bluuebunny/crossref_metadata_2025 huggingface dataset:
Expedient Synthesis of N‐Methyl‐ and N‐Alkylamines by Reductive Amination using Reusable Cobalt Oxide Nanoparticles
Authors: Senthamarai Thirusangumurugan , Murugesan Kathiravan , Natte Kishore , Kalevaru Narayana V. , Neumann Helfried , Kamer Paul C. J. , Jagadeesh Rajenahally V.
Published: November 2017

N‐Methyl‐ and N‐alkylamines represent important fine and bulk chemicals that are extensively used in both academic research and industrial production. Notably, these structural motifs are found in a large number of life‐science molecules and play vital roles in regulating their activities. Therefore, the development of convenient and cost‐effective methods for the synthesis and functionalization of amines by using earth‐abundant metal‐based catalysts is of scientific interest. In this regard, herein we report an expedient reductive amination process for the selective synthesis of N‐methylated and N‐alkylated amines by using nitrogen‐doped, graphene‐activated nanoscale Co3O4‐based catalysts. Starting from inexpensive and easily accessible nitroarenes or amines and aqueous formaldehyde or aldehydes in the presence of formic acid, this cost‐efficient reductive amination protocol allows the synthesis of various N‐methyl‐ and N‐alkylamines, amino acid derivatives, and existing drug molecules.
Oxidation of Polynuclear Aromatic Hydrocarbons using Ruthenium‐Ion‐Catalyzed Oxidation: The Role of Aromatic Ring Number in Reaction Kinetics and Product Distribution
Authors: Nowicka Ewa , Clarke Tomos J. , Sankar Meenakshisundaram , Jenkins Robert L. , Knight David W. , Golunski Stanislaw , Hutchings Graham J. , Willock David J. , Francisco Manuel , Taylor Stuart H.
Published: November 2017

Oxidation of aromatic hydrocarbons with differing numbers of fused aromatic rings (2–5), have been studied in two solvent environments (monophasic and biphasic) using ruthenium‐ion‐catalyzed oxidation (RICO). RICO reduces the aromaticity of the polyaromatic core of the molecule in a controlled manner by selective oxidative ring opening. Moreover, the nature of the solvent system determines the product type and distribution, for molecules with more than two aromatic rings. Competitive oxidation between substrates with different numbers of aromatic rings has been studied in detail. It was found that the rate of polyaromatic hydrocarbon oxidation increases with the number of fused aromatic rings. A similar trend was also identified for alkylated aromatic hydrocarbons. The proof‐of‐concept investigation provides new insight into selective oxidation chemistry for upgrading of polyaromatic molecules.
Potential Therapeutic Applications of MnSODs and SOD‐Mimetics
Authors: Bonetta Rosalin
Published: November 2017

Natural as well as synthetic antioxidants are constantly being investigated for their efficiency in combatting the effects of oxidative stress, which appears to be the responsible cause of several diseases, including cancer, central nervous system disorders, ischaemia‐reperfusion disorders, cardiovascular conditions, and diabetes. Superoxide dismutases (SODs) constitute the ubiquitous antioxidant defences against oxidative stress that underlies numerous pathological conditions. Therefore, the development of therapeutics aimed at either delivering MnSOD more effectively to target tissues in the body in the form of MnSOD gene therapy, or the synthesis of molecules that mimic the activity of superoxide dismutase is constantly being explored. Classes that have been developed as SOD mimetics include the Mn‐metalloporphyrins, Mn‐cyclic polyamines, Mn‐salen complexes, MnPLED derivatives as well as the nitroxides. Thus far, SOD mimetics have shown remarkable efficacy in several animal models suffering from oxidative stress injuries. A promising approach for the future of SOD and SOD mimic therapeutics appears to involve combination treatment of the antioxidants with radiotherapy or chemotherapy.
Redox‐Dependent Metal−Metal Bonding in Trinuclear Metal Chains: Probing the Transition from Covalent Bonding to Exchange Coupling
Authors: Obies Mohammed , Perkins Nicholas R. , Arcisauskaite Vaida , Heath Graham A. , Edwards Alison J. , McGrady John E.
Published: November 2017

The synthesis and physical properties of two new cationic tri‐metallic chains, [(PEt3)3RuCl3M′Cl3Ru(PEt3)3]1+, M′=Rh and Ir are reported. These are isostructural with a previously reported 17‐electron all‐ruthenium analogue, but replacing a d5 RuIII ion in the central position with d6 RhIII/IrIII has a significant impact on the nature of the metal‐metal interactions. All three materials have been characterized electrochemically at the 18‐, 17‐ and 16‐electron levels. X‐ray crystallography and spectroelectrochemistry, complemented by electronic structure analysis at the DFT and CASPT2 levels, indicate that whilst the presence of a RuIII ion in the center of the chain allows multi‐center covalent bonding to develop, a closed‐shell RhIII/IrIII ion pushes the system towards the exchange‐coupled limit, where the outer Ru centers are only weakly interacting. This family of three isostructural compounds reveals how changes in metal composition can have subtle effects on physical properties of systems that lie close to the localized/delocalized borderline.
Control of Enantioselectivity in Rhodium(I) Catalysis by Planar Chiral Dibenzo[a,e]cyclooctatetraenes
Authors: Melcher Michaela‐Christina , Ivšić Trpimir , Olagnon Charlotte , Tenten Christina , Lützen Arne , Strand Daniel
Published: November 2017

