bluuebunny/crossref_metadata_2025 huggingface dataset:
Wood‐based composites with thermoplastic polyurethane as matrix polymer
Authors: Diestel Sylvia , Krause Andreas
Published: March 2018

This research reports the influence of the mechanical properties of thermoplastic polyurethane (TPU) as a function of wood filler percentage. Wood flour was mixed with two different chemically based TPUs. Also, moisture content during compounding process as well as the origin of moisture (wood or TPU) were studied. All experimental designs and statistical analysis were done with the software Design Expert Version 10. Composite preparation took place in a multi‐stage process. The results showed that 70% wood filler can be incorporated in the composite manufacture. The properties of the composite were mainly influenced by the proportion of wood and TPU. Wood flour increased the density, hardness, water absorption, and tensile modulus with a decrease in impact resistance and abrasion resistance of the composite. Tensile strength exhibited a decrease up to ∼35% wood content, but an increase with further addition of wood. Moisture content had only a minor influence on the mechanical and water absorption properties despite the noted severe moisture sensitivity of TPU, which usually leads to decline in mechanical properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46344.
Systematically engineering Escherichia coli for enhanced shikimate biosynthesis co‐utilizing glycerol and glucose
Authors: Bilal Muhammad , Yue Shengjie , Hu Hongbo , Wang Wei , Zhang Xuehong
Published: March 2018

In this study, an Escherichia coli strain with the capability to utilize glycerol/glucose simultaneously was genetically engineered to produce high shikimate. To achieve this, the ptsG gene encoding EIICBglc protein was inactivated in the BW25113 strain to alleviate carbon catabolite repression. The shikimate kinase genes aroK and aroL were also eliminated to construct the SA‐B2 strain, which led to a 42.3% increase in shikimate production. Thereafter, three critical genes, namely mutant aroGfbr, ppsA, and tktA, were overexpressed in strain SA‐B2, and the resulting engineered SA‐B7 strain produced 0.92 g/L shikimate in shake flask cultures, which were 2.5 times higher than strain SA‐B2. The influence of varying carbon mole numbers ratios of glycerol to glucose on the production of shikimate was also investigated, where the highest shikimate production was attained at a glycerol‐to‐glucose ratio of 12:1 by SA‐B7. Moreover, the amount of NADPH was 3.5‐times higher in the mixed culture medium as compared to sole glycerol‐based medium. RT‐PCR data indicated that the addition of glucose upregulated the transcriptional levels of genes pertaining to shikimate biosynthesis. In conclusion, the findings demonstrated that E. coli could be modified as a potential cell factory to produce shikimate and other high‐value derived aromatic compounds by genetic and metabolic engineering strategies. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd
Nutrient intake in women before conception and risks of anophthalmia and microphthalmia in their offspring
Authors: Weber Kari A. , Yang Wei , Carmichael Suzan L. , Shaw Gary M. ,   National Birth Defects Prevention Study
Published: March 2018

Background

We previously explored associations between nutrients including folate and other macro and micronutrients and risks of anophthalmia or microphthalmia in the National Birth Defects Prevention Study. In the current study, we expand those previous results with larger sample sizes and conduct analyses with an additional diet quality index using more recent data.

Methods

The National Birth Defects Prevention Study is a population‐based, multicenter case‐control study of over 30 major birth defects, with estimated due dates from October 1997 to December 2011. Cases were 224 infants diagnosed with anophthalmia or microphthalmia. Controls were 11,109 live‐born, nonmalformed infants randomly selected by each study center. Mothers completed a standardized, computer‐assisted telephone interview between 6 weeks and 24 months after delivery. Mothers responded to a shortened food frequency questionnaire, assessing their nutrient intake for the year before pregnancy, and questions about periconceptional (2 months before to 2 months after conception) vitamin supplement use. Nutrient intake quartiles were based on the intake among controls.

Results

Among vitamin supplement users, odds of anophthalmia/microphthalmia were decreased for women with intake levels in the highest quartile of folate (0.56, 95% confidence interval [CI] 0.32–0.98), magnesium (0.42, 95% CI 0.22–0.82), and vitamin E (0.50, 95% CI 0.29–0.89). Among women not reporting vitamin supplement use, the odds were significantly increased for beta‐carotene (2.5, 95% CI 1.10–5.68) and decreased for retinol (0.37, 95% CI 0.19–0.73).

Conclusions

In this expanded analysis, we observed associations for a few nutrients, specifically forms of vitamin A. However, the heterogeneity of results by form and vitamin use necessitates further inquiry.
Quantitative determination of meloxicam in dog plasma by high performance liquid chromatography–tandem mass spectrometry and its application in a pharmacokinetic study
Authors: Tian Yongzhi , Wu Xiao , Zhang Mingjie , Zhao Longshan , Xiong Zhili , Qin Feng
Published: March 2018

A rapid, selective and sensitive high‐performance liquid chromatography–tandem mass spectrometry (HPLC‐MS/MS) method was developed to determine meloxicam in beagle dog plasma. Sample pretreatment involved a one‐step protein precipitation with methanol of 0.1 mL plasma. Analysis was performed on a Venusil ASB‐C18 column with mobile phase consisting of methanol–water (containing 0.1% formic acid) (75:25, v/v). The detection was performed on a triple quadrupole tandem mass spectrometer by multiple reaction monitoring mode via electrospray ionization source. Each plasma sample was chromatographed within 4.1 min. The linear calibration curves for meloxicam was obtained in the concentration range of 10.3–4.12 × 103 ng/mL (r ≥ 0.99). The intra‐ and inter‐day precisions (relative standard deviation) were ≤ 15%, and accuracy (relative error) was within ±7.3%. The method herein described was fully validated and successfully applied to the pharmacokinetic study of meloxicam tablets in beagle dog.
A single liquid chromatography–quadrupole time‐of‐flight mass spectrometric method for the quantification of total antibody, antibody‐conjugated drug and free payload of antibody–drug conjugates
Authors: Byeon Jin‐Ju , Park Min‐Ho , Shin Seok‐Ho , Lee Byeong ill , Park Yuri , Choi Jangmi , Kim Nahye , Kang Yeonjae , Shin Young G.
Published: March 2018

