bluuebunny/crossref_metadata_2025 huggingface dataset:
The effect of iron on the biodegradation of natural dissolved organic matter
Authors: Xiao Yi‐Hua , Hoikkala Laura , Kasurinen Ville , Tiirola Marja , Kortelainen Pirkko , Vähätalo Anssi V.
Published: September 2016

Iron (Fe) may alter the biodegradation of dissolved organic matter (DOM), by interacting with DOM, phosphorus (P), and microbes. We isolated DOM and a bacterial community from boreal lake water and examined bacterial growth on DOM in laboratory experiments. Fe was introduced either together with DOM (DOM‐Fe) or into bacterial suspension, which led to the formation of insoluble Fe precipitates on bacterial surfaces (Fe coating). In the latter case, the density of planktonic bacteria was an order of magnitude lower than that in the corresponding treatment without introduced Fe. The association of Fe with DOM decreased bacterial growth, respiration, and growth efficiency compared with DOM alone at the ambient concentration of dissolved P (0.16 µmol L−1), indicating that DOM‐associated Fe limited the bioavailability of P. Under a high concentration (21 µmol L−1) of P, bacterial biomass and respiration were similar or several times higher in the treatment where DOM was associated with Fe than in a corresponding treatment without Fe. Based on the next generation sequencing of 16S rRNA genes, Caulobacter dominated bacterial communities grown on DOM‐Fe. This study demonstrated that association of Fe with a bacterial surface or P reduces bacterial growth and the consumption of DOM. In contrast, DOM‐Fe is bioavailable and bound Fe can even stimulate bacterial growth on DOM when P is not limiting.
It Must Be My Favourite Brand: Using Retroactive Brand Replacements in Doctored Photographs to Influence Brand Preferences
Authors: Hellenthal Maria V. , Howe Mark L. , Knott Lauren M.
Published: September 2016

We examined whether memories for personally chosen brands could be altered by retroactive exposure to less‐liked competitor brands embedded in manipulated photographs. In addition, we investigated whether memory errors would lead to preference change for falsely remembered brands. Fifty participants were asked to compile their personal ‘brand lifestyle basket’, which was then captured in a photo showing the basket and participant. After 1 week, participants were exposed to the photograph in which some of the originally chosen brands were replaced by different brands of the same category. Results of a memory test revealed a robust misinformation effect. The analysis of premanipulation and postmanipulation preference ratings indicated a positive shift in attitude and behaviour towards falsely accepted misinformation brands. Our findings contribute to what we know about the behavioural consequences of false memories and extend the generalizability of false memory effects to what might be considered a futuristic advertising measure. Copyright © 2016 John Wiley & Sons, Ltd.
Copper(I)‐Catalyzed Asymmetric 1,3‐Dipolar [3+4] Cycloaddition of Nitrones with Azoalkenes
Authors: Wei Liang , Yao Lu , Wang Zuo‐Fei , Li Hua , Tao Hai‐Yan , Wang Chun‐Jiang
Published: September 2016

The first copper(I)‐catalyzed asymmetric 1,3‐dipolar [3+4] cycloaddition of nitrones with azoalkenes has been developed, affording a variety of biologically important 1,2,4,5‐oxatriazepane derivatives in good yields with exclusive regioselectivities and excellent enantioselectivities.

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Recent Advances of Oxidative Radical Cross‐Coupling Reactions: Direct α‐C(sp3)–H Bond Functionalization of Ethers and Alcohols
Authors: Guo Sheng‐rong , Kumar Pailla Santhosh , Yang Minghua
Published: September 2016

Oxygen‐containing heterocycles are an important class of compounds with diverse biological activities. In recent years, direct α‐C–H functionalization of inexpensive and abundant readily available ethers and alcohols by oxidative radical cross‐coupling with different nucleophilic partners (C–H, N–H, O–H and S–S), leading to the construction of C–C and C–X (X=C, N, O, S) bonds, has emerged as one of the vital strategies among oxidative cross‐coupling reactions. Owing to the features of being atom‐economic, environmentally benign, having a simple operation and biologically properties, a series of ether α‐C(sp3)–H bond activation reactions have been developed by metal or metal‐free systems via the radical oxidative coupling pathway, since the radical oxidative coupling reactions have wide range of applications. This review aims to highlight the recent advances in direct α‐C(sp3)–H bond functionalization of ethers and alcohols via radical oxidative process.

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A Convenient Ruthenium‐Catalysed α‐Methylation of Carbonyl Compounds using Methanol
Authors: Dang Tuan Thanh , Seayad Abdul Majeed
Published: September 2016

An efficient ruthenium catalyst is reported, for the first time, to catalyse the α‐methylation of ketones and esters using methanol as a green methylating agent. The in situ generated catalyst from the complexes [RuCp*Cl2]2 or [RuCp*Cl2]n with dpePhos provided up to quantitative yields in the presence of only 20 mol% of lithium tert‐butoxide (LiO‐t‐Bu) as a base. Regioselective mono‐ or multi‐methylation could be effectively controlled by temperature. This catalyst system was also effective for the one‐pot sequential α‐alkylation–α‐methylation of methyl ketones and conjugate reduction–α‐methylation of α,β‐unsaturated ketones to synthesise α‐branched ketones. An application of the α‐methylation of esters using the ruthenium catalyst was demonstrated for an alternative catalytic synthesis of Ketoprofen.