Planar chiral 5,11‐disubstiuted dibenzo[a,e]cyclo‐octatetraenes (dbCOTs) have been developed as the first useful chiral homologs to dbCOT‐ligands for asymmetric applications. Methods enabling the preparation of such compounds on a gram‐scale in enantiomerically pure form are described. Evaluated as ligands in rhodium(I)‐catalyzed 1,4‐ and 1,2‐arylation reactions, tertiary and quarternary stereogenic centers were formed with excellent yields and selectivities of up to >99 % ee. A catalytic asymmetric synthesis of a key cyclization precursor to (−)‐penifulvin A highlights the system in an applied context.
Synthesis of Fucosylated Chondroitin Sulfate Glycoclusters: A Robust Route to New Anticoagulant Agents
Authors: Zhang Xiao , Yao Wang , Xu Xiaojiang , Sun Huifang , Zhao Jinhua , Meng Xiangbao , Wu Mingyi , Li Zhongjun
Published: November 2017

Fucosylated chondroitin sulfate (FuCS) is a structurally distinct glycosaminoglycan with excellent anticoagulant activity. Studies show that FuCS and its depolymerized fragments exhibit a different anticoagulant mechanism from that of heparin derivatives, with decreased risks of adverse effects and bleeding. However, further exploitation has been hindered by the scarcity of structurally defined oligosaccharides. Herein, facile method is reported for the synthesis of the repeating trisaccharide unit of FuCS based on the degradation of chondroitin sulfate polymers. A series of simplified FuCS glycomimetics that have highly tunable structures, controllable branches, and defined sulfation motifs were generated by copper‐catalyzed alkyne–azide cycloaddition. Remarkable improvement in activated partial thromboplastin time (APTT) assay activities was observed as the branches increased, but no significant influences were observed for prothrombin time (PT) and thrombin time (TT) assay activities. Further FXase inhibition tests suggested that glycoclusters 33 b–40 b selectively inhibited intrinsic anticoagulant activities, but had little effect on the extrinsic and common coagulation pathways. Notably, glycoclusters with the 2,4‐di‐O‐sulfated fucosyl residue displayed the most potency, which was in consistent with that of natural polysaccharides. These FuCS clusters demonstrated potency to mimic linear glycosaminoglycans and offer a new framework for the development of novel anticoagulant agents.
Dichromatic Photocatalytic Substitutions of Aryl Halides with a Small Organic Dye
Authors: Neumeier Michael , Sampedro Diego , Májek Michal , de la Peña O'Shea Víctor A. , Jacobi von Wangelin Axel , Pérez‐Ruiz Raúl
Published: November 2017

Photocatalytic bond activations are generally limited by the photon energy and the efficiency of energy and electron transfer processes. Direct two‐photon processes provide sufficient energy but the ultra‐short lifetimes of the excited states prohibit chemical reactions. The commercial dye 9,10‐dicyanoanthracene enabled photocatalytic aromatic substitutions of non‐activated aryl halides. This reaction operates under VIS‐irradiation via sequential photonic, electronic, and photonic activation of the simple organic dye. The resultant highly reducing excited photocatalyst anion readily effected C−H, C−C, C−P, C−S, and C−B bond formations. Detailed synthetic, spectroscopic, and theoretical studies support a biphotonic catalytic mechanism.
Numerical simulation of a semi‐industrial scale CFB riser using coarse‐grained DDPM‐EMMS modelling
Authors: Adnan Muhammad , Zhang Nan , Sun Fangfang , Wang Wei
Published: November 2017

In this work, a coarse‐grained Dense Discrete Phase Model (DDPM) coupled with the Energy‐Minimization Multi‐Scale (EMMS) drag, was used to simulate the hydrodynamics of a 3D semi‐industrial scale Circulating Fluidized Bed (CFB) with Geldart A particles. The effect of particle numbers in a parcel, an important parameter in a coarse‐grained approach, was investigated. It was found that when parcel diameter falls into the size range of clusters, simulation results are insensitive to particle number in a parcel and generally agree with the experimental data. Further, a comparison between DDPM and Eulerian Two‐Fluid Modelling (TFM) approaches was investigated, both coupled with EMMS and conventional homogenous drag. The simulation results suggested that the effect of meso‐scale structures on drag force needs to be considered in both modelling approaches.
Diagnostic challenges and problem cases in salivary gland cytology: A 20‐year experience
Authors: Salehi Sajad , Maleki Zahra
Published: November 2017

BACKGROUND

Fine‐needle aspiration (FNA) is routinely performed to evaluate salivary gland lesions, and provides valuable information regarding the cytomorphologic features of the lesions. Occasionally, there are overlaps between benign and malignant conditions due to heterogeneity of the cell types, metaplastic changes, and sampling issues. Herein, the authors present a retrospective study of diagnostic pitfalls in salivary gland cytology and the simulating conditions.

METHODS

A 20‐year retrospective review (1995‐2015) of medical records was performed searching for the cytology reports of patients who underwent FNA of the salivary gland with the words “amendment” or “revision.” Medical records of the revised cases were reviewed for the subsequent surgical follow‐up. All cases with a diagnostic discrepancy between the primary cytologic diagnosis and the final histology diagnosis were included in the current study. The histologic diagnosis was considered the gold standard.

RESULTS

A total of 19 cases were included in the current study. The cases were divided into 7 categories based on their cytologic diagnoses: 1) nondiagnostic (1 case); 2) benign, nonneoplastic lesion (2 cases); 3) benign salivary gland neoplasm (2 cases); 4) salivary gland neoplasm (4 cases); 5) epithelial neoplasm, not otherwise specified (1 case); 6) markedly atypical cells suspicious for a malignant neoplasm (1 case); and 7) malignant neoplasms (8 cases).

