bluuebunny/crossref_metadata_2025 huggingface dataset:
Selective Conversion of Various Monosaccharaides into Sugar Acids by Additive‐Free Dehydrogenation in Water
Authors: Mollar‐Cuni Andres , Byrne Joseph P. , Borja Pilar , Vicent Cristian , Albrecht Martin , Mata Jose A.
Published: April 2020

Abundant sugars of five and six carbon atoms are promising candidates for the production of valuable platform chemicals. Here, we describe the catalytic dehydrogenation of several pentoses and hexoses into their corresponding sugar acids with the concomitant formation of molecular hydrogen. This biomass transformation is promoted by highly active and selective catalysts based on iridium(III) complexes containing a triazolylidene (trz) as ligand. Monosaccharides are converted into sugar acids in an easy and sustainable manner using only catalyst and water, and in contrast to previously reported procedures, in the absence of any additive. The reaction is therefore very clean, and highly selective, which avoids the tedious purification and product separation. Mechanistic investigations using 1H NMR and UV‐vis spectroscopies and ESI mass spectrometry (ESI‐MS) indicate the formation of an unprecedented diiridium‐hydride as dormant species that correspond to the catalyst resting state.
Lead‐Free, Water‐Stable A3Bi2I9 Perovskites: Crystal Growth and Blue‐Emitting Quantum Dots [A=CH3NH3+, Cs+, and (Rb0.05Cs2.95)+]
Authors: Babu Ramavath , Bhandary Subhrajyoti , Chopra Deepak , Singh Surya Prakash
Published: April 2020

Despite the great success in the increase in the power conversion efficiency of lead halide perovskite solar cells, the toxicity of lead and the unstable nature of the materials are still major concerns for their wider implementation at the industrial level. Herein, large‐size single crystals (SCs) are developed in HI solution by using a temperature lowering method and nanocrystals (NCs) of A3Bi2I9 perovskites [where A=CH3NH3+ (MA)+, Cs+, and (Rb0.05Cs2.95)+] are formed in ethanol (EtOH) and toluene (TOL). The stability of A3Bi2I9 perovskite is investigated by immersing the SCs for 24 h and pellets for 12 h in water. Moreover, the A3Bi2I9 perovskite NCs displays a promising photoluminescence quantum yield of 17.63 % and a long lifetime of 8.20 ns.
Engineering of Laccase CueO for Improved Electron Transfer in Bioelectrocatalysis by Semi‐Rational Design
Authors: Zhang Lingling , Cui Haiyang , Dhoke Gaurao V. , Zou Zhi , Sauer Daniel F. , Davari Mehdi D. , Schwaneberg Ulrich
Published: April 2020

Invited for the cover of this issue is the group of Ulrich Schwaneberg at the Institute of Biotechnology, RWTH‐Aachen University and DWI Lebniz Institute of Interactive Materials. The picture calls for special attention to be paid to the extra Cu binding site of Copper efflux Oxidase (CueO), due to its predominant function in tuning the electrocatalytic kinetics towards oxygen reduction. Read the full text of the article at 10.1002/chem.201905598.
Phenothiazine‐Biaryl‐Containing Fluorescent RGD Peptides
Authors: Ghabraie Elmira , Kemker Isabell , Tonali Nicolo , Ismail Mohamed , Dodero Veronica I. , Sewald Norbert
Published: April 2020

Cyclic RGD peptides are well‐known ligands of integrins. The integrins αVβ3 and α5β1 are involved in angiogenesis, and integrin αVβ3 is abundantly present on cancer cells, thus representing a therapeutic target. Hence, synthetic and biophysical studies continuously are being directed towards the understanding of ligand‐integrin interaction. In this context, the development of versatile synthetic strategies to obtain fluorescent building blocks that can add molecular diversity and modular spectral characteristics while not compromising binding affinity or selectivity is a relevant task. An on‐resin intramolecular Suzuki–Miyaura cross‐coupling (SMC) between l‐ or d‐7‐bromotryptophan (7BrTrp) and a phenothiazine (Ptz) boronic acid affords fluorescent cyclic RGD pseudopeptides, c(RGD(W/w)Ptz). Ring closure by SMC establishes a phenothiazine–indole moiety with axial chirality. An array of eight novel compounds has been synthesized, among them one fluorescent compound with good affinity to integrin αVβ3. The fluorescence properties of the analogues can be efficiently tuned depending on the substituents in Ptz moiety even for fluorescence emission in the visible (red) spectral range.
Experimental and Theoretical Evidence of Spin‐Orbit Heavy Atom on the Light Atom 1H NMR Chemical Shifts Induced through H⋅⋅⋅I− Hydrogen Bond
Authors: Vícha Jan , Švec Petr , Růžičková Zdeňka , Samsonov Maksim A. , Bártová Kateřina , Růžička Aleš , Straka Michal , Dračínský Martin
Published: April 2020

