markus , Seehafer Kai , Bunz Uwe H. F.
Published: April 2017

We report the development of a two‐component probe system as fluorescence turn‐on assay of simple saccharides. The quenching of an anionic conjugated water‐soluble polymer by a cationic quencher has been reported previously. Three different boronic acid functionalized benzyl viologens and three conjugated polymers of the poly(aryleneethynylene) type form nine non‐fluorescent complexes. This small library discriminates nine different simple saccharides in aqueous solutions by fluorescence turn‐on in a displacement assay. The saccharides can be discriminated and identified with this simple system.
Synthesis of N‐Propargylsulfoximines by Copper‐Catalyzed A3‐Couplings
Authors: Cheng Hanchao , Wen Jian , Bolm Carsten
Published: April 2017

An efficient synthesis of N‐propargylsulfoximines was developed through a copper‐catalyzed coupling of aldehydes, alkynes, and NH‐sulfoximines. The reaction requires no co‐catalyst or ligand and shows a wide substrate scope with moderate to good yields.
Stable NiII Porphyrin meso‐Oxy Radical with a Quartet Ground State
Authors: Stähler Cosima , Shimizu Daiki , Yoshida Kota , Furukawa Ko , Herges Rainer , Osuka Atsuhiro
Published: April 2017

10,15,20‐Tris(pentafluorophenyl)‐substituted NiII–porphyrin meso‐oxy radical bearing two coordinating pyridines was synthesized as a stable radical with a quartet ground state (S=3/2). X‐ray structural analysis revealed that the NiII porphyrin moiety is fairly planar and the Ni−N bond lengths are considerably longer, indicating the high‐spin state of the NiII center. The radical exhibited a quartet ground state, indicating the ferromagnetic interaction between the high‐spin NiII center (S=1) and the porphyrin meso‐oxy radical (S=1/2).
Synthesis, Structures, and Photophysical Properties of Alternating Donor–Acceptor Cycloparaphenylenes
Authors: Nishigaki Shuhei , Fukui Miho , Sugiyama Haruki , Uekusa Hidehiro , Kawauchi Susumu , Shibata Yu , Tanaka Ken
Published: April 2017

The synthesis of alternating donor–acceptor [12] and [16]cycloparaphenylenes (CPPs) has been achieved by the rhodium‐catalyzed intermolecular cross‐cyclotrimerization followed by imidation and/or aromatization. These alternating donor–acceptor CPPs showed positive solvatofluorochromic properties and smaller HOMO–LUMO gaps compared with nonfunctionalized CPPs, which was confirmed by the theoretical study.
Conducting Molecular Nanomagnet of DyIII with Partially Charged TCNQ Radicals
Authors: Zhang Xuan , Xie Haomiao , Ballesteros‐Rivas Maria , Woods Toby J. , Dunbar Kim R.
Published: April 2017

Bifunctional electrically conducting single‐molecule magnets are highly promising platforms for non‐volatile memory devices and quantum computing applications. The development of these molecular materials, however, has largely been hindered by the lack of straightforward synthetic methods. Herein a facile and modular approach is demonstrated for the realization of bifunctional materials that does not require electrochemical or chemical oxidation to obtain partially charged organic radicals. Magnetic and electrical conductivity studies reveal that the DyIII compound exhibits slow relaxation of the magnetization between 5.0–8.0 K and semiconducting behavior over the range 180–350 K. DC magnetic fields have been found to suppress the quantum tunneling of the magnetization and affect the spin‐canted antiferromagnetic interactions.
CDSpecTech: A single software suite for multiple chiroptical spectroscopic analyses
Authors: Covington Cody L. , Polavarapu Prasad L.
Published: April 2017

The program CDSpecTech was developed to facilitate the analysis of chiroptical spectra, which include the following: vibrational circular dichroism (VCD) and corresponding vibrational absorption (VA) spectra; vibrational Raman optical activity (VROA) and corresponding vibrational Raman spectra; electronic circular dichroism (ECD) and corresponding electronic absorption (EA) spectra. In addition, the program allows for generating optical rotatory dispersion (ORD) as the Kramers–Kronig transform of ECD spectra. The simulation of theoretical spectra from transition strengths can be achieved using different bandshape profiles. The experimental and simulated theoretical spectra can be visually compared by displaying them together. A unique feature of CDSpecTech is performing spectral analysis using the ratio spectra; i.e., the dimensionless dissymmetry factor (DF) spectrum, which is the ratio of CD to absorption spectra, and the dimensionless circular intensity difference (CID) spectrum, which is the ratio of VROA to vibrational Raman spectra. The quantitative agreement between experimental and simulated theoretical spectra can also be assessed from the numerical similarity overlap between them. Two different similarity overlap methods are available. The program uses a graphical user interface which allows for ease of use and facilitates the analysis. All these features make CDSpecTech a valuable tool for the analysis of chiroptical spectra. The program is freely available on the World Wide Web.
Herstellung von Clathrat‐Hydraten im Verlauf einer Unterrichtsstunde
Authors: Lehde Viktoria , Flint Alfred , Ludwig Ralf
Published: April 2017

Im Unterricht werden häufig die „konventionellen“ fossilen Energieressourcen Erdgas, Erdöl und Kohle vorgestellt. Hier wird vorgeschlagen, auch Methanhydrate als potentielle fossile Energielieferanten im Unterricht zu thematisieren und den Schülerinnen und Schülern so die Möglichkeit zu geben, an einem aktuellen und nicht abgeschlossenen Forschungsthema teilzuhaben. Zur Veranschaulichung der Hydrat‐Strukturen lassen sich THF‐Clathrat‐Hydrate mit einfachen Mitteln in einer Unterrichtsstunde herstellen.