A single hybrid affinity‐captured‐LC‐TOF‐MS/MS method was developed and applied for the quantification of total antibody, antibody conjugated drug and free payload of antibody drug conjugate (ADC). Adcetris®, a valine–citrulline monomethyl auristatin E conjugated ADC, was used as a model ADC compound. A quadratic regression (weighted 1/concentration) was used to fit calibration curves over the concentration range 30.65–613.00 ng/mL with an equation y = ax2 + bx + c for the antibody‐conjugated drug of Adcetris®. The qualification run met the acceptance criteria of ±25% accuracy and precision values for quality control samples. For the analysis of total antibody, a signature peptide (TTPPVLDSDGSFFLYSK, molecular weight 1874) was used after affinity capture using magnetic beads and on‐bead trypsin digestion. A quadratic regression (weighted 1/concentration) was used to fit calibration curves over the concentration range 5.00–100.00 μg/mL with an equation y = ax2 + bx + c for total antibody. For free payload analysis of monomethyl auristatin E, a protein precipitation method followed by LC‐TOF‐MS/MS analysis was used. A quadratic regression (weighted 1/concentration) was used to fit calibration curves over the concentration range 1.01–2200 ng/mL with an equation y = ax2 + bx + c for free payload. Pharmacokinetic study samples and in vitro stability samples in rat were successfully analyzed by this a hybrid affinity‐captured‐LC‐TOF‐MS/MS method. This single platform method is a useful complementary method for the pharmacokinetics study of ADC with valine–citrulline linker at the early drug discovery stage.
Improving the Activity and Stability of Human Galactokinase for Therapeutic and Biotechnological Applications
Authors: McAuley Margaret , Mesa‐Torres Noel , McFall Aisling , Morris Sarah , Huang Meilan , Pey Angel L. , Timson David J.
Published: March 2018

Galactokinase catalyses the site‐ and stereospecific phosphorylation of α‐d‐galactose. As such it has attracted interest as a biocatalyst for the introduction of phosphate groups into monosaccharides. However, attempts to broaden the substrate range of human galactokinase have generally resulted in substantially reduced activity. The enzyme also has biotechnological potential in enzyme replacement therapy (ERT) for type II galactosaemia. The return‐to‐consensus approach can be used to identify residues that can be altered to increase protein stability and enzyme activity. This approach identified six residues of potential interest in human galactokinase. Some of the single consensus variants (M60V, D268E, A334S and G373S) increased the catalytic turnover of the enzyme, but none resulted in improved stability. When all six changes were introduced into the protein (M60V/M180V/D268E/A334S/R366Q/G373S), thermal stability was increased. Molecular dynamics simulations suggested that these changes altered the protein's conformation at key sites. The number of salt bridges and hydrogen bonds was also increased. Combining the six consensus variations with Y379W (a variant with greater substrate promiscuity) increased the stability of this variant and its turnover towards some substrates. Thus, the six consensus variants can be used to stabilise catalytically interesting variants of human galactokinase and might also be useful if the protein were to be used in ERT.
Invasive tracheobronchial aspergillosis developed during radioimmunotherapy for malignant lymphoma
Authors: Sato Shuku , Tamai Yotaro , Sugimoto Hideyasu , Watanabe Shinji , Kumagae Tomohiro , Kannbe Emiko , Tanaka Eri
Published: March 2018

Key Clinical Message

Invasive pulmonary aspergillosis (IPA) often occurs during the treatment of malignant lymphoma. However, invasive tracheobronchial aspergillosis (ITBA) is a rare form of IPA. Particularly, due to the decrease in immunity associated with chemotherapy, it is difficult to diagnose ITBA only by CT imaging and serological findings. Pathologic diagnosis by bronchoscopy is important.
Synthesis and Characterization of the Perthiatriarylmethyl Radical and Its Dendritic Derivatives with High Sensitivity and Selectivity to Superoxide Radical
Authors: Tan Xiaoli , Tao Shanqing , Liu Wenbo , Rockenbauer Antal , Villamena Frederick A. , Zweier Jay L. , Song Yuguang , Liu Yangping
Published: March 2018

EPR spectroscopy, coupled with the use of tetrathiatriarylmethyl (TAM) radicals, has been a reliable method to detect the superoxide radical (O2.−). However, the specificity and biocompatibility of TAM radicals need to be further improved. Although derivatization may overcome the drawbacks of current TAM radicals, esterification or amidation through the carboxylic groups greatly changes their redox properties and makes them inert to O2.−. Herein, the synthesis of a perthiatriarylmethyl (PST) radical and its dendritic derivatives, PST‐TA and PST‐NA, in which PST is covalently linked with dendrons containing three (TA) and nine (NA) carboxylic acids, respectively. The results show that PST rapidly reacts with O2.− to yield a unique quinone methide product. Dendritic modification of PST slightly decreases the reactivities of PST‐TA and PST‐NA, but notably increases their biostability toward various oxidoreductants. The detection limit of PST‐NA to O2.− was estimated to be 2.1 nm min−1 over 60 min of detection. Importantly, PST‐NA shows threefold higher sensitivity to O2.− in the presence and absence of ascorbic acid than that of the classic spin‐trapping technique. In addition, the application of PST‐NA to detect extracellular O2.− generation in stimulated RAW 264.7 macrophages was also explored. This study demonstrates that PST‐NA has great potential for specific detection and quantitation of O2.− in extracellular sites.
Protecting‐Group‐Free Amidation of Amino Acids using Lewis Acid Catalysts
Authors: Sabatini Marco T. , Karaluka Valerija , Lanigan Rachel M. , Boulton Lee T. , Badland Matthew , Sheppard Tom D.
Published: March 2018