Spin‐orbit (SO) heavy‐atom on the light‐atom (SO‐HALA) effect is the largest relativistic effect caused by a heavy atom on its light‐atom neighbors, leading, for example, to unexpected NMR chemical shifts of 1H, 13C, and 15N nuclei. In this study, a combined experimental and theoretical evidence for the SO‐HALA effect transmitted through hydrogen bond is presented. Solid‐state NMR data for a series of 4‐dimethylaminopyridine salts containing I−, Br− and Cl− counter ions were obtained experimentally and by theoretical calculations. A comparison of the experimental chemical shifts with those calculated by a standard DFT methodology without the SO contribution to the chemical shifts revealed a remarkable error of the calculated proton chemical shift of a hydrogen atom that is in close contact with the iodide anion. The addition of the relativistic SO correction in the calculations significantly improves overall agreement with the experiment and confirms the propagation of the SO‐HALA effect through hydrogen bonds.
Interventional Pharmacoeconomics: A Novel Mechanism for Unlocking Value
Authors: Serritella Anthony V. , Strohbehn Garth W. , Goldstein Daniel A. , Lichter Allen S. , Ratain Mark J.
Published: April 2020

Cancer care’s sustainability is challenged by drug expenditures. In the absence of systemic change, innovation is needed to curtail drug costs. Interventional pharmacoeconomics (IVPE) utilizes clinical research to identify safe, efficacious, cost‐conscious dosing regimens to extract maximum value from expensive therapies. Strategies include de‐escalation of dosage, treatment duration and administration frequency, and substitution with therapeutic alternatives. In this review, we discuss how IVPE strategies have been successfully used and could be implemented going forward.
Higher Dosage of Ciprofloxacin Necessary in Critically Ill Patients: A New Dosing Algorithm Based on Renal Function and Pathogen Susceptibility
Authors: Gieling Emilie M. , Wallenburg Eveline , Frenzel Tim , de Lange Dylan W. , Schouten Jeroen A. , ten Oever Jaap , Kolwijck Eva , Burger David M. , Pickkers Peter , ter Heine Rob , Brüggemann Roger J. M.
Published: April 2020

The objective of the present study was to develop a dosing algorithm for ciprofloxacin based on both renal function and pathogen susceptibility in critically ill patients. In this observational prospective multicenter pharmacokinetic study, a total of 39 adult intensive care unit patients receiving ciprofloxacin were included. On two occasions a total of 531 samples of ciprofloxacin were collected. Renal function is a significant covariate on ciprofloxacin clearance. A dose of 400 mg every 12 hours was sufficient to reach the preestablished target of area under the curve (AUC) in relation to the minimum inhibitory concentration (MIC) (AUC/MIC) > 125 in patients with an estimated glomerular filtration rate (eGFR) < 130 mL/min and an infection caused by a pathogen with an MIC ≤ 0.125 mg/L. For patients with infections caused by pathogens with an MIC ≥ 0.5 mg/L and eGFR> 100 mL/min, doses up to 600 mg four times daily or more were estimated to be required. This study provides a new dosing algorithm for ciprofloxacin in critically ill patients. In order to achieve adequate target attainment, the dosing of ciprofloxacin should be based on renal function and the MIC of the causative pathogen. Higher doses than the standard licensed dose are necessary to obtain target attainment for less susceptible pathogens and patients with high renal clearance. In the setting of impaired renal function, a daily dose of 400 mg (which is currently recommended) will not result in adequate target attainment for less susceptible pathogens.
Intraparotid metastasis from lung adenocarcinoma diagnosed by FNAC—Report of a rare case
Authors: Stephen Norton , Raman Arthy , Kumari Sinku , Dineshbabu Sekar , Gochhait Debasis , Siddaraju Neelaiah
Published: April 2020