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Vanadium‐Catalyzed Oxidative Debenzylation of O‐Benzyl Ethers at ppm Level
Authors: Urgoitia Garazi , SanMartin Raul , Herrero María Teresa , Domínguez Esther
Published: September 2016

An advantageous methodology for the oxidative debenzylation of ethers has been developed. Very low amounts of a catalyst system based on vanadyl acetylacetonate and a triazole type pincer ligand allow the selective oxidative cleavage of a number of O‐benzyl ethers in the presence of oxygen as the sole oxidant. The methodology tolerates a number of functional groups such as halo‐, alkoxy‐, or trifluoromethylarenes, alkyne, alkene, ether, and acetal units. Large‐scale deprotections can be also carried out by the optimized procedure, which is amenable to enantioenriched reactants as well.

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Organo‐ and Iron(0) Catalysis for an Enantioselective Michael Addition–Hemiketalization–Fragmentation Sequence to Protected ω‐Hydroxy‐nitroketones
Authors: Quintard Adrien , Rodriguez Jean
Published: September 2016

By combining an organocatalyzed Michael addition of 1,3‐diketones to hydroxy‐nitroolefins with a subsequent, innovative iron(0)‐catalyzed fragmentation, key enantioenriched ketones possessing additional nitro and protected alcohol functions could efficiently be prepared under excellent enantiocontrol (typically 95% ee). The reaction was made possible by the discovery that photochemical activation of iron pentacarbonyl [Fe(CO)5], a cheap widely available complex, efficiently catalyzed a Claisen‐type fragmentation under mild conditions, avoiding decomposition of the intermediates and products.

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A multianalytical approach to evaluate the association of 55 SNPs in 28 genes with obesity risk in North Indian adults
Authors: Srivastava Apurva , Mittal Balraj , Prakash Jai , Srivastava Pranjal , Srivastava Nimisha , Srivastava Neena
Published: September 2016

Objectives

The aim of the study was to investigate the association of 55 SNPs in 28 genes with obesity risk in a North Indian population using a multianalytical approach.

Methods

Overall, 480 subjects from the North Indian population were studied using strict inclusion/exclusion criteria. SNP Genotyping was carried out by Sequenom Mass ARRAY platform (Sequenom, San Diego, CA) and validated Taqman® allelic discrimination (Applied Biosystems®). Statistical analyses were performed using SPSS software version 19.0, SNPStats, GMDR software (version 6) and GENEMANIA.

Results

Logistic regression analysis of 55 SNPs revealed significant associations (P < .05) of 49 SNPs with BMI linked obesity risk whereas the remaining 6 SNPs revealed no association (P > .05). The pathway‐wise G‐score revealed the significant role (P = .0001) of food intake‐energy expenditure pathway genes. In CART analysis, the combined genotypes of FTO rs9939609 and TCF7L2 rs7903146 revealed the highest risk for BMI linked obesity. The analysis of the FTO‐IRX3 locus revealed high LD and high order gene‐gene interactions for BMI linked obesity. The interaction network of all of the associated genes in the present study generated by GENEMANIA revealed direct and indirect connections. In addition, the analysis with centralized obesity revealed that none of the SNPs except for FTO rs17818902 were significantly associated (P < .05).

Conclusions

In this multi‐analytical approach, FTO rs9939609 and IRX3 rs3751723, along with TCF7L2 rs7903146 and TMEM18 rs6548238, emerged as the major SNPs contributing to BMI linked obesity risk in the North Indian population.
The turbinal flap: an additional option for anterior skull base reconstruction. Cadaveric feasibility study and case report
Authors: Schreiber Alberto , Mattavelli Davide , Ferrari Marco , Rampinelli Vittorio , Lancini Davide , Belotti Francesco , Rodella Luigi Fabrizio , Nicolai Piero
Published: September 2016

Background

Over the past decade, the treatment of complex intradural and extradural pathologies via expanded endonasal approaches has been made possible by progresses and refinements in skull base reconstruction techniques. The aim of this anatomic study is to describe a novel endonasal flap, the turbinal flap (TF), based on the middle and superior turbinate mucosa and pedicled on the ethmoidal arteries system.

Methods

Three fresh‐frozen (6 sides) cadaver heads previously injected with colored silicone were dissected. A step‐by‐step description of the surgical technique is provided. Vascularization of the TF and its range of possibilities to cover anterior skull base defects were studied. Flap dimensions and area were measured. A case report where the TF was successfully used is also described.

Results

The TF was adequate to repair defects along the entire ethmoid roof. Its pedicle along the skull base was 3.0 cm in length and sagittally oriented. Mean measures of the TF were 3.4 cm (anterior height), 5.5 cm (posterior height), and 4.8 cm (inferior length). Its mean area was 8.6 cm2. The flap was supplied by rich network of vessels. A demonstrative case of anterior skull base repair after the endoscopic resection of meningocephalocele of the ethmoid roof is reported.

Conclusion

The main indication for the TF is the repair of anterior skull base defects involving the ethmoid roof. Its advantages include the double pedicle, rich vascularization, autonomy from the maxillary artery system, and preservation of the olfactory mucosa.
Sterisch anspruchsvolle 2,6‐disubstituierte Aniline durch direkte C‐N‐Bindungsknüpfung an Iod(III)‐Zentren
Authors: Lucchetti Nicola , Scalone Michelangelo , Fantasia Serena , Muñiz Kilian
Published: September 2016

2,6‐Disubstitutierte Aniline werden bequem durch eine direkte Reaktion zwischen Amiden und Diaryliodonium‐Salzen synthetisiert. Wie anhand von 24 unterschiedlichen Beispielen gezeigt wird, weist die Reaktion eine ungewöhnlich große Substratbreite bezüglich der sterisch anspruchsvollen Aren‐ und der Stickstoffgruppierung auf, benötigt keinen weiteren Promotor und verläuft über eine direkte reduktive Eliminierung am Iod(III)‐Zentrum. Die Effizienz dieses Kupplungsprotokolls wird zudem anhand der kurzen Synthese eines Chemerin‐Bindungsinhibitors demonstriert.
Independent Control of Elastomer Properties through Stereocontrolled Synthesis
Authors: Bell Craig A. , Yu Jiayi , Barker Ian A. , Truong Vinh X. , Cao Zhen , Dobrinyin Andrey V. , Becker Matthew L. , Dove Andrew P.
Published: September 2016