CONCLUSIONS

The interpretation of salivary gland FNA can be influenced by several factors including prominent metaplasia, focal atypia, cystic changes, variable cellular components within the lesions, scant cellularity, variants of neoplasms, and a prior history of malignancy. Multiple passes representing the entire mass, imaging findings, and familiarity with salivary gland cytomorphology may improve the diagnostic accuracy. Cancer Cytopathol 2018;126:101‐11. © 2017 American Cancer Society.
Performance comparison between Hadoop and Spark frameworks using HiBench benchmarks
Authors: Samadi Yassir , Zbakh Mostapha , Tadonki Claude
Published: November 2017

Big Data has become one of the major areas of research for cloud service providers due to a large amount of data produced every day and the inefficiency of traditional algorithms and technologies to handle these large amounts of data. Big Data with its characteristics such as volume, variety, and veracity (3V) requires efficient technologies to process in real time. To solve this problem and to process and analyze this vast amount of data, there are many powerful tools like Hadoop and Spark, which are mainly used in the context of Big Data. They work following the principles of parallel computing. The challenge is to specify which Big Data's tool is better depending on the processing context. In this paper, we present and discuss a performance comparison between two popular Big Data frameworks deployed on virtual machines. Hadoop MapReduce and Apache Spark are used to efficiently process a vast amount of data in parallel and distributed mode on large clusters, and both of them suit for Big Data processing. We also present the execution results of Apache Hadoop in Amazon EC2, a major cloud computing environment. To compare the performance of these two frameworks, we use HiBench benchmark suite, which is an experimental approach for measuring the effectiveness of any computer system. The comparison is made based on three criteria: execution time, throughput, and speedup. We test Wordcount workload with different data sizes for more accurate results. Our experimental results show that the performance of these frameworks varies significantly based on the use case implementation. Furthermore, from our results we draw the conclusion that Spark is more efficient than Hadoop to deal with a large amount of data in major cases. However, Spark requires higher memory allocation, since it loads the data to be processed into memory and keeps them in caches for a while, just like standard databases. So the choice depends on performance level and memory constraints.
Understanding the Reactive Adsorption of H2S and CO2 in Sodium‐Exchanged Zeolites
Authors: Fetisov Evgenii O. , Shah Mansi S. , Knight Christopher , Tsapatsis Michael , Siepmann J. Ilja
Published: November 2017

Purifying sour natural gas streams containing hydrogen sulfide and carbon dioxide has been a long‐standing environmental and economic challenge. In the presence of cation‐exchanged zeolites, these two acid gases can react to form carbonyl sulfide and water (H2S+CO2⇌H2O+COS), but this reaction is rarely accounted for. In this work, we carry out reactive first‐principles Monte Carlo (RxFPMC) simulations for mixtures of H2S and CO2 in all‐silica and Na‐exchanged forms of zeolite beta to understand the governing principles driving the enhanced conversion. The RxFPMC simulations show that the presence of Na+ cations can change the equilibrium constant by several orders of magnitude compared to the gas phase or in all‐silica beta. The shift in the reaction equilibrium is caused by very strong interactions of H2O with Na+ that reduce the reaction enthalpy by about 20 kJ mol−1. The simulations also demonstrate that the siting of Al atoms in the framework plays an important role. The RxFPMC method presented here is applicable to any chemical conversion in any confined environment, where strong interactions of guest molecules with the host framework and high activation energies limit the use of other computational approaches to study reaction equilibria.
Synthesis and Properties of Open Fullerenes Encapsulating Ammonia and Methane
Authors: Bloodworth Sally , Gräsvik John , Alom Shamim , Kouřil Karel , Elliott Stuart J. , Wells Neil J. , Horsewill Anthony J. , Mamone Salvatore , Jiménez‐Ruiz Mónica , Rols Stéphane , Nagel Urmas , Rõõm Toomas , Levitt Malcolm H. , Whitby Richard J.
Published: November 2017

We describe the synthesis and characterisation of open fullerene (1) and its reduced form (2) in which CH4 and NH3 are encapsulated, respectively. The 1H NMR resonance of endohedral NH3 is broadened by scalar coupling to the quadrupolar 14N nucleus, which relaxes rapidly. This broadening is absent for small satellite peaks, which are attributed to natural abundance 15N. The influence of the scalar relaxation mechanism on the linewidth of the 1H ammonia resonance is probed by variable temperature NMR. A rotational correlation time of τc=1.5 ps. is determined for endohedral NH3, and of τc=57±5 ps. for the open fullerene, indicating free rotation of the encapsulated molecule. IR spectroscopy of NH3@2 at 5 K identifies three vibrations of NH3 (ν1, ν3 and ν4) redshifted in comparison with free NH3, and temperature dependence of the IR peak intensity indicates the presence of a large number of excited translational/ rotational states. Variable temperature 1H NMR spectra indicate that endohedral CH4 is also able to rotate freely at 223 K, on the NMR timescale. Inelastic neutron scattering (INS) spectra of CH4@1 show both rotational and translational modes of CH4. Energy of the first excited rotational state (J=1) of CH4@1 is significantly lower than that of free CH4.
Gut microbiota and body composition in anorexia nervosa inpatients in comparison to athletes, overweight, obese, and normal weight controls
Authors: Mörkl Sabrina , Lackner Sonja , Müller Wolfram , Gorkiewicz Gregor , Kashofer Karl , Oberascher Andreas , Painold Annamaria , Holl Anna , Holzer Peter , Meinitzer Andreas , Mangge Harald , Holasek Sandra
Published: November 2017

Objectives

Anorexia nervosa (AN) is a heterogeneous eating disorder associated with alterations of body structure and the gut microbiome. We aimed to investigate the gut microbiota composition of a large female cohort including different BMI groups and activity levels along with body composition parameters.