Metastasis to the parotid gland accounts for 10%‐16% of parotid malignancies. Head and neck malignancies constitute the major bulk of metastatic lesions to the parotid. The other common primaries include the breast, kidney, lung, and prostate. Metastasis from the lung to the parotid is a relatively rare occurrence whose exact percentage is not known. Though intralymphatic spread into the parotid is known, intraparenchymal spread through hematogenous route is rare. The presence of intraparenchymal spread of lung Adenocarcinoma to the contralateral parotid diagnosed on fine needle aspiration (FNA) makes it a case worth reporting, highlighting the utility of cell block preparation and immunohistochemistry for a precise and early diagnosis.
Ordovician ironstone of the Iberian margin: Coastal upwelling, ocean anoxia and Palaeozoic biodiversity
Authors: Pufahl Peir K. , Squires Alexandra D. , Murphy J. Brendan , Quesada Cecilio , Lokier Stephen W. , Álvaro J. Javier , Hatch Jason
Published: April 2020

Middle to Upper Ordovician ironstone and associated sedimentary rocks of the West Asturian‐Leonese and Cantabrian tectonostratigraphic zones, Spain, provide new information regarding the Palaeozoic Fe cycle and the palaeoceanography of the Rheic Ocean. Examination of drill cores and outcrops indicates the southeastern margin of this narrow seaway was a dynamic continental shelf where upwelling of ferruginous seawater and storm currents controlled lithofacies character. Parasequence composition and stacking relationships suggest ironstone accumulated during marine transgression as accommodation increased from lowstand conditions. Proximal parasequences record aggradation from deep subtidal to shoreface environments. Hummocky cross‐stratified sandstone and organic‐rich siltstone grade upwards into swaley cross‐stratified sandstone and granular Fe‐silicate‐rich ironstone capped by a flooding surface. Distal parasequences were deposited below storm wave base on the distal shelf and are composed of variably bioturbated organic‐rich siltstone with thin Fe‐chlorite and phosphorite layers. These differences in parasequence character define two different ironstone factories where Fe was concentrated and precipitated in sediment. Lithofacies associations support an emerging model for ironstone deposition where coastal upwelling delivered and stimulated the precipitation of Fe within shelf sediment. This notion provides further evidence for the development of intermittent anoxic water masses in an Ordovician ocean that was near the threshold of becoming fully ventilated. This style of Fe delivery probably represents a tipping point in the oxygenation history of the Phanerozoic oceans and is a throwback to the Precambrian when widespread anoxia allowed hydrothermal Fe to concentrate in the global ocean. New data suggest that minor extinction events punctuating the Great Ordovician Biodiversification Event may be traced to these anoxic waters, which in addition to Fe, were also enriched in biologically toxic, redox sensitive trace elements. Conversely, precipitation of upwelling‐related ironstone may have helped sequester these trace elements, providing a negative feedback response that would aid post‐extinction recovery.
Long‐term restoration success of insect herbivore communities in seminatural grasslands: a functional approach
Authors: Neff Felix , Resch M. Carol , Marty Anja , Rolley Jacob D. , Schütz Martin , Risch Anita C. , Gossner Martin M.
Published: April 2020

Seminatural grasslands are important biodiversity hotspots, but they are increasingly degraded by intensive agriculture. Grassland restoration is considered to be promising in halting the ongoing loss of biodiversity, but this evaluation is mostly based on plant communities. Insect herbivores contribute substantially to grassland biodiversity and to the provisioning of a variety of ecosystem functions. However, it is unclear how they respond to different measures that are commonly used to restore seminatural grasslands from intensively used agricultural land. We studied the long‐term success of different restoration techniques, which were originally targeted at reestablishing seminatural grassland plant communities, for herbivorous insect communities on taxonomic as well as functional level. Therefore, we sampled insect communities 22 yr after the establishment of restoration measures. These measures ranged from harvest and removal of biomass to removal of the topsoil layer and subsequent seeding of plant propagules. We found that insect communities in restored grasslands had higher taxonomic and functional diversity compared to intensively managed agricultural grasslands and were more similar in composition to target grasslands. Restoration measures including topsoil removal proved to be more effective, in particular in restoring species characterized by functional traits susceptible to intensive agriculture (e.g., large‐bodied species). Our study shows that long‐term success in the restoration of herbivorous insect communities of seminatural grasslands can be achieved by different restoration measures and that more invasive approaches that involve the removal of the topsoil layer are more effective. We attribute these restoration successes to accompanying changes in the plant community, resulting in bottom‐up control of the herbivore community. Our results are of critical importance for management decisions aiming to restore multi‐trophic communities, their functional composition and consequently the proliferation of ecosystem functions.
Genetic connectivity of lionfish (Pterois volitans) in marine protected areas of the Gulf of Mexico and Caribbean Sea
Authors: Guzmán‐Méndez Irán A. , Rivera‐Madrid Renata , Planes Serge , Boissin Emilie , Cróquer Aldo , Agudo-Adriani Esteban , González‐Gándara Carlos , Perez‐España Horacio , Giro‐Petersen Ana , Luque Jenny , García‐Rivas María del C. , Aguilar‐Espinosa Margarita , Arguelles Jiménez Jimmy , Arias‐González Jesus E.
Published: April 2020