Amidation of unprotected amino acids has been investigated using a variety of ‘classical“ coupling reagents, stoichiometric or catalytic group(IV) metal salts, and boron Lewis acids. The scope of the reaction was explored through the attempted synthesis of amides derived from twenty natural, and several unnatural, amino acids, as well as a wide selection of primary and secondary amines. The study also examines the synthesis of medicinally relevant compounds, and the scalability of this direct amidation approach. Finally, we provide insight into the chemoselectivity observed in these reactions.
Salt‐Free Strategy for the Insertion of CO2 into C−H Bonds: Catalytic Hydroxymethylation of Alkynes
Authors: Wendling Timo , Risto Eugen , Krause Thilo , Gooßen Lukas J.
Published: March 2018

A copper(I) catalyst enables the insertion of carbon dioxide into alkyne C−H bonds by using a suitable organic base with which hydrogenation of the resulting carboxylate salt with regeneration of the base becomes thermodynamically feasible. In the presence of catalytic copper(I) chloride/4,7‐diphenyl‐1,10‐phenanthroline, polymer‐bound triphenylphosphine, and 2,2,6,6‐tetramethylpiperidine as the base, terminal alkynes undergo carboxylation at 15 bar CO2 and room temperature. After filtration, the ammonium alkynecarboxylate can be hydrogenated to the primary alcohol and water at a rhodium/molybdenum catalyst, regenerating the amine base. This demonstrates the feasibility of a salt‐free overall process, in which carbon dioxide serves as a C1 building block in a C−H functionalization.
Catalytic [1,3] O‐to‐C Rearrangement: Rapid Access to Bridged Bicyclic Systems
Authors: Zhang Jiantao , Liao Zhehui , Chen Lianfen , Jiang Huanfeng , Zhu Shifa
Published: March 2018

A catalytic [1,3] O‐to‐C rearrangement from enyne‐ethers was developed for the rapid synthesis of diverse bridged bicyclic systems. In this reaction, a vinyl oxonium intermediate, generated in situ from enyne‐ether, was the precursor for the [1,3] O‐to‐C rearrangement. This versatile protocol represents the first example of catalytic [1,3] O‐to‐C rearrangement based on ring‐expansion strategy, enabling efficient access to bridged bicyclic scaffolds.
Encapsulation Efficiency and Release Behavior of Fat Microcapsules with Lipophilic Emulsifiers
Authors: Scholz Rebecca , Davico Luca , Jakobi Victoria , Kareth Sabine , Rosenhahn Axel , Weidner Eckhard
Published: March 2018

Verkapselte Systeme sind vor allem für die Lebensmittelindustrie und Pharmazie von großer Bedeutung. Die Herausforderung bei der Herstellung von Mikrokapseln liegt darin, eine möglichst große Menge an verkapseltem Material zu erreichen und das Freisetzungsverhalten des verkapselten Materials zu kontrollieren. In dieser Studie werden zwei lipophile Emulgatoren und deren Einfluss auf die Verkapselungseffizienz sowie das Freisetzungsverhalten der erhaltenen Mikrokapseln, bestehend aus einem Hartfett und einer Salzlösung, hinsichtlich der Freisetzung in wässriger Umgebung gegenübergestellt.
Why names matter for women: MINOCA/INOCA (myocardial infarction/ischemia and no obstructive coronary artery disease)
Authors: Pacheco Claudio Christine , Quesada Odayme , Pepine Carl J. , Noel Bairey Merz C.
Published: March 2018

The syndromes of myocardial infarction/myocardial ischemia with No Obstructive Coronary Artery Disease (MINOCA/INOCA) are increasingly evident. A majority of these patients have coronary microvascular dysfunction. These patients have elevated risk for a cardiovascular event (including acute coronary syndrome, myocardial infarction, stroke, and repeated cardiovascular procedures) and appear to be at higher risk for development of heart failure with preserved ejection fraction. Terminology such as coronary artery disease or coronary heart disease is often synonymous with obstructive atherosclerosis in the clinician's mind, leaving one at a loss to recognize or explain the phenomenon of MINOCA and INOCA with elevated risk. We review the available literature regarding stable and unstable ischemic heart disease that suggests that use of the ischemic heart disease (IHD) terminology matters for women, and should facilitate recognition of risk to provide potential treatment targets and optimized health.
Synthesis and Biological Evaluation of Imidazole‐Bearing α‐Phosphonocarboxylates as Inhibitors of Rab Geranylgeranyl Transferase (RGGT)
Authors: Joachimiak Łukasz , Marchwicka Aleksandra , Gendaszewska‐Darmach Edyta , Błażewska Katarzyna M.
Published: March 2018

Rab geranylgeranyl transferase (RGGT) is an interesting therapeutic target, as it ensures proper functioning of Rab GTPases, a class of enzymes responsible for the regulation of vesicle trafficking. Relying on our previous studies, we synthesized a set of new α‐phosphonocarboxylic acids as potential RGGT inhibitors, with emphasis on the elaboration of imidazole‐containing analogues. We identified two compounds with activity similar to that of previously reported RGGT inhibitors, showing structural similarity to imidazo[1,2‐a]pyridine‐containing analogues in terms of their substitution pattern. Interestingly, analogues of the N‐series, derived from another phosphonocarboxylate RGGT inhibitor, 2‐fluoro‐3‐(1H‐imidazol‐1‐yl)‐2‐phosphonopropanoic acid, turned out to be inactive in our model, indicating that an additional substituent localized at positions C2 or C4 of the imidazole ring, may adversely affect the potency against the targeted enzyme.
Ionic Liquid Immobilized on Graphene‐Oxide‐Containing Palladium Metal Ions as an Efficient Catalyst for the Alkoxy, Amino, and Phenoxy Carbonylation Reactions
Authors: Gaikwad Vinayak V. , Saptal Vitthal B. , Harada Kei , Sasaki Takehiko , Nishio‐Hamane Daisuke , Bhanage Bhalchandra M.
Published: March 2018