Method

106 female participants were included in this cross‐sectional study: AN patients (n = 18), athletes (n = 20), normal weight (n = 26), overweight (n = 22), and obese women (n = 20). DNA was extracted from stool samples and subjected to 16S rRNA gene analysis. The software Quantitative Insights Into Microbial Ecology (QIIME) was used to analyze data. Additionally, we performed anthropometric assessments, ultrasound measurements of subcutaneous adipose tissue thickness, bioimpedance analysis, administered depression inventories, and ascertained laboratory parameters and dietary intakes.

Results

Alpha diversity was particularly lower in AN patients and obese participants compared to other groups, while athletes showed highest alpha diversity. Several categories significantly associated with community structure were identified: body fat parameters, serum lipids, CRP, depression scales and smoking. Comparative analysis revealed Coriobacteriaceae as the only enriched phylotype in AN compared to other entities (LDA score >3.5).

Discussion

This study provides further evidence of intestinal dysbiosis in AN and sheds light on characteristics of the gut microbiome in different BMI and physical activity groups. These insights point to new modulation possibilities of the gut microbiota which could improve the standard therapy of AN.
Hemiparasites can transmit indirect effects from their host plants to herbivores
Authors: Haan Nathan L. , Bakker Jonathan D. , Bowers M. Deane
Published: November 2017

Parasitic plants can serve as critical intermediaries between their hosts and other organisms; however these relationships are not well understood. To investigate the relative importance of plant traits in such interactions, we studied the role of the root hemiparasite,Castilleja levisecta(Orobanchaceae), as a mediator of interactions between the host plants it parasitizes and the lepidopteran herbivoreEuphydryas editha(Nymphalidae), whose caterpillars feed onCastillejaand sequester iridoid glycosides from it. We tested whether the hemiparasite's size, leaf N concentration, and iridoid glycoside concentrations were influenced by the identity of its host plant, and then whether these traits influenced outcomes for the herbivore. We found that the hemiparasite's size and leaf N depended on the host it parasitized, and these traits in turn affected outcomes forE. editha. Specifically,Euphydryas edithasurvival increased with hemiparasite size and caterpillar mass increased with leaf N; caterpillars with greater mass were more likely to survive during diapause. We also found preliminary evidence that host identity influenced iridoid glycoside sequestration by the herbivore. Mean iridoid glycoside concentrations in caterpillars ranged from 1–12% depending on the host being parasitized byCastilleja. This study demonstrates that root parasitism can result in strong indirect effects on higher trophic levels, influencing organisms’ survival, growth, and chemical interactions.
TEMPO‐Mediated Oxidative Deformylation of Aldehydes: Applications in the Synthesis of Polyketide Fragments
Authors: Kipke Andreas , Schöning Kai‐Uwe , Yusubov Mekhman , Kirschning Andreas
Published: November 2017

A TEMPO‐mediated oxidative deformylation of aldehydes is reported that yields the TEMPO adducts, which can be further oxidized to the corresponding ketones. The focus of this work was on the optimization of a synthetic protocol for use in natural product synthesis, specifically for the preparation of chiral backbones with 1,2‐oxo functionalization found in polyketide antibiotics. In addition, the oxidative deformylation was combined with the oxidation of the alcohol to the precursor aldehyde in a one‐pot protocol.
Conductance‐based profiling of nanopores: Accommodating fabrication irregularities
Authors: Bandara Y. M. N. D. Y. , Nichols Jonathan W. , Iroshika Karawdeniya Buddini , Dwyer Jason R.
Published: November 2017

Solid‐state nanopores are nanoscale channels through otherwise impermeable membranes. Single molecules or particles can be passed through electrolyte‐filled nanopores by, e.g. electrophoresis, and then detected through the resulting physical displacement of ions within the nanopore. Nanopore size, shape, and surface chemistry must be carefully controlled, and on extremely challenging <10 nm‐length scales. We previously developed a framework to characterize nanopores from the time‐dependent changes in their conductance as they are being formed through solution‐phase nanofabrication processes with the appeal of ease and accessibility. We revisited this simulation work, confirmed the suitability of the basic conductance equation using the results of time‐dependent experimental conductance measurements during nanopore fabrication by Yanagi et al., and then deliberately relaxed the model constraints to allow for (i) the presence of defects; and (ii) the formation of two small pores instead of one larger one. Our simulations demonstrated that the time‐dependent conductance formalism supports the detection and characterization of defects, as well as the determination of pore number, but with implementation performance depending on the measurement context and results. In some cases, the ability to discriminate numerically between the correct and incorrect nanopore profiles was slight, but with accompanying differences in candidate nanopore dimensions that could yield to post‐fabrication conductance profiling, or be used as convenient uncertainty bounds. Time‐dependent nanopore conductance thus offers insight into nanopore structure and function, even in the presence of fabrication defects.
An Electrochemical Method for Monitoring the Acidity of Water for Fuel Cell and Environmental Applications
Authors: Gao Xiangming , Dai Chencheng , Xu Zhichuan J. , Lawrence Nathan S. , Fisher Adrian C.
Published: November 2017