Lionfish (Pterois volitans) have rapidly invaded the tropical Atlantic and spread across the wider Caribbean in a relatively short period of time. Because of its high invasion capacity, we used it as a model to identify the connectivity among nine marine protected areas (MPAs) situated in four countries in the Gulf of Mexico and the Caribbean Sea. This study provides evidence of local genetic differentiation of P. volitans in the Gulf of Mexico and the Caribbean Sea. A total of 475 lionfish samples were characterized with 12 microsatellites, with 6–20 alleles per locus. Departures from Hardy–Weinberg equilibrium (HWE) were found in 10 of the 12 loci, all caused by heterozygous excess. Moderate genetic differentiation was observed between Chiriviche, Venezuela and Xcalak, México localities (FST = 0.012), and between the Los Roques and the Veracruz (FST = 0.074) sites. STRUCTURE analysis found that four genetic entities best fit our data. A unique genetic group in the Gulf of Mexico may imply that the lionfish invasion unfolded both in a counterclockwise manner in the Gulf of Mexico. In spite of the notable dispersion of P. volitans, our results show some genetic structure, as do other noninvasive Caribbean fish species, suggesting that the connectivity in some MPAs analyzed in the Caribbean is limited and caused by only a few source individuals with subsequent genetic drift leading to local genetic differentiation. This indicates that P. volitans dispersion could be caused by mesoscale phenomena, which produce stochastic connectivity pulses. Due to the isolation of some MPAs from others, these findings may hold a promise for local short‐term control of by means of intensive fishing, even in MPAs, and may have regional long‐term effects.
When parks work: Effect of anthropogenic disturbance on occupancy of tropical forest mammals
Authors: Oberosler Valentina , Tenan Simone , Zipkin Elise F. , Rovero Francesco
Published: April 2020

Protected areas (PAs) in the tropics are vulnerable to human encroachment, and, despite formal protection, they do not fully mitigate anthropogenic threats to habitats and biodiversity. However, attempts to quantify the effectiveness of PAs and to understand the status and changes of wildlife populations in relation to protection efficiency remain limited. Here, we used camera‐trapping data collected over 8 consecutive years (2009–2016) to investigate the yearly occurrences of medium‐to‐large mammals within the Udzungwa Mountains National Park (Tanzania), an area of outstanding importance for biological endemism and conservation. Specifically, we evaluated the effects of habitat and proxies of human disturbance, namely illegal hunting with snares and firewood collection (a practice that was banned in 2011 in the park), on species' occurrence probabilities. Our results showed variability in species' responses to disturbance: The only species that showed a negative effect of the number of snares found on occurrence probability was the Harvey's duiker, a relatively widespread forest antelope. Similarly, we found a moderate positive effect of the firewood collection ban on only the suni, another common antelope, and a negative effect on a large opportunistic rodent, the giant‐pouched rat. Importantly, we found evidence of temporal stability in occurrence probability for all species over the 8‐year study period. Our findings suggest that well‐managed PAs can sustain mammal populations in tropical forests. However, variability among species in their responses to anthropogenic disturbance necessitates consideration in the design of conservation action plans for multiple taxa.
Reduced dispersal at nonexpanding range margins: A matter of disperser identity
Authors: Ben Zvi Gilad , Seifan Merav , Giladi Itamar
Published: April 2020