In most synthetic elastomers, changing the physical properties by monomer choice also results in a change to the crystallinity of the material, which manifests through alteration of its mechanical performance. Using organocatalyzed stereospecific additions of thiols to activated alkynes, high‐molar‐mass elastomers were isolated via step‐growth polymerization. The resulting controllable double‐bond stereochemistry defines the crystallinity and the concomitant mechanical properties as well as enabling the synthesis of materials that retain their excellent mechanical properties through changing monomer composition. Using this approach to elastomer synthesis, further end group modification and toughening through vulcanization strategies are also possible. The organocatalytic control of stereochemistry opens the realm to a new and easily scalable class of elastomers that will have unique chemical handles for functionalization and post synthetic processing.
Self‐Organized Stationary Patterns in Networks of Bistable Chemical Reactions
Authors: Kouvaris Nikos E. , Sebek Michael , Mikhailov Alexander S. , Kiss István Z.
Published: September 2016

Experiments with networks of discrete reactive bistable electrochemical elements organized in regular and nonregular tree networks are presented to confirm an alternative to the Turing mechanism for the formation of self‐organized stationary patterns. The results show that the pattern formation can be described by the identification of domains that can be activated individually or in combinations. The method also enabled the localization of chemical reactions to network substructures and the identification of critical sites whose activation results in complete activation of the system. Although the experiments were performed with a specific nickel electrodissolution system, they reproduced all the salient dynamic behavior of a general network model with a single nonlinearity parameter. Thus, the considered pattern‐formation mechanism is very robust, and similar behavior can be expected in other natural or engineered networked systems that exhibit, at least locally, a treelike structure.
Oxidation State Dependent Coordination Modes: Accessing an Amidate‐Supported Nickel(I) δ‐bis(C−H) Agostic Complex
Authors: Beattie D. Dawson , Bowes Eric G. , Drover Marcus W. , Love Jennifer A. , Schafer Laurel L.
Published: September 2016

Amidate‐supported two‐ and three‐coordinate NiI complexes were synthesized by reduction of the corresponding NiII precursors. A dramatic change in binding mode is observed upon reduction from NiII to NiI. The NiI derivatives include an unprecedented NiI bis(C−H) agostic complex and a two‐coordinate NiI complex.
Oxidative Cleavage of C=S and P=S Bonds at an AlI Center: Preparation of Terminally Bound Aluminum Sulfides
Authors: Chu Terry , Vyboishchikov Sergei F. , Gabidullin Bulat , Nikonov Georgii I.
Published: September 2016

The treatment of cyclic thioureas with the aluminum(I) compound NacNacAl (1; NacNac=[ArNC(Me)CHC(Me)NAr]−, Ar=2,6‐Pri2C6H3) resulted in oxidative cleavage of the C=S bond and the formation of 3 and 5, the first monomeric aluminum complexes with an Al=S double bond stabilized by N‐heterocyclic carbenes. Compound 1 also reacted with triphenylphosphine sulfide in a similar manner, which resulted in cleavage of the P=S bond and production of the adduct [NacNacAl=S(S=PPh3)] (8). The Al=S double bond in 3 can react with phenyl isothiocyanate to furnish the cycloaddition product 9 and zwitterion 10 as a result of coupling between the liberated carbene and PhN=C=S. All novel complexes were characterized by multinuclear NMR spectroscopy, and the structures of 5, 9, and 10 were confirmed by X‐ray diffraction analysis. The nature of the Al=S bond in 5 was also probed by DFT calculations.
First Episode Psychosis: A Magical Realist Guide Through Liminal Terrain
Authors: Bar‐Am Sonja
Published: September 2016

This paper presents a narrative of a client, ‘Eva’, who experienced what is termed by psychiatry a first episode psychosis. As a family and relationship counsellor practicing narrative therapy with its backdrop of post‐structuralism and curiosity of exploring new entry points for narratives of identity, I tentatively sought new ways to engage with Eva's story. My endeavour in meeting with ‘First Episode Psychosis’ is described through adopting a listening position from a reading of magical realist literature. This extends Michael White's political exploration of ethnographer Arnold van Gennep's liminal spaces (in the rites of passage metaphor) to understand units of experience, units of meaning, and the fluidity of identity in psychosis, which is contextualised as a response to events in the client's story.
Mindful of the Intersession Break in Family Therapy: The Time to Think Experiment
Authors: O'Brien Cathy , Yule Elisa
Published: September 2016

The Time to Think Experiment researches the experience of clinicians, consumers, and families of an intersession break, which has been used historically in various models of family therapy training. This qualitative pilot study explores the experiences of 21 clinicians, 19 consumers, and six family members using this break for reflection, across the domains of family and couple therapy, individual therapy, group work, and supervision in a mental health service covering the whole age range. Using a phenomenological design, the analysis included narrative, thematic, content, and comparative techniques. The paper considers the impact of privileging reflection in the therapy process, in a climate where models, work cultures, and general lifestyles may not encourage it. Using the intersession break to create space to ‘be’ in the therapy process is one way to integrate mindful and family therapy practice. The emerging themes of an intersession break to promote a richer and deeper therapy experience, and the apparent shift of responsibility for change from clinicians to consumers is discussed.
Self‐Assembly of Amphiphilic Drug–Dye Conjugates into Nanoparticles for Imaging and Chemotherapy
Authors: Sun Tingting , Lin Wenhai , Zhang Wei , Xie Zhigang
Published: September 2016