Maintaining energy and water supplies is still a prime global challenge and hydrogen fuels are set to offer a solution to this challenge, as the combination of hydrogen and oxygen as a fuel stock with the generation of pure water as by‐product is extremely attractive. However, ensuring that the water supply is clean and contaminant‐free is key to ensuring that it can be incorporated into the drinking supply. Contaminants from the fuel cell catalysts or breakdown of materials within the fuel cell over its working life will affect the water quality. The measurement of acidity (pH) is an important indicator for understanding water quality. This article reports a calibration‐free, affordable, screen‐printed electrode (SPE) capable of measuring pH within these waters. This device is fabricated by screen printing pH‐insensitive ferrocene, in conjunction with a pH‐active (and redox‐active) alizarin compound. This electrode reveals consistent voltammetric response to both buffered and low‐buffered media with sufficient supporting electrolytes, achieving a working range from pH 2 to 9.5. This approach provides a disposable, reproducible, low‐cost method for pH monitoring in harsh environments, for example in low‐buffered water quality monitoring and the food industry.
Ractopamine in particulate matter emitted from beef cattle feedyards and playa wetlands in the Central Plains
Authors: Wooten Kimberly J. , Sandoz Melissa A. , Smith Philip N.
Published: November 2017

Beef cattle in the United States are routinely administered ractopamine, a β-adrenergic receptor agonist, to enhance growth. The present study is the first to quantify ractopamine in feedyard-emitted particulate matter and playa wetlands near feedyards. Ractopamine was present in 92% of particulate matter samples, 16% of playa sediment samples, and 3% of playa water samples, at maximum concentrations of 4.7 μg/g, 5.2 ng/g (dry wt), and 271 ng/L, respectively. These data suggest that aerial transmission and deposition of particulate matter is a transport mechanism for ractopamine between feedyards and aquatic systems in the region. Environ Toxicol Chem 2018;37:970–974. © 2017 SETAC
Finger gesture input utilizing the rear camera of a mobile phone: A perspective of mobile CAD
Authors: Lee Sangwon , Ha Taehyun , Lim Seong‐Jae
Published: November 2017

Various interfaces have been suggested for mobile devices, including touch gesture and embedded sensor‐based interfaces. However, if a user's task requires a thorough look, these interfaces hinder sight of view in display and thus can be inappropriate for the tasks. This problem is more important especially in the mobile computer aided design (CAD) context, which performs visually demanding tasks on the limited screen. To address this point, this study suggests a mobile interface utilizing the rear camera of the device and describes the function mapping for CAD. The suggested interface detects finger attachment and movement direction. The number of colors in camera vision and local binary pattern are used as features, and a support vector machine (SVM) is used for feature classification. A prototype application is designed for validation, and appropriate SVM models are selected through benchmarking tests. The validation results show that the suggested interface can perform with high accuracy and low computational resources.
High HSF4 expression is an independent indicator of poor overall survival and recurrence free survival in patients with primary colorectal cancer
Authors: Yang Yingchi , Jin Lan , Zhang Jinghui , Wang Jin , Zhao Xiaomu , Wu Guocong , Yao Hongwei , Zhang Zhongtao
Published: November 2017

Heat shock factor 4 (HSF4) is a member of the HSF family. In this study, by using data from the Cancer Genome Atlas‐Colorectal Cancer (TCGA‐CRC), we investigated the expression profile and the prognostic value of the HSF4 in terms of overall survival (OS) and recurrence free survival (RFS) in CRC patients. RNA‐Seq data showed that HSF4 RNA expression was significantly higher in CRC tissues (N = 380) than in the corresponding normal tissues (N = 51) (mean ± SD: 3.56 ± 1.28 vs. 1.85 ± 0.87, P < 0.0001). High HSF4 expression group had significantly higher ratio of stages III/IV patients (52/86, 60.5%) than low HSF4 expression group (110/264, 41.7%; P = 0.0024). Besides, the high HSF4 expression group also had significantly increased expression of CEA (CEA ≥ 5, 26/51, 51.0% vs. 64/186, 34.4%), higher proportion of recurrence (32/86, 37.2% vs. 48/254, 18.9%, P = 0.0005) and death (36/90, 40.0% vs. 49/277, 17.7%, P < 0.0001) compared with the low HSF4 expression group. Multivariate analysis confirmed that high HSF4 expression was an independent prognostic factor of poor OS (HR = 2.111, 95%CI: 1.350–3.302, P = 0.001) and RFS (HR = 1.958, 95%CI: 1.224–3.131, P = 0.005). Bioinformatic analysis showed that HSF4 can directly interact with DUSP26, ZBED8, and MAPK14. It is also coexpressed with PTGER1, COL11A2, CLPS, and ARSA and colocalized with PTGER1, ADRB1, PEX12, CLPS, PSEN2, KCNJ5, CPA1, ARSA, PNLIP, IRX4, CPA2, IDUA, BCKDHA, and CTRL. We hypothesized that HSF4 might exert its oncogenic effects in CRC via some of these genes. © 2017 IUBMB Life, 69(12):956–961, 2017
The toxicological effects of some avermectins on goat liver carbonic anhydrase enzyme
Authors: Caglayan Cuneyt , Gulcin İlhami
Published: November 2017