The Immobilization of homogeneous metal catalysts onto the solid surface is an important challenge in the field of catalysis because these types of catalysts provide the homogeneous nature as well as reusability of catalysts. In this report, novel Palladium ion containing ionic liquid immobilized onto graphene oxide (Pd@GOIL) and characterized using various analytical techniques like FT‐IR, XPS, TGA, SEM, TEM, BET and EXAFS analysis. This synthesized material acts as a highly efficient catalyst for the alkoxycarbonylation, aminocarbonylation and phenoxycarbonylation reactions from easily available aryl iodides. Effect of various reaction parameters like CO pressure, base, solvent, the effect of time and temperature using Pd@GOIL catalyst were examined. This catalyst also tolerates the wide variety of substrates with the effective electronic factor. Specifically, this catalyst shows excellent catalytic performance towards the esterification and amidation without the need of any ligands, co‐catalysts and additives. Additionally, the catalyst shows superior recyclability up to eight recycle runs without discernible activity and selectivity deterioration.
Visual customization: Diversity in color preferences in the automotive interior and implications for interior design
Authors: Wagner Alexa‐Sibylla , Kilincsoy Ümit , Vink Peter
Published: March 2018

Evolving multimodal mobility needs influences established human–product relationships and requires a deeper insight into color preferences for car interiors. Hence, a study was conducted in which 204 members of a web contest created 1,265 designs. After a peer‐evaluation process, 53 most‐appreciated and 34 least‐preferred interior color compositions were identified and compared to identify patterns in color choices. Besides, visual lightweight design by layering of large interior components such as the seat, a modest use of color and patterns accompanied by repetition and the framing of the entire interior to create a feeling of spaciousness were found. Additionally, differences in the type of color between most and least favored color designs were found. Brown and beige occur more frequently among the top‐ than the worst‐rated designs. Larger surfaces are favored in lighter hues and smaller components in darker hues.
Method Evaluations for Adsorption Free Energy Calculations at the Solid/Water Interface through Metadynamics, Umbrella Sampling, and Jarzynski's Equality
Authors: Wei Qichao , Zhao Weilong , Yang Yang , Cui Beiliang , Xu Zhijun , Yang Xiaoning
Published: March 2018

The front cover artwork is provided by the groups of Prof. Zhijun Xu at Nanjing Tech University and Prof. Yang Yang at Haverford College. The image shows the surface‐bound water layers playing a crucial role in determining the accuracy and efficiency of the adsorption free energy calculations, especially at the region close to the surface. Read the full text of the Article at 10.1002/cphc.201701241.
Templated DNA Cross‐Linking: Towards a Non‐Invasive Singlet‐Oxygen‐Based Triggering Method
Authors: De Laet Nathalie , Llamas Eva M. , Madder Annemieke
Published: March 2018

Singlet‐oxygen‐induced DNA interstrand cross‐linking was achieved at intracellularly relevant concentrations using a templated reaction setup. The target oligonucleotide serves as a template ensuring proximity between a “furan warhead”‐containing probe and an activator probe containing a photosensitizer able to generate 1O2. Visible light irradiation of this self‐activating assembly allows us to achieve highly selective interstrand crosslinking at concentration levels relevant for intracellular applications.
Simple MOS‐based circuit designed to show pinched hysteresis behavior
Authors: Maundy Brent , Elwakil Ahmed , Psychalinos Costas
Published: March 2018

We propose and validate a simple 3‐transistor MOS circuit that shows an all‐positive pinched hysteresis behavior. Complete analysis of the circuit is provided along with experimental results using a commercial CMOS transistor array.
On the development of a deployable cold plasma endoscope
Authors: Winter Jörn , Nishime Thalita M.C. , Glitsch Sven , Lühder Heike , Weltmann Klaus‐Dieter
Published: March 2018

A novel non‐thermal atmospheric‐pressure plasma jet source for endoscopic application is presented. Specific challenges in the endoscopic plasma source development, such as small dimensions, flexibility, operation in half‐closed cavities, and the avoidance of in‐tube plasma, are addressed. Besides plasma characterization of the jet freely operating in ambient air, special focus is laid on the investigation of in‐cavity operation. In order to avoid saturation of the cavity atmosphere with the feed gas and at the same time allow a distinct jet formation, a second gas with electronegative properties is introduced as shielding gas. Depending on the flow rate ratios between feed gas and the shielding gas, arcing and jet‐to‐glow transition can be suppressed.
Investigation of statistical behaviour of electrical breakdown voltage distribution for nitrogen‐filled diode at 13.3 mbar pressure
Authors: Živanović Emilija N. , Maluckov Čedomir A.
Published: March 2018

The results of statistical analysis of the electrical breakdown voltage distribution in nitrogen are presented in this paper. For obtaining the experimental results, a nitrogen‐filled diode at 13.3 mbar pressure was used. The dynamic method was used for estimating the static breakdown voltage. One‐hundred voltage measurements were carried out for each value of the increase in the voltage rate from 1 up to 10 V/s. Wilcoxon test was used for checking the measurements' randomness for each rate. The experimental distribution functions are fitted with the three‐parameter Weibull distribution function. The coefficients of the Weibull distribution are also estimated.
Endoscopic ultrasound guided brush/fine‐needle aspiration cytology: A 15‐month study
Authors: Tummidi Santosh , Kothari Kanchan , Sathe Pragati , Agnihotri Mona , Fernandes Gwendolyn , Naik Leena , Jain Aleena , Chaturvedi Rachana
Published: March 2018

Background

Endoscopic ultrasound‐guided fine‐needle aspiration (EUS‐FNA) has become increasingly popular for the diagnosis and staging of gastrointestinal diseases and peri‐gastrointestinal lesions. The application of FNA/Brush has dramatically expanded the clinical utility of EUS.