An amphiphilic drug–dye conjugate (PTX‐Pt‐BDP) was designed and synthesized with a platinum compound as the hydrophilic head. The precursor of PTX‐Pt‐BDP was obtained under mild conditions by means of a three‐component Passerini reaction. PTX‐Pt‐BDP could self‐assemble into nanoparticles (PTX‐Pt‐BDP NPs) in aqueous solution via a nanoprecipitation method. The obtained nanoparticles exhibited favorable structural stability in both water and physiological environment. PTX‐Pt‐BDP NPs could be endocytosed by cancer cells as revealed by confocal laser scanning microscopy and exert potent cytotoxicity. This work highlights the potential of nanomedicines from amphiphilic drug–dye conjugates for cancer cell imaging and chemotherapy.
Beyond the hype and hope: Critical considerations for intranasal oxytocin research in autism spectrum disorder
Authors: Alvares Gail A. , Quintana Daniel S. , Whitehouse Andrew J.O.
Published: September 2016

Extensive research efforts in the last decade have been expended into understanding whether intranasal oxytocin may be an effective therapeutic in treating social communication impairments in individuals with autism spectrum disorder (ASD). After much hyped early findings, subsequent clinical trials of longer‐term administration have yielded more conservative and mixed evidence. However, it is still unclear at this stage whether these more disappointing findings reflect a true null effect or are mitigated by methodological differences masking true effects. In this review, we comprehensively evaluate the rationale for oxytocin as a therapeutic, evaluating evidence from randomized controlled trials, case reports, and open‐label studies of oxytocin administration in individuals with ASD. The evidence to date, including reviews of preregistered trials, suggests a number of critical considerations for the design and interpretation of research in this area. These include considering the choice of ASD outcome measures, dosing and nasal spray device issues, and participant selection. Despite these limitations in the field to date, there remains significant potential for oxytocin to ameliorate aspects of the persistent and debilitating social impairments in individuals with ASD. Given the considerable media hype around new treatments for ASD, as well as the needs of eager families, there is an urgent need for researchers to prioritise considering such factors when conducting well‐designed and controlled studies to further advance this field. Autism Res 2017, 10: 25–41. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Techno‐economic assessment of biorefinery technologies for aviation biofuels supply chains in Brazil
Authors: Alves Catarina M. , Valk Misha , de Jong Sierk , Bonomi Antonio , van der Wielen Luuk A.M. , Mussatto Solange I.
Published: September 2016

Production of aviation biofuels has been strongly encouraged by the volatility of oil prices and environmental concerns. Brazilian society, companies, and government are taking a step forward in the production of renewable jet fuel from biomass feedstocks largely available in the territory. This study evaluated the use of different feedstocks (sugar crops, oil crops, and lignocellulosic biomass) for co‐production of biojet fuel and higher value‐added products in a biorefinery platform. The co‐production of biofuels and biochemicals in a biorefinery context was demonstrated to be economically feasible. The main cost drivers of such a platform are feedstock biomass cost, selling price of the biochemicals, investment costs, and key process‐inherent parameters such as conversion yields, obtained fermentable sugars, or oil content in the feedstock. Sugarcane was the most promising feedstock for a biorefinery in the region of Minas Gerais, while soybean was the most promising feedstock for a biorefinery in the region of Rio Grande do Sul, despite its higher uncertainty. Succinic acid was the most promising chemical intermediate for biopolymers industry due to its relatively high market value, unique market opportunity as a substitute of conventional petrochemicals, and forecast for future growth. Ethanol‐to‐jet (ETJ) and hydro‐processed esters and fatty acids (HEFA) were the most attractive biojet fuel production routes in the present study. Scenarios for co‐production of biofuels and biochemicals in Brazil present large uncertainties and high financial risk, mainly due to the use of second‐generation feedstocks, and the introduction of new technologies and products. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd
Integration of growth factor gene delivery with collagen‐triggered wound repair cascades using collagen‐mimetic peptides
Authors: Urello Morgan A. , Kiick Kristi L. , Sullivan Millicent O.
Published: September 2016

Growth factors (GFs) play vital roles in wound repair. Many GF therapies have reached clinical trials, but success has been hindered by safety concerns and a lack of efficacy. Previously, we presented an approach to produce protein factors in wound beds through localized gene delivery mediated by biomimetic peptides. Modification of polyethylenimine (PEI) DNA polyplexes with collagen‐mimetic peptides (CMPs) enabled tailoring of polyplex release/retention and improved gene transfer activity in a cell‐responsive manner. In this work, CMP‐mediated delivery from collagen was shown to improve expression of platelet‐derived growth factor–BB (PDGF‐BB) and promote a diverse range of cellular processes associated with wound healing, including proliferation, extracellular matrix production, and chemotaxis. Collagens were pre‐exposed to physiologically‐simulating conditions (complete media, 37°C) for days to weeks prior to cell seeding to simulate the environment within typical wound dressings. In cell proliferation studies, significant increases in cell counts were demonstrated in collagen gels containing CMP‐modified polyplex versus unmodified polyplex, and these effects became most pronounced following prolonged preincubation periods of greater than a week. Collagen containing CMP‐modified polyplexes also induced a twofold increase in gel contraction as well as enhanced directionality and migratory activity in response to cell‐secreted PDGF‐BB gradients. While these PDGF‐BB‐triggered behaviors were observed in collagens containing unmodified polyplexes, the responses withstood much longer preincubation periods in CMP‐modified polyplex samples (10 days vs. <5 days). Furthermore, enhanced closure rates in an in vitro wound model suggested that CMP‐based PDGF‐BB delivery may have utility in actual wound repair and other regenerative medicine applications.
Folate receptor‐targeted aminoglycoside‐derived polymers for transgene expression in cancer cells
Authors: Godeshala Sudhakar , Nitiyanandan Rajeshwar , Thompson Brian , Goklany Sheba , Nielsen David R. , Rege Kaushal
Published: September 2016