Avermectins are used worldwide as antiparasitic drugs in the field of veterinary medicine and as agricultural pesticides and insecticides. Carbonic anhydrase (CA, E.C. 4.2.1.1) is a zinc‐containing metalloenzyme that catalyzes the reversible hydration of carbon dioxide (CO2) to yield protons (H+) and bicarbonate (HCO3−). In this study, some avermectins, including abamectin, doramectin, eprinomectin, and moxidectin, were investigated for in vitro inhibitory effects on the CA enzyme purified from goat liver, which was purified (125.00‐fold) using sepharose 4B‐l‐tyrosine‐sulfanilamide affinity chromatography, with a yield of 68.27% and a specific activity of 21765.31 EU/mg proteins. The inhibition results obtained from this study showed Ki values of 0.283, 0.153, 0.232, and 0.317 nM for abamectin, doramectin, eprinomectin, and moxidectin, respectively. On the other hand, acetazolamide, well‐known clinically established CA inhibitor, possessed a Ki value of 0.707 nM against goat liver CA.
New insights of subfertility among transplanted women: Immunosuppressive drug FK506 leads to calcium leak and oocyte activation before fertilization
Authors: Liu Linlin , Yang Man , Wang Naiqiang , Li Li , Chen Zi‐Jiang , Zhang Cong
Published: November 2017

FKBP12, known as FK506 binding protein, binds to immunosuppressive drug FK506, which must be taken by patients who received organ transplant. The side effect of FK506 is that women have difficulties in bearing a baby, so it is important to find the reason of their subfertility. This research explored the expression of FKBP12 in pre‐implantation embryos and investigated its potential effect on reproduction. The results demonstrate that FKBP12 had good co‐localization with endoplasmic reticulum and inositol‐1, 4, 5‐ trisphosphate receptor in pre‐implantation stages. Inhibiting FKBP12 by FK506 significantly increased the rate of 1‐cell and fragmented embryos, greatly reduced the rate of 2‐cell embryos during in vitro fertilization. When the mice received FK506 by gavage for 21 days, the calcium intensity of oocytes was decreased, these mice were subfertile and gave birth to significantly less pups during 6‐month breeding period. QPCR demonstrated that Fbxo43 and P27kip, which are related to the release of MII oocyte arrest, and calcium channel partner protein Orai1 were downregulated, while Cdc2 and Ca2+ sensor at ER, stromal interaction molecule 1 (Stim1) were upregulated for a short time after adding FK506. Further exploration discovered that FK506 treatment increased Ca2+ concentration in the cytoplasm and caused pronucleus formation, however, the rate of parthenogenetic activation was lower compared to SrCl2 group. These findings identify the previously unknown role of FKBP12 in female reproduction which contributes to the release of calcium via IP3R channel and might open up new strategies for women who want to bear a baby after transplantation.
Examining the characteristics and clinical features of in‐ and between‐session suicide risk assessments among psychiatric outpatients
Authors: Hom Melanie A. , Stanley Ian H. , Rogers Megan L. , Sheffler Julia L. , Nelson Katherine R. , Joiner Thomas E. , Schramm Elisabeth
Published: November 2017

Objective

To evaluate the characteristics of suicide risk assessments completed using the Decision Tree framework both in and between psychotherapy sessions, clinical features of patients for whom between‐session assessments are indicated, and data collected across assessments.

Method

Data were collected from 1,358 suicide risk assessments conducted with psychiatric outpatients (N = 41) at elevated suicide risk engaged in care at a psychology training clinic.

Results

Participants completed an average of 4.75 (standard deviation = 4.95) suicide risk assessments (2.81 ± 4.43 between‐session assessments) per each month in treatment. Assessment frequency and patient ratings of suicidal desire and intent were each significantly associated with therapist risk level categorizations.

Conclusion

The Decision Tree framework's in‐ and between‐session assessments have the potential to be implemented in a routinized format among psychiatric outpatients at elevated suicide risk. Additional research is needed to establish the feasibility and clinical utility of this framework across samples and providers.
The impact of rape acknowledgment on survivor outcomes: The moderating effects of rape myth acceptance
Authors: Wilson Laura C. , Newins Amie R. , White Susan W.
Published: November 2017

Objective

Little is known about how rape acknowledgment relates to posttrauma functioning; recent research suggests the effect may depend on additional factors. In the current study, the moderating effect of rape myth acceptance (RMA) on the relationships between rape acknowledgment and mental health outcomes was examined.

Method

A sample of 181 female rape survivors recruited from a university completed an online survey assessing RMA, rape acknowledgment, depression symptoms, and alcohol use.

Results

Generally, the results supported that RMA moderated the influence of rape acknowledgment on depression symptoms and average quantity per drinking episode, but not frequency of alcohol use. The findings demonstrated that when individuals endorsed high levels of RMA, acknowledged rape survivors reported worse outcomes than unacknowledged rape survivors. Among individuals low on RMA, unacknowledged rape survivors reported worse outcomes than acknowledged rape survivors.

Conclusion

It is recommended that clinicians recognize the role of survivor beliefs, such as RMA, in the relationship between labeling sexual assault experiences and mental health consequences.
Airyscan super‐resolution microscopy of mitochondrial morphology and dynamics in living tumor cells
Authors: Kolossov Vladimir L. , Sivaguru Mayandi , Huff Joseph , Luby Katherine , Kanakaraju Kaviamuthan , Gaskins H. Rex
Published: November 2017