Aims and objective

To evaluate the diagnostic accuracy, study the spectrum of lesions encountered in EUS‐FNAC/brush cytology of gastrointestinal and peri‐gastrointestinal lesions.

Materials and methods

Total of 124 patients during the period from August 2015 to November 2016 was included in the study. Routine staining was done.

Results

A total of 124 cases were studied with 86% (107 cases) being satisfactory for evaluation. M:F ratio was 1:1.03, mean age of 50.5 years. The most common site was common bile duct (CBD) (37%) followed by lymph node (21%), pancreas (17.7%), esophagus (17%), stomach (3.5%), liver (1.8%), gallbladder (1%), and spleen (1%). In total, 53.4% lesions were benign, in 6.5% atypical cells were seen, 12.1% were suspicious for malignancy, and 28% cases were positive for malignancy. Follow‐up was available in 102 cases with cyto‐histopathological concordance rate of 90%.

Conclusion

EUS‐FNA/Brush is a reliable, sensitive, specific and minimally invasive way to establish a diagnosis. It can be utilized as a pre‐operative procedure for the management of many intra‐abdominal lesions and prevent unnecessary invasive procedures.
Dietary protein supplementation and its consequences for intake, digestion, and physical activity of a carnivorous marsupial, Sminthopsis crassicaudata
Authors: Yuan Lihong , Wilder Shawn , Raubenheimer David , Simpson Stephen J. , Shaw Michelle , McAllan Bronwyn M.
Published: March 2018

Diet regulation behavior can mediate the consequences of imbalanced diets for animal well‐being, particularly for captive species that have little dietary choice. Dasyurids (carnivorous marsupials) are of conservation concern in Australia, and many species are in captive breeding programmes. However, their nutrient targets and dietary regulation behaviors are poorly understood, a limitation that may decrease the breeding success and well‐being of captive animals. We tested how dietary protein content influenced the intake and utilization of nutrients, physical activity, and body mass of fat‐tailed dunnarts Sminthopsis crassicaudata. Twelve adult dunnarts from six sibling pairs (one female and one male per pair) were provided ad libitum access to three diets in a repeated measures design: cat food, cat food supplemented with raw lean beef (1:1), and cat food supplemented with cooked lean beef (1:1). Food intake, activity level, and fecal output were measured daily. Dunnarts significantly decreased food intake, increased protein digestion, and physical activity, but body mass was unchanged when on the high‐protein diet compared to the normal cat food diet. These observations suggest a capacity of dunnarts to maintain constant body mass using a dynamic balance of feeding, digestion, and activity. We also found a significant effect of family, with differences between families as large as the difference between the diet treatments, suggesting a genetic component to diet selection. The nutrient regulation responses of dunnarts to high‐protein diets and the strong family effects provide important messages for the management of populations of small carnivores, including the aspects of dietary manipulation and conservation of genetic diversity.
The Diphosphorus Complex [Cp2Cr2(CO)4(η2‐P2)] as a Building Block in the Coordination Chemistry of Silver
Authors: Elsayed Moussa Mehdi , Welsch Stephan , Gregoriades Laurence J. , Balázs Gábor , Seidl Michael , Scheer Manfred
Published: March 2018

The reaction of the tetrahedral diphosphorus complex [Cp2Cr2(CO)4(η2‐P2)] (Cp = C5H5) (2) with Ag[Al{OC(CF3)3}4] (AgTEF) (3) leads to the formation of the AgI dimer [Ag2(η2‐2) (η1‐2)(η1:η1‐2)2][TEF]2 (5). This dimer can be used as a suitable precursor for the synthesis of the unprecedented 1D organometallic‐organic hybrid polymer [Ag2(η1‐2)2(η1:η1‐2)2{µ,η1:η1‐(C8H4N2)}]n[TEF]2n (8) upon its reaction with 1,4‐dicyanobenzene (7). The driving force for this supramolecular assembly reaction is supported by DFT calculations.
Hydrogen Atom vs. Hydride Transfer in Cytochrome P450 Oxidations: A Combined Mass Spectrometry and Computational Study
Authors: Cantú Reinhard Fabián G. , Fornarini Simonetta , Crestoni Maria Elisa , de Visser Sam P.
Published: March 2018

Biomimetic models of short‐lived enzymatic reaction intermediates can give useful insight into the properties and coordination chemistry of transition metal complexes. In this work, we investigate a high‐valent iron(IV)‐oxo porphyrin cation radical complex, namely [FeIV(O)(TPFPP+·)]+, for which TPFPP is the dianion of 5,10,15,20‐tetrakis(pentafluorophenyl) porphyrin. The [FeIV(O)(TPFPP+·)]+ ion was studied by ion‐molecule reactions in a Fourier transform ion cyclotron resonance mass spectrometer through reactivities with 1,3,5‐cycloheptatriene, 1,3‐cyclohexadiene and toluene. The different substrates give dramatic changes in reaction mechanism and efficiencies, whereby cycloheptatriene leads to hydride transfer, whereas cyclohexadiene and toluene react through hydrogen atom abstraction. Detailed computational studies point to major differences in ionization energy, as well as C–H bond energies of the substrates that influence the hydrogen atom abstraction vs. electron transfer pathways. The various variables that determine the pathways for hydride transfer vs. hydrogen atom transfer are elucidated and discussed.
Development of Photoactivatable Nitroxyl (HNO) Donors Incorporating the (3‐Hydroxy‐2‐naphthalenyl)methyl Phototrigger
Authors: Zhou Yang , Cink Ruth B. , Fejedelem Zachary A. , Cather Simpson M. , Seed Alexander J. , Sampson Paul , Brasch Nicola E.
Published: March 2018