Targeted delivery of anticancer therapeutics can potentially overcome the limitations associated with current chemotherapeutic regimens. Folate receptors are overexpressed in several cancers, including ovarian, triple‐negative breast and bladder cancers, making them attractive for targeted delivery of nucleic acid therapeutics to these tumors. This work describes the synthesis, characterization and evaluation of folic acid‐conjugated, aminoglycoside‐derived polymers for targeted delivery of transgenes to breast and bladder cancer cell lines. Transgene expression was significantly higher with FA‐conjugated aminoglycoside‐derived polymers than with Lipofectamine, and these polymers demonstrated minimal cytotoxicty. Competitive inhibition using free folic acid significantly reduced transgene expression efficacy of folate‐targeted polymers, suggesting a role for folate receptor‐mediated uptake. High efficacy FA‐targeted polymers were employed to deliver a plasmid expressing the TRAIL protein, which induced death in cancer cells. These results indicate that FA‐conjugated aminoglycoside‐derived polymers are promising for targeted delivery of nucleic acids to cancer cells that overexpress folate receptors.
MiR‐24‐3p enhances cell growth in hepatocellular carcinoma by targeting metallothionein 1M
Authors: Dong Xiaogang , Ding Wei , Ye Jianwei , Yan Dong , Xue Feng , Xu Lin , Yin Jiwei , Guo Wenjia
Published: September 2016

Dysregulation of microRNAs has been demonstrated to contribute to malignant progression of cancers, including hepatocellular carcinoma (HCC). MiR‐24‐3p was previously reported to be significantly upregulated in HCC. However, the potential role and mechanism of action of miR‐24‐3p in the initiation and progression of HCC remain largely unknown. Quantitative reverse transcription polymerase chain reaction demonstrated that miR‐24‐3p was significantly upregulated in HCC tumor tissues compared with nontumor tissues. The cell viability, colony formation assay, and tumorigenicity assays in nude mice showed that miR‐24‐3p could enhance HCC cell growth in vitro and in vivo. Metallothionein 1M was verified as an miR‐24‐3p target gene by using dual‐luciferase reporter assays, quantitative reverse transcription polymerase chain reaction, and Western blotting, which was involved in miR‐24‐3p regulated HCC cell growth. These results indicated that miR‐24‐3p plays an important role in the initiation and progression of HCC by targeting metallothionein 1M, and the miR‐24‐3p/metallothionein 1M pathway may contribute to the development of novel therapeutic strategies for HCC in the future.
Comparative Case–Control analysis of a dedicated self‐expanding Biolimus A9‐eluting Bifurcation stent versus provisional or mandatory side branch intervention strategies in the treatment of coronary bifurcation lesions
Authors: Ohlow Marc‐Alexander , Farah Ahmed , Richter Stefan , El‐Garhy Mohamad , von Korn Hubertus , Lauer Bernward
Published: September 2016

Background

In a number of coronary bifurcation lesions, both the main vessel and the side branch (SB) need stent coverage.

Objectives

To analyze the procedural performance and the impact on radiation times (RT) and contrast medium consumption (CMC) of the Axxess™ stent system (Biosensors, Switzerland) treating de novo bifurcation lesions (DBL).

Methods

One hundred and ten consecutive prospectively enrolled cases (Axxess Group) and 110 age, sex, and lesion location matched controls undergoing mandatory (Group A, n = 56) or provisional (Group B, n = 54) SB intervention were analyzed.

Results

Although more pre‐dilatation was performed in the Axxess Group (92.7% vs. 46.4% [Group A] vs. 24.1% [Group B]), and more stents were used (2.4 vs. 1.2 vs. 1.05), RT and CMC were significantly lower in the Axxess Group [7.9 min/129 ml vs. 14.2 min/209 ml vs. 7.8 min/152 ml; P < 0.001]. Final Thrombolysis In Myocardial Infarction three flow in both branches was significantly more frequent in the Axxess Group (98.2% vs. 94.6% vs. 88.9%; P = 0.02), and post‐interventional troponin T elevations were the lowest in the Axxess Group. Eighty one percent of the Axxess‐stents could be implanted without technical difficulties. Difficult implantations procedures were mainly related to coronary anatomy. There was no safety concerns (cardiac death, stent‐thrombosis) compared to controls. Cumulative 6‐months MACE rates were 11% versus 23% versus 25%. TLR rates at 6‐months were 5%, 18%, and 15%, respectively.

Conclusions

Axxess bifurcation stent system procedures were associated with significantly less RT and CMC compared to conventional DBL therapy strategies. Difficult coronary anatomy may hinder successful implantation and a learning curve has to be considered. © 2016 Wiley Periodicals, Inc.
First reported use of drug‐coated balloon for bioresorbable in‐scaffold restenosis
Authors: Latini Roberto Adriano , Buccheri Dario , Cortese Bernardo
Published: September 2016

This is the first documented case of a drug‐coated balloon strategy for the treatment of bioresorbable in‐scaffold restenosis caused by diffuse neointimal proliferation. This case can provide an alternative treatment option in this setting, avoiding potential problems related to further bulky metallic stents in a patient where a different strategy was initially planned. © 2016 Wiley Periodicals, Inc.
Copper(II)‐Catalyzed Direct Azidation of N‐Acylated 8‐Aminoquinolines by Remote C−H Activation
Authors: Dou Yandong , Xie Zhenda , Sun Zongguo , Fang Hongli , Shen Chao , Zhang Pengfei , Zhu Qing
Published: September 2016