Mitochondrial morphology is regulated by continuous fusion‐and‐fission events that are essential for maintaining normal function. Despite the prominence of mitochondrial function in energy generation and cell signaling, understanding of processes of fusion and fission dynamics has been hampered by the lack of high‐resolution optical systems that accommodate live‐cell imaging. We have examined different confocal modalities in terms of resolution and signal‐to‐noise ratio (SNR) in a point scanning confocal microscope with Airyscan super‐resolution (AS‐SR). Results indicated that Airyscan (AS) provided speed, super‐resolution, and high SNR. This modality was then used for monitoring mitochondrial dynamics in live tumor cells modified to harbor green‐fluorescent protein localized to mitochondria. We then compared regular AS and fast‐Airyscan modalities in terms of gentleness on the live‐cell samples. The fast mode provided unprecedented imaging speed that permits monitoring dynamics both in 2D and also in three‐dimensional dataset with time lapses (4D). Alterations to the mitochondrial network in U87 glioblastoma cells occurred within seconds and the cells were not affected by modest inhibition of fission. The super‐resolution permitted quantitative measurements of mitochondrial diameter with a precision that enabled detection of significant differences in mitochondrial morphology between cell lines. We have observed swelling of mitochondrial tubules in A549 lung cancer cells after 2 hr treatment with deoxynyboquinone, an ROS‐generating pharmacologic drug. We also tested different 3D analytical parameters and how they can affect morphometric quantitation. The AS‐SR imaging enabled high‐speed imaging of mitochondrial dynamics without the compromise to cell morphology or viability that is common with conventional fluorescence imaging due to photo‐oxidation.
Synthesis and Antibacterial Activity of Novel 1H‐indol‐2‐ol Derivatives
Authors: Tu Hong , Wu Shou‐Qun , Li Xiao‐Qin , Wan Zhen‐Chao , Wan Jin‐Lin , Tian Kun , Ouyang Gui‐Ping
Published: November 2017

A series of novel 1H‐indol‐2‐ol derivatives were synthesized and evaluated their antibacterial activities against rice bacterial leaf blight, tobacco bacterial wilt, and citrus canker caused by Xanthomonas oryzae pv. oryzae (Xoo), Ralstonia solanacearum, and Xanthomonas axonopodis pv. citri via the turbidimeter test in vitro. Antibacterial bioassay indicated that most compounds demonstrated good inhibitory effect against Xoo and Ralstonia solanacearum. Especially, compound 4k demonstrated the best inhibitory effect against Xoo with half‐maximal effective concentration (EC50) value of 8.27 μg/mL, which was even better than those of commercial agents Bismerthiazol and Thiodiazole copper.
Dynamics of H2O ligands and ReO4− anions at the phase transition in [Mn(H2O)2](ReO4)2 studied by complementary spectroscopic methods
Authors: Hetmańczyk Joanna , Hetmańczyk Łukasz
Published: November 2017

The vibrational and reorientational motions of H2O ligands and
anions in high‐ and low‐temperature phases were investigated by means of Fourier transform far‐ and mid‐infrared and Raman light‐scattering spectroscopy and neutron scattering (inelastic/quasi‐elastic incoherent neutron scattering) methods. The dynamics of H2O and
molecules in high‐ (I) and low‐temperature (II) phases was investigated by means of band shape analysis performed for Raman and IR bands. The temperature dependencies of full width at half maximum values of the Raman bands at 874 (νas(ReO)) and 943 cm−1 (νs(ReO)) exhibit changes in their behaviour in the vicinity of transformation, suggesting that the observed phase transition is connected with a change in the reorientational dynamics of
. However, anions also perform fast (τR ≈ 10−12 to 10−13 s) stochastic reorientational motions in Phase II. The estimated mean value of activation energy for
anions in the low‐temperature phase is Ea(II) = 8.1 kJmol−1. In infrared band shape analysis it was found that H2O ligands perform fast (picosecond correlation time scale) motions in both phases with a mean value of activation energies of 7.68 kJmol−1. These reorientational motions of H2O ligands do not contribute to the phase transition mechanism. Moreover, the observed phase transition was accompanied by the splitting of some bands, suggesting a reduction in crystal structure symmetry.

Quasi‐elastic neutron scattering measurements furnished evidence that H2O motion in Phase I can be fairly accurately described by a simple model of 180° jumps around a twofold axis within a picosecond time scale. Additionally, infrared, Raman light‐scattering spectra were calculated using the density functional theory method for the isolated equilibrium model Mn(H2O)2(ReO4)2, and qualitative agreement with the experimental data was achieved. The theoretical vibrational spectra of the title compound were interpreted by means of potential energy distributions using the VEDA 4 program.
Effect of farming system on donkey milk composition
Authors: Valle Emanuela , Pozzo Luisa , Giribaldi Marzia , Bergero Domenico , Gennero Maria Silvia , Dezzutto Daniela , McLean Amy , Borreani Giorgio , Coppa Mauro , Cavallarin Laura
Published: November 2017

BACKGROUND

Donkey milk is considered as a functional food for sensitive consumers, such as children who are allergic to cow milk. No information is available regarding the effect of farming systems on the quality of donkey milk. The present study aimed to evaluate the effect of the farming system and lactation stage on donkey milk with respect to gross composition, as well as fat‐soluble vitamins and fatty acids (FA).

RESULTS

Individual milk samples were collected from lactating jennies (n = 53) on the six of the largest farms located in North West Italy. The performance of lactating jennies, herd characteristics and feeding strategies were recorded at each milk sampling. The gross composition of the milk, along with the fat‐soluble vitamin content, differed in accordance with the farming system. The lactation stage had limited effects on milk quality. A higher milk fat content corresponded to a higher amount of fresh herbage proportion in the diet, with the highest polyunsaturated fatty acid (PUFA), C18:1c9, C18:3n‐3, n‐3 FA, retinol and α‐tocopherol content and the lowest concentrations of the FA that are less favorable for human health in the milk of animals fed on only forage diets.