A new family of photoactivatable HNO donors of general structure RSO2NHO‐PT [where PT represents the (3‐hydroxy‐2‐naphthalenyl)methyl (3,2‐HMN) phototrigger] has been developed, which rapidly releases HNO. Photogeneration of HNO was demonstrated using the vitamin B12 derivative aquacobalamin as a trapping agent. The amount of sulfonate RSO2– produced was essentially the same as the amount of HNO released upon photolysis, providing a convenient method to indirectly quantify HNO release. Two competing pathways were also observed; a pathway involving O–N bond cleavage leading to release of a sulfonamide, and a pathway resulting in release of the parent Nhydroxysulfonamide RSO2NHOH (for HNO donors with Me‐ and Ph‐containing leaving groups only). Up to approximately 70 % of the HNO‐generating pathway was observed with the CF3‐containing leaving group, with HNO generation favored for small percentages of aqueous buffer in the acetonitrile/pH 7.00 phosphate buffer solvent mixture. Characterization of the photoproducts obtained from steady‐state irradiation by NMR spectroscopy showed that the desired HNO‐generating pathway was less favored for HNO donors with Me‐ and Ph‐containing leaving groups compared to the CF3‐containing leaving group, suggesting that the excellent CF3‐containing leaving group promotes HNO generation.
Transition Metal‐Free sp3 C–H Functionalization of Arylacetic Acids for the Synthesis of 1,3,5‐Triazines
Authors: Pardeshi Sachin D. , Sathe Pratima A. , Pawar Balu V. , Vadagaonkar Kamlesh S. , Chaskar Atul C.
Published: March 2018

A one‐pot simple, efficient and practically viable protocol for the synthesis of substituted 1,3,5‐triazines has been reported from arylacetic acids and benzamidine hydrochloride. In addition, we demonstrated first transition metal‐free conversion of phenylacetic acid to benzaldehyde which on condensation with two equivalents of benzamidine hydrochloride offered 2,4,6‐trisubstituted 1,3,5‐triazines. This protocol is environmentally benign and economically viable which makes it feasible for gram scale synthesis.
Regio‐, Diastereo‐ and Enantioselective Synthesis of Piperidines with Three Stereogenic Centers from Isoxazolinones by Palladium/Iridium Relay Catalysis
Authors: Rieckhoff Stefan , Frey Wolfgang , Peters René
Published: March 2018

Piperidines are currently the most frequently used heterocycles in the development of new pharmaceuticals. A straightforward efficient stereo‐ and regioselective asymmetric access to chiral polysubstituted piperidines creating multiple stereogenic centers is often still a challenge. Herein we report a rapid approach towards trisubstituted piperidines, which is notable for the use of a readily accessible isoxazolinone starting material and for creating three stereocenters in a single step. 3,4‐Dihydropyridines, which are probably formed by a Pd‐catalyzed cycle via a decarboxylative oxidative addition of the substrates, appear to be useful intermediates in this relay catalysis, in which Ir acts as enantioselective hydrogenation catalyst to form the valuable chiral heterocycles under mild conditions.
Language mapping with navigated transcranial magnetic stimulation in pediatric and adult patients undergoing epilepsy surgery: Comparison with extraoperative direct cortical stimulation
Authors: Lehtinen Henri , Mäkelä Jyrki P. , Mäkelä Teemu , Lioumis Pantelis , Metsähonkala Liisa , Hokkanen Laura , Wilenius Juha , Gaily Eija
Published: March 2018

Objective

Navigated transcranial magnetic stimulation (nTMS) is becoming increasingly popular in noninvasive preoperative language mapping, as its results correlate well enough with those obtained by direct cortical stimulation (DCS) during awake surgery in adult patients with tumor. Reports in the context of epilepsy surgery or extraoperative DCS in adults are, however, sparse, and validation of nTMS with DCS in children is lacking. Furthermore, little is known about the risk of inducing epileptic seizures with nTMS in pediatric epilepsy patients. We provide the largest validation study to date in an epilepsy surgery population.

Methods

We compared language mapping with nTMS and extraoperative DCS in 20 epilepsy surgery patients (age range 9‐32 years; 14 children and adolescents).

Results

In comparison with DCS, sensitivity of nTMS was 68%, specificity 76%, positive predictive value 27%, and negative predictive value 95%. Age, location of ictal‐onset zone near or within DCS‐mapped language areas or severity of cognitive deficits had no significant effect on these values. None of our patients had seizures during nTMS.

Significance

Our study suggests that nTMS language mapping is clinically useful and safe in epilepsy surgery patients, including school‐aged children and patients with extensive cognitive dysfunction. Similar to in tumor surgery, mapping results in the frontal region are most reliable. False negative findings may be slightly more likely in epilepsy than in tumor surgery patients. Mapping results should always be verified by other methods in individual patients.
A rational H∞‐norm–based approach for the optimal design of seismically excited reinforced concrete frames
Authors: Venini P. , Ceresa P.
Published: March 2018