A simple and efficient copper(II)‐catalyzed C5 azidation of N‐acylated 8‐aminoquinolines by remote C−H activation was developed. On the basis of this reaction, a series of new C5‐azidated 8‐amidequinolines were synthesized in moderate to good yields.
Unraveling the “Seesaw” Competition between the Electrically Driven Reduction and Reoxidation Processes in Ceria with In Situ Electron Microscopy
Authors: Li Xiaomin , Qi Kuo , Sun Muhua , Huang Qianming , Wei Jiake , Xu Zhi , Wang Wenlong , Bai Xuedong
Published: September 2016

An improved mechanistic understanding of the redox behavior of ceria (CeO2) is central to controlling its catalytic and ionic properties, which are involved in a variety of technologically important applications. Here, as enabled by the real‐time temporal resolution of in situ electron microscopy, we present strong evidence to help elucidate the complex interplay and dynamics of the electrically driven redox equilibria in ceria. Under an external electric field, a CeO2 film sandwiched between a Nb‐doped SrTiO3 substrate (cathode) and a tungsten probing tip (anode) was observed to dynamically exhibit a seesaw‐like, reversible forward/backward propagation of the modulation wave formed in the cubic ceria lattice as a consequence of ordering and migration of oxygen vacancies. Such an interesting seesaw‐like behavior indicates subtle competition between the electrically driven reduction (forming oxygen vacancies) of ceria and its dynamic reoxidation (repairing oxygen vacancies) by residual oxygen gas in the chamber (≈10−6 Pa). This result provides important new insight that can be used to understand the redox chemistry of ceria, for which, in previous studies, the reduction and oxidation processes were assumed to be two seemingly separate events that could occur only after switching the external thermodynamic conditions.
Aeration of Liquid‐Liquid Systems Using Various Agitators in a Mixer Equipped with a Membrane Diffuser
Authors: Szaferski Waldemar , Mitkowski Piotr T.
Published: September 2016

Efficient aeration of liquid mixtures is essential in many biochemical and chemical processes. The power requirements needed to obtain three‐phase gas‐liquid‐liquid systems containing air, mineral oil, and water as modeling mixture were analyzed. The influence of using various kinds of agitators consisting of two stirrers on a common shaft and different volume fractions of oil ranging from 0.111 to 0.429 were investigated experimentally. The studies were performed for three configurations of stirrers consisting of Smith disc, Rushton, or flat‐blade turbines.
Comparison of Response Surface Methodology and Artificial Neural Network for Modeling Xylose‐to‐Xylitol Bioconversion
Authors: Sampaio Fábio Coelho , de Faria Janaína Teles , de Lima Silva Gabriel Dumond , Gonçalves Ricardo Melo , Pitangui Cristiano Grijó , Casazza Alessandro Alberto , Arni Saleh Al , Converti Attilio
Published: September 2016

Previous experimental data of xylose‐to‐xylitol bioconversion by Debaryomyces hansenii carried out according to a 33 full factorial design were used to model this process by two different artificial neural network (ANN) training methods. Models obtained for four responses were compared with those of response surface methodology (RSM). ANN models were shown to be superior to RSM in the predictive capacity, whereas the latter showed better performance in the generalization capability step. RSM with optimization using a genetic algorithm was revealed as a whole to be the best modeling option, which suggests that the comparative performances of RSM and ANN may be a highly problem‐specific issue.
Influence of Ester versus Amide Linkers on the Supramolecular Polymerization Mechanisms of Planar BODIPY Dyes
Authors: Rödle Alexander , Ritschel Benedikt , Mück‐Lichtenfeld Christian , Stepanenko Vladimir , Fernández Gustavo
Published: September 2016

We report the H‐type supramolecular polymerization of two new hydrophobic BODIPY derivatives equipped with ester and amide linkages. Whereas the ester‐containing BODIPY derivative undergoes an isodesmic supramolecular polymerization in which the monomers are parallel‐oriented, the replacement of the ester by amide groups leads to a highly cooperative self‐assembly process into H‐type aggregates with a rotational displacement of the dye molecules within the stack. The dye organization imposed by simultaneous π–π and hydrogen bonding interactions is the driving force for the cooperative supramolecular polymerization, whereas the absence of additional hydrogen bonds for the ester‐containing moiety does not suffice to induce cooperative phenomena.
Ferroxidase Activity in Eukaryotic Ferritin is Controlled by Accessory‐Iron‐Binding Sites in the Catalytic Cavity
Authors: Bernacchioni Caterina , Pozzi Cecilia , Di Pisa Flavio , Mangani Stefano , Turano Paola
Published: September 2016

Ferritins are iron‐storage nanocage proteins that catalyze the oxidation of Fe2+ to Fe3+ at ferroxidase sites. By a combination of structural and spectroscopic techniques, Asp140, together with previously identified Glu57 and Glu136, is demonstrated to be an essential residue to promote the iron oxidation at the ferroxidase site. However, the presence of these three carboxylate moieties in close proximity to the catalytic centers is not essential to achieve binding of the Fe2+ substrate to the diferric ferroxidase sites with the same coordination geometries as in the wild‐type cages.
Crystal Structures and Phase Sequences of Metallocenium Salts with Fluorinated Anions: Effects of Molecular Size and Symmetry on Phase Transitions to Ionic Plastic Crystals
Authors: Mochida Tomoyuki , Funasako Yusuke , Ishida Mai , Saruta Shingo , Kosone Takashi , Kitazawa Takafumi
Published: September 2016