CONCLUSION

Extensive farming of dairy donkeys increased the fat content and fat‐soluble vitamin concentration of milk and also altered the FA composition to a more favorable profile for human nutrition. © 2017 Society of Chemical Industry
Modified dispersive liquid‐phase microextraction based on sequential injection solidified floating organic drop combined with HPLC for the determination of phenobarbital and phenytoin
Authors: Amiri Pebdani Arezou , Dadfarnia Shayessteh , Haji Shabani Ali Mohammad , Khodadoust Saeid , Talebianpoor Mohammad Sharif
Published: November 2017

A modified dispersive liquid phase microextraction based on sequential injection solidified floating organic drop was developed for simultaneous separation/preconcentration of trace amounts of phenobarbital and phenytoin. The important factors affecting on the extraction recovery including pH, the volume of extraction solvent, ionic strength, and the number of injections were investigated and optimized by Box–Behnken design and desirability function. Under the optimum experimental conditions, the calibration graph was linear in the concentration range of 1.0–300.0 μg/L (r2 = 0.997) for phenobarbital and 2.0–400.0 μg/L (r2 = 0.996) for phenytoin. The limit of detection and limit of quantification were 0.35 and 1.2 μg/L for phenobarbital and 0.65 and 2.2 μg/L for phenytoin, respectively. The relative standard deviation for six replicate determinations at 10 μg/L was 3.3 and 4.1% for phenobarbital and phenytoin, respectively. The developed method was successfully applied to the determination of phenobarbital and phenytoin in urine and plasma samples.
Development of a capillary electrophoresis method for the determination of the chiral purity of dextromethorphan by a dual selector system using quality by design methodology
Authors: Krait Sulaiman , Heuermann Matthias , Scriba Gerhard K. E.
Published: November 2017

Dextromethorphan is a centrally acting antitussive drug, while its enantiomer levomethorphan is an illicit drug with opioid analgesic effects. As capillary electrophoresis has been proven as an ideal technique for enantiomer analysis, the present study was conducted in order to develop a capillary electrophoresis‐based limit test for levomethorphan. The analytical target profile was defined as a method that should be able to determine levomethorphan with acceptable precision and accuracy at the 0.1 % level. From initial scouting experiments, a dual selector system consisting of sulfated β‐cyclodextrin and methyl‐α‐cyclodextrin was identified. The critical process parameters were evaluated in a fractional factorial resolution IV design followed by a central composite face‐centered design and Monte Carlo simulations for defining the design space of the method. The selected working conditions consisted of a 30/40.2 cm, 50 μm id fused‐silica capillary, 30 mM sodium phosphate buffer, pH 6.5, 16 mg/mL sulfated β‐cyclodextrin, and 14 mg/mL methyl‐α‐cyclodextrin at 20°C and 20 kV. The method was validated according to ICH guideline Q2(R1) and applied to the analysis of a capsule formulation. Furthermore, the apparent binding constants between the enantiomers and the cyclodextrins as well as complex mobilities were determined to understand the migration behavior of the analytes.
Kinetics and Mechanism of Cumene Oxidation Initiated by N‐Hydroxyphthalimide
Authors: Sapunov V. N. , Kurganova E. A. , Koshel G. N.
Published: November 2017

This paper discusses the results of investigations on the kinetics of cumene oxidation to cumene hydroperoxide by molecular oxygen in the presence of N‐hydroxyphthalimide as a catalyst. A mathematical model has been developed on the basis of the regularities of hydroperoxide and by‐products formation. The model adequately describes changes in all reaction components in the course of the reaction. It has also been established that the role of N‐hydroxyphthalimide in the process consists in the creation of a steady‐state concentration of N‐phthalimide radicals initiating oxidation by interacting with the hydrocarbon.
A new porcine vascularized tibial bone allotransplantation model. Anatomy and surgical technique
Authors: Kotsougiani Dimitra , Willems Joost I. , Shin Alexander Y. , Friedrich Patricia F. , Hundepool Caroline A. , Bishop Allen T.
Published: November 2017

Introduction

Vascularized bone allotransplantation may provide new options for reconstruction of segmental defects if problems of long‐term immune modulation can be solved. The current literature lacks an orthotopic large animal model, limited to bone and without the confounding effects of other tissue types, permitting a multifaceted evaluation before new methods are used clinically. The purpose of this study was to develop a large animal model for vascularized bone allotransplantation.

Materials and methods

Eight porcine hind limbs were dissected. Length, diameter, and location of all hindlimb vessels were measured and a single nutrient vessel supplying the tibial diaphysis identified enabling its use as a vascularized bone allotransplant. Four Yucatan minipigs were divided into two pairs with a major swine leukocyte antigen mismatch. A 3.5 cm tibial segment including its nutrient pedicle was raised simultaneously from each pig and transplanted into the matched defect of the other animal. Microarterial anastomosis of the pedicle and 3‐drug immunosuppression maintained VCA viability. Bone healing and limb function were followed for 16 weeks.

Results

A consistent tibia diaphyseal nutrient artery arose from the caudal tibial artery to enter bone a mean 2.8 mm distal to the tibial tubercle with a pedicle length of 6.6 ± 3.3 mm and diameter of 1.6 ± 0.2 mm. Using this pedicle, we reconstructed a 3.5 cm tibial defect with a vascularized bone allotransplant in four animals. Immediate weightbearing as well as progressive bone healing was demonstrated.

Conclusion

We have developed a vascularized tibial bone allotranplantation large‐animal model suitable for future bone‐only allotranplantation research in mini‐pigs.