A rational approach is presented for minimizing the dynamic response of reinforced concrete framed structures forced by a seismic base acceleration. Reference is made to EC8 regulations, but the presented approach may in principle be applied to structures ruled by any regulation code. Governing equations are set in the frequency domain (and not in the periods domain as usual) so as to enable the adoption of sound approaches for analysis and design of dynamic structures that are typical of automatics. Among these, a novel usage of the H∞‐norm concept is proposed that determines a rational design approach capable to minimize the structural response with reference to any quantity of engineering interest, eg, the overall compliance and the displacement of a specific point or the interstorey drift. A numerical investigation on a 6‐storey 3‐bay frame is performed, and relevant analysis and design results are presented in much detail to validate the theoretical framework.
Triassic alkaline magmatism and mineralization in the Xiong'ershan area, East Qinling, China
Authors: Tang Li , Zhang Shou‐Ting , Yang Fan , Santosh M. , Li Jun‐Jun , Kim Sung Won , Hu Xin‐Kai , Zhao Yu , Cao Hua‐Wen
Published: March 2018

The Qinling orogenic belt is a complex subduction–accretion–collision orogen that welded the North China Craton and the Yangtze Craton during the final continental collision in the Triassic. The Xiong'ershan area, located in east Qinling, exposes a typical Triassic syenite pluton and several contemporaneous Mo, Au, and Cu deposits. The aegirine–augite syenites and syenites from the Mogou pluton are characterized by alkalic to peralkalic (total alkali Na2O + K2O = 13.95–14.63 wt.%, CaO = 0.06–2.87 wt.%), and shoshonitic features (K2O = 11.86–14.34 wt.%). Zircon LA–ICP–MS U–Pb dating of the aegirine–augite syenite and syenite yield emplacement ages of 232.5 ± 0.6 and 221.8 ± 0.7 Ma, indicating multiple pulses of magmatism. Evidence from zircon Hf isotopes; occurrence of mafic microgranular enclaves; heterogeneous peralkaline composition; and wide ranges of MgO, Ni, and other trace elements suggest that the parental magma was mainly sourced from partial melting of Archean to Paleoproterozoic crustal sources, mixed with juvenile mantle‐derived mafic magmas. The Mogou pluton was probably emplaced in the tectonic transition from syn‐collision to post‐collision settings and accompanying slab break‐off process, from the commencement of collision at approximately 245 Ma and post‐collisional extension at approximately 210 Ma. Gold, molybdenum, and copper deposits formed during the interval of 255–208 Ma, and the close temporal and spatial relationship between these Triassic polymetallic deposits and the Mogou alkaline pluton invokes a genetic linkage. The heat source for magmatism and related metallogeny is correlated to a hot upwelling asthenospheric mantle that caused partial melting of the Archean to Paleoproterozoic crustal basement, resulting in magma mixing between the two end‐members.
Petrogenesis of two stages of Cretaceous granites in south‐west Fujian Province: Implications for the tectonic transition of South‐east China
Authors: Zhao Xilin , Yu Shengyao , Jiang Yang , Mao Jianren , Yu Minggang , Chen Zhihong , Xing Guangfu
Published: March 2018

Zircon U–Pb data indicate that Cretaceous magmatism in Fujian Province occurred in two pulses, with the Xiyang, Yangshan, Wuci, Dehua, Juzhou, and Xiandu plutons emplaced between 147 ± 1 and 126 ± 1 Ma and the Hutou and Guangqiao plutons emplaced at 109 ± 1 Ma. Combining these previously published ages with the new data obtained during this study indicates that the magmatism in the study area occurred in two distinct stages at 145–125 and 110–100 Ma, both have I‐type characteristics. The earlier I‐type granites are characterized by relatively high concentrations of SiO2 (mean = 75.73 wt.%) and low concentrations of MgO (mean of 0.21 wt.%) and are metaluminous to weakly peraluminous (mean A/CNK = 1.03). They contain relatively high total rare‐earth element (ΣREE) concentrations (mean of 139.3 ppm) with well‐developed Eu anomalies and are relatively enriched in the large‐ion lithophile elements (LILE) and the light REE (LREE) but depleted in Ba, Sr, P, Ti, Nb, and Ta. In contrast, the younger I‐type granites contain lower concentrations of SiO2 (mean of 67.63 wt.%), higher concentrations of MgO (mean of 1.47 wt.%), and are metaluminous to weakly peraluminous (mean A/CNK = 0.96). They also have moderate REE values (mean of 150.26 ppm) without significant Eu anomalies and are relatively enriched in LREE, Rb, Th, U, K, Sr, and Pb and depleted in Nb, Ta, P, Ti, Y, and Yb. The two‐stage Nd model ages (T2DM) of Cretaceous granites are 1.46 to 1.88 Ga (mean of 1.57 Ga) and 1.16–1.60 Ga (mean of 1.36 Ga), respectively. The two‐stage Hf model ages (T2DM) of Cretaceous granites are 1.19–1.82 Ga (mean of 1.54 Ga) and 0.46–1.20 Ga (mean of 0.91 Ga), respectively. It is likely that the earlier I‐type granites were derived from magmas generated by the partial melting of Mesoproterozoic metabasaltic material, whereas the later I‐type granites were derived from magmas generated by partial melting of a mixed lithology containing Mesoproterozoic to Neoproterozoic metabasaltic to metatonalitic rocks that were underplated by medium‐ to high‐K basaltic magmas. A geological comparison between south‐western Fujian Province and adjacent areas indicates that the earlier I‐type granites were emplaced in a compressional environment associated with the subduction of the paleo‐Pacific Plate at 145–125 Ma. In contrast, the later I‐type plutons are associated with intraplate extension accompanied by the post‐subduction slab roll‐back of the paleo‐Pacific Plate. The two magmatic stages represent a transition from compressional to intraplate extensional tectonics between 125 and 110 Ma, with mantle‐derived material playing a crucial role in the formation of the I‐type granites.
Brain dynamics in ASD during movie‐watching show idiosyncratic functional integration and segregation
Authors: Bolton Thomas A.W. , Jochaut Delphine , Giraud Anne‐Lise , Van De Ville Dimitri
Published: March 2018