Sandwich compounds often exhibit various phase transitions, including those to plastic phases. To elucidate the general features of the phase transitions in metallocenium salts, the thermal properties and crystal structures of [Fe(C5Me5)2]X ([1]X), [Co(C5Me5)2]X ([2]X), and [Fe(C5Me4H)2]X ([3]X) have been investigated, where the counter anions (X) are Tf2N (=(CF3SO2)2N−), OTf (=CF3SO3−), PF6, and BF4. The Tf2N salts commonly undergo phase transitions from an ordered phase at low temperatures to an anion‐disordered phase, followed by a plastic phase and finally melt at high temperatures. All these salts exhibit a phase transition to a plastic phase, and the transition temperature generally decreases with decreasing cation size and increasing anion size. The crystal structures of these salts comprise an alternating arrangement of cations and anions. About half of these salts exhibit phase transitions at low temperatures, which are mostly correlated with the order–disorder of the anion.
A Masked Phosphinidene Trapped in a Fluxional NCN Pincer
Authors: Hyvl Jakub , Yoshida Wesley Y. , Rheingold Arnold L. , Hughes Russell P. , Cain Matthew F.
Published: September 2016

The trapping of a phosphinidene (R‐P) in an NCN pincer is presented. Stabilized phosphinidene 1 was characterized by 31P{1H}, 1H, and 13C{1H} NMR spectroscopy, exhibiting an averaged C2v symmetry in solution between −60 and 60 °C. In the solid state, the phosphinidene is coordinated by one adjacent N atom featuring a formal P−N bond (1.757(2) Å) to give a five‐membered ring with some aromatic character, confirmed by DFT calculations (B3LYP‐D3/6‐311G**++) to be the ground‐state structure. Equilibration of the two N ligands occurs rapidly in solution via a “bell‐clapper”‐type process through an associative symmetric transition state calculated to lie 4.0 kcal mol−1 above the ground state.
Fucoidan Induces ROS‐Dependent Apoptosis in 5637 Human Bladder Cancer Cells by Downregulating Telomerase Activity via Inactivation of the PI3K/Akt Signaling Pathway
Authors: Han Min Ho , Lee Dae‐Sung , Jeong Jin‐Woo , Hong Su‐Hyun , Choi Il‐Whan , Cha Hee‐Jae , Kim Suhkmann , Kim Heui‐Soo , Park Cheol , Kim Gi‐Young , Moon Sung‐Kwon , Kim Wun‐Jae , Hyun Choi Yung
Published: September 2016

Preclinical Research

Fucoidan, a sulfated polysaccharide, is a compound found in various species of seaweed that has anti‐viral, anti‐bacterial, anti‐oxidant, anti‐inflammatory, and immunomodulatory activities; however, the underlying relationship between apoptosis and anti‐telomerase activity has not been investigated. Here, we report that fucoidan‐induced apoptosis in 5637 human bladder cancer cells was associated with an increase in the Bax/Bcl‐2 ratio, the dissipation of the mitochondrial membrane potential (MMP, Δψm), and cytosolic release of cytochrome c from the mitochondria. Under the same experimental conditions, fucoidan‐treatment decreased hTERT (human telomerase reverse transcriptase) expression and the transcription factors, c‐myc and Sp1. This was accompanied by decreased telomerase activity. Fucoidan‐treatment also suppressed activation of the PI3K/Akt signaling pathway. Inhibition of PI3K/Akt signaling enhanced fucoidan‐induced apoptosis and anti‐telomerase activity. Meanwhile, fucoidan treatment increased the generation of intracellular ROS, whereas the over‐elimination of ROS by N‐acetylcysteine, an anti‐oxidant, attenuated fucoidan‐induced apoptosis, inhibition of hTERT, c‐myc, and Sp1 expression, and reversed fucoidan‐induced inactivation of the PI3K/Akt signaling pathway. Collectively, these data indicate that the induction of apoptosis and the inhibition of telomerase activity by fucoidan are mediated via ROS‐dependent inactivation of the PI3K/Akt pathway. Drug Dev Res 78 : 37–48, 2017.   © 2016 Wiley Periodicals, Inc.
Assessment of wildland fire impacts on watershed annual water yield: Analytical framework and case studies in the United States
Authors: Hallema Dennis W. , Sun Ge , Caldwell Peter V. , Norman Steven P. , Cohen Erika C. , Liu Yongqiang , Ward Eric J. , McNulty Steven G.
Published: September 2016

More than 50% of water supplies in the conterminous United States originate on forestland or rangeland and are potentially under increasing stress as a result of larger and more severe wildfires. Little is known, however, about the long‐term impacts of fire on annual water yield and the role of climate variability within this context. We here propose a framework for evaluating wildland fire impacts on streamflow that combines double‐mass analysis with new methods (change point analysis, climate elasticity modeling, and process‐based modeling) to distinguish between multiyear fire and climate impacts. The framework captures a wide range of fire types, watersheds characteristics, and climate conditions using streamflow data, as opposed to other approaches requiring paired watersheds. The process is illustrated with three case studies. A watershed in Arizona experienced a +266% increase in annual water yield in the 5 years after a wildfire, where +219% was attributed to wildfire and +24% to precipitation trends. In contrast, a California watershed had a lower (−64%) post‐fire net water yield, comprised of enhanced flow (+38%) attributed to wildfire offset (−102%) by lower precipitation in the post‐fire period. Changes in streamflow within a watershed in South Carolina had no apparent link to periods of prescribed burning but matched a very wet winter and reports of storm damage. The presented framework is unique in its ability to detect and quantify fire or other disturbances, even if the date or nature of the disturbance event is uncertain, and regardless of precipitation trends.
A Family of Titanium Complexes with Catechol Ligands: Structural Investigation and Catalytic Application
Authors: Bazhenova Tamara A. , Kovaleva Nadezhda V. , Shilov Gennady V. , Petrova Galina N. , Kuznetsov Denis A.
Published: September 2016