To refine our understanding of autism spectrum disorders (ASD), studies of the brain in dynamic, multimodal and ecological experimental settings are required. One way to achieve this is to compare the neural responses of ASD and typically developing (TD) individuals when viewing a naturalistic movie, but the temporal complexity of the stimulus hampers this task, and the presence of intrinsic functional connectivity (FC) may overshadow movie‐driven fluctuations. Here, we detected inter‐subject functional correlation (ISFC) transients to disentangle movie‐induced functional changes from underlying resting‐state activity while probing FC dynamically. When considering the number of significant ISFC excursions triggered by the movie across the brain, connections between remote functional modules were more heterogeneously engaged in the ASD population. Dynamically tracking the temporal profiles of those ISFC changes and tying them to specific movie subparts, this idiosyncrasy in ASD responses was then shown to involve functional integration and segregation mechanisms such as response inhibition, background suppression, or multisensory integration, while low‐level visual processing was spared. Through the application of a new framework for the study of dynamic experimental paradigms, our results reveal a temporally localized idiosyncrasy in ASD responses, specific to short‐lived episodes of long‐range functional interplays.
A single blood test adjusted for different liver fibrosis targets improves fibrosis staging and especially cirrhosis diagnosis
Authors: Calès Paul , Boursier Jérôme , Oberti Frédéric , Moal Valérie , Fouchard Hubert Isabelle , Bertrais Sandrine , Hunault Gilles , Rousselet Marie Christine ,   multicentric groups (SNIFF, ANRS HC 23)
Published: March 2018

Fibrosis blood tests are usually developed using significant fibrosis, which is a unique diagnostic target; however, these tests are employed for other diagnostic targets, such as cirrhosis. We aimed to improve fibrosis staging accuracy by simultaneously targeting biomarkers for several diagnostic targets. A total of 3,809 patients were included, comprising 1,012 individuals with chronic hepatitis C (CHC) into a derivation population and 2,797 individuals into validation populations of different etiologies (CHC, chronic hepatitis B, human immunodeficiency virus/CHC, nonalcoholic fatty liver disease, alcohol) using Metavir fibrosis stages as reference. FibroMeter biomarkers were targeted for different fibrosis‐stage combinations into classical scores by logistic regression. Independent scores were combined into a single score reflecting Metavir stages by linear regression and called Multi‐FibroMeter Version Second Generation (V2G). The primary objective was to combine the advantages of a test targeted for significant fibrosis (FibroMeterV2G) with those of a test targeted for cirrhosis (CirrhoMeterV2G). In the derivation CHC population, we first compared Multi‐FibroMeterV2G to FibroMeterV2G and observed significant increases in the cirrhosis area under the receiver operating characteristic curve (AUROC), Obuchowski index (reflecting all fibrosis‐stage AUROCs), and classification metric (six classes expressed as a correctly classified percentage) and a nonsignificant increase in significant fibrosis AUROC. Thereafter, we compared it to CirroMeterV2G and observed a nonsignificant increase in the cirrhosis AUROC. In all 3,809 patients, respective accuracies for Multi‐FibroMeterV2G and FibroMeterV2G were the following: cirrhosis AUROC, 0.906 versus 0.878 (P < 0.001; versus CirroMeterV2G, 0.897, P = 0.014); Obuchowski index, 0.795 versus 0.791 (P = 0.059); classification, 86.0% versus 82.1% (P < 0.001); significant fibrosis AUROC, 0.833 versus 0.832 (P = 0.366). Multi‐FibroMeterV2G had the highest correlation with the area of portoseptal fibrosis and the highest reproducibility over time. Correct classification rates of Multi‐FibroMeter with hyaluronate (V2G, 86.0%) or without (V3G, 86.1%) did not differ (P = 0.938). Conclusion: Multitargeting biomarkers significantly improves fibrosis staging and especially cirrhosis diagnosis compared to classical single‐targeted blood tests. (Hepatology Communications 2018;2:455‐466)
Total Synthesis of the Polyoxygenated Sesquiterpenes Guignarderemophilanes C and D
Authors: Ilazi Agron , Liffert Raphael , Gademann Karl
Published: March 2018

The total syntheses of the neural anti‐inflammatory agents guignarderemophilanes C and D have been accomplished for the first time starting from γ‐hydroxy carvone in 15 and 14 steps, respectively. The presented synthetic route proceeds via a known intermediate, whose synthesis has been elaborated in our group in the course of the total synthesis of the sesquiterpenoid periconianone A. Key for the successful conversion of this intermediate into both targets was finding a suitable strategy to install the 1,2,3‐trihydroxylated A‐ring scaffold. For this purpose, we effectively employed a Mitsunobu inversion, epoxidation, and regioselective epoxide opening sequence, before the bicyclic ring system was constructed by an aldol condensation reaction on a sterically demanding substrate. Our reported synthesis set the stage for SAR studies to prepare even more potent compounds by modification and derivatization of the natural product's scaffold.
Ab initio potential energy surface and vibration–rotation energy levels of germanium dicarbide, GeC2
Authors: Koput Jacek
Published: March 2018

The accurate ground‐state potential energy surface of germanium dicarbide, GeC2, has been determined from ab initio calculations using the coupled‐cluster approach. The core–electron correlation, higher‐order valence‐electron correlation, and scalar relativistic effects were taken into account. The potential energy surface of GeC2 was shown to be extraordinarily flat near the T‐shaped equilibrium configuration. The potential energy barrier to the linear CCGe configuration was predicted to be 1218 cm−1. The vibration–rotation energy levels of some GeC2 isotopologues were calculated using a variational method. The vibrational bending mode ν3 was found to be highly anharmonic, with the fundamental wavenumber being only 58 cm−1. Vibrational progressions due to this mode were predicted for the
,
, and
states of GeC2. © 2018 Wiley Periodicals, Inc.