Four new titanium catecholate complexes – [Ti2(Cat)2(CatH)2(OCH3)2(CH3OH)2] (1; Cat = C6H4O22–), [Ti2(4tBuCat)4(CH3OH)2]·2CH3OH (2·2CH3OH; 4tBuCat = [4‐t‐C4H9‐C6H3O2]2–), [Ti(Cat)2(dmf)2] (3; dmf = N,N‐dimethylformamide), and [Na(dme)Ti(Cat)3]2[Na(dme)CH3OH]2 (4; dme = 1,2‐dimethoxyethane) – have been obtained by treatment of Ti(OCH3)4 with catechols in methanol and structurally characterized. Complex 3 is the first example of a neutral mononuclear titanium catecholate containing more than one catechol molecule per titanium atom. Complexes 1 and 2 are neutral dimers in the solid state, each with a catechol/Ti ratio equal to 2 and featuring one of the catechol ligands bridging two titanium centres in a singly bridging chelate µ2‐(O,O′,O′) mode. The other catechol molecule is either a terminal bidentate chelating ligand (complex 2) or a Ti monodentate ligand (complex 1). Complex 4 is a heterometallic aryloxide complex with a tetrameric [{Na(dme)Ti(Cat)3)2]2– (Ti2Na2) core as an anionic moiety and Na ions, solvated by methanol and dme ligands – [{Na(dme)(CH3OH)}2]2+ – as a cationic counterpart. Each Ti centre in 4 is octahedrally coordinated by three catechol ligands, demonstrating three distinct types of bridging modality. It was shown that 1–4 effectively catalyze the selective homogeneous hydrogenation of acetylene to ethylene. Various kinetic relationships were determined and analyzed, enabling a reaction pathway for this catalytic reaction to be proposed.
Capturing Hydrophobic Trifluoroiodomethane in Water into an M4L6 Cage
Authors: Giri Chandan , Sahoo Prasit Kumar , Rissanen Kari , Mal Prasenjit
Published: September 2016

Synthetically important trifluoroiodomethane (CF3I) was trapped in water by using a metal–organic supramolecular anionic cage. Under ambient conditions, nearly 1:1 encapsulation of the hydrophobic, gaseous CF3I substrate with the cage was observed, and its binding constant was calculated by relative comparison with benzene encapsulation.
The Key Heterolysis Selectivity of Divalent Sulfur–Sulfur Bonds for a Unified Mechanistic Scheme in the Thiosulfatolysis and Sulfitolysis of the Pentathionate Ion
Authors: Ji Chen , Yan Xiangdong , Pan Changwei , Lv Fengpeng , Gao Qingyu
Published: September 2016

The thiosulfatolysis and sulfitolysis of pentathionate were studied in the pH ranges 4.50–8.0 and 4.0–5.0 at T = (25.0 ± 0.1) °C by HPLC monitoring of the time‐dependence and distribution of different sulfur species. The two systems are first order with respect to both reactants. In contrast to tetrathionate, pentathionate and higher polythionates contain inequivalent divalent sulfur atoms; therefore, the complexity of the mechanism increases. The selective heterolytic cleavages of sulfur–sulfur bonds are essential steps for the time evolution and equilibrium distribution of the divalent sulfur species. A proposed eight‐step mechanistic model, which incorporates the proton equilibrium of sulfite and the heterolytic cleavage of divalent sulfur–sulfur bonds of hexathionate, was applied to evaluate the thiosulfatolysis and sulfitolysis of the pentathionate ion, and the kinetics of both systems are modulated by this mechanistic network.
RGGI's Experience To Date Could Provide Nationwide Model
Authors: Stutt Jordan
Published: September 2016

Through seven‐and‐a‐half years of operation, the Regional Greenhouse Gas Initiative (RGGI) has helped nine northeastern and Mid‐Atlantic states1 achieve significant reductions in emissions of carbon dioxide and other pollutants from the electric power sector. Over the same period, RGGI states' economies have outpaced the rest of the country, and electricity prices within the region have fallen, even as prices in other states have increased. Through reforms considered in the 2016 Program Review, states can build on this success and solidify RGGI's role in achieving state‐level climate commitments and requirements of the Environmental Protection Agency's (EPA's) Clean Power Plan (CPP).
Coal‐Bed Methane Provides Less‐Invasive Production Method
Authors: Rundgren Elizabeth J.
Published: September 2016

If the twenty‐first century has done anything, it's allowed the extrapolation of “personalization” on a global scale. Once limited to purchasing items during set business hours from a local store's inventory, consumers now acquire everything from tailored clothing to kits of gourmet food every minute of the day—sometimes delivered to their doorsteps within hours. This revolution has redefined what it means to “provide” and “consume.”
Will LNG Rescue World Gas Market? Maybe a Little
Authors: Makholm Jeff D.
Published: September 2016

The use of natural gas in the world is growing.
The ACA's Provision on Nondiscrimination Takes Shape
Authors: Johnson Sandra H.
Published: September 2016

The Department of Health and Human Services has issued far‐reaching regulations to implement the nondiscrimination requirement of the Affordable Care Act. Now commonly called “Section 1557,” this ACA provision prohibits discrimination by “any health program or activity, any part of which is receiving Federal financial assistance,” on grounds prohibited under previously enacted federal antidiscrimination statutes. The DHHS Office of Civil Rights enforces Section 1557. These new regulations and accompanying commentary give warning of the standards the agency will use in its enforcement efforts. Courts will also give some deference to the DHHS regulations in interpreting the statute in lawsuits by individuals claiming damages against covered health care providers for illegal discrimination under Section 1557. Three central issues are the nature of the rights created in Section 1557 and their relation to the listed federal antidiscrimination statutes, the sorts of health care programs and activities that are covered by Section 1557, and the definition of the personal characteristics, including sexual orientation and gender identity, against which discrimination is prohibited.