The evolution of dispersal at range margins received much attention recently, especially in the context of dynamic range shifts, such as those following climate change. However, much less attention has been devoted to study variation in and selection on dispersal at nonexpanding range margins, where populations are often small and isolated, and empirical test is dearly missing. To fill this gap, we tested whether dispersal of an ant‐dispersed perennial plant (Sternbergia clusiana) is quantitatively and/or qualitatively reduced toward a nonexpanding range margin. We evaluated plant investment in dispersal structures (elaiosome), seed removal rates, and the relative abundance, activity, and behavior of low‐ and high‐quality seed‐dispersing ants in six sites ranging from mesic Mediterranean site to arid site (>600 to <100 mm of annual rainfall, respectively), which marks the southern range margin of the species. In a set of cafeteria and baiting experiments, we found that overall seed removal rates, the contribution of high‐quality dispersers, maximum dispersal distance and dispersal‐conducive ant behavior decreased toward range margins. These findings agree with a lower investment in reward by range margin plant populations, as reflected by lower elaiosome/seed ratio, but not by variation in the reward chemistry. More than variation in traits controlled by the plants, the variation in ant–seed interactions could be attributed to reduced presence and activity of the more efficient seed‐dispersing ants in the marginal populations. Specifically, we found a mismatch between local distribution of potentially effective seed dispersers and that of the plant, even though those dispersers were observed in the study site. Interestingly, although the observed variation in the outcome of ant–seed interactions supported the prediction of reduced dispersal at nonexpanding range margins with small and isolated populations, the underlying mechanism seems to be incidental difference in the seed‐dispersing ant community rather than a plant‐mediated response to selection.
Unraveling the habitat preferences of two closely related bumble bee species in Eastern Europe
Authors: Geue Julia C. , Thomassen Henri A.
Published: April 2020

Co‐occurrence of closely related species is often explained through resource partitioning, where key morphological or life‐history traits evolve under strong divergent selection. In bumble bees (genus Bombus), differences in tongue lengths, nest sites, and several life‐history traits are the principal factors in resource partitioning. However, the buff‐tailed and white‐tailed bumble bee (Bombus terrestris and B. lucorum respectively) are very similar in morphology and life history, but their ranges nevertheless partly overlap, raising the question how they are ecologically divergent. What little is known about the environmental factors determining their distributions stems from studies in Central and Western Europe, but even less information is available about their distributions in Eastern Europe, where different subspecies occur. Here, we aimed to disentangle the broad habitat requirements and associated distributions of these species in Romania and Bulgaria. First, we genetically identified sampled individuals from many sites across the study area. We then not only computed species distributions based on presence‐only data, but also expanded on these models using relative abundance data. We found that B. terrestris is a more generalist species than previously thought, but that B. lucorum is restricted to forested areas with colder and wetter climates, which in our study area are primarily found at higher elevations. Both vegetation parameters such as annual mean Leaf Area Index and canopy height, as well as climatic conditions, were important in explaining their distributions. Although our models based on presence‐only data suggest a large overlap in their respective distributions, results on their relative abundance suggest that the two species replace one another across an environmental gradient correlated to elevation. The inclusion of abundance enhances our understanding of the distribution of these species, supporting the emerging recognition of the importance of abundance data in species distribution modeling.
Short‐and long‐term administration of imeglimin counters cardiorenal dysfunction in a rat model of metabolic syndrome
Authors: Lachaux Marianne , Soulié Matthieu , Hamzaoui Mouad , Bailly Anaëlle , Nicol Lionel , Rémy‐Jouet Isabelle , Renet Sylvanie , Vendeville Cathy , Gluais‐Dagorn Pascale , Hallakou‐Bozec Sophie , Monteil Christelle , Richard Vincent , Mulder Paul
Published: April 2020

Introduction

Imeglimin, a glucose‐lowering agent targeting mitochondrial bioenergetics, decreases reactive oxygen species (ROS) overproduction and improves glucose homeostasis. We investigated whether this is associated with protective effects on metabolic syndrome‐related left ventricular (LV) and vascular dysfunctions.

Methods

We used Zucker fa/fa rats to assess the effects on LV function, LV tissue perfusion, LV oxidative stress and vascular function induced by imeglimin administered orally for 9 or 90 days at a dose of 150 mg/kg twice daily.

Results

Compared to untreated animals, 9‐ and 90‐day imeglimin treatment decreased LV end‐diastolic pressure and LV end‐diastolic pressure‐volume relation, increased LV tissue perfusion and decreased LV ROS production. Simultaneously, imeglimin restored acetylcholine‐mediated coronary relaxation and mesenteric flow‐mediated dilation. One hour after imeglimin administration, when glucose plasma levels were not yet modified, imeglimin reduced LV mitochondrial ROS production and improved LV function. Ninety‐day imeglimin treatment reduced related LV and kidney fibrosis and improved kidney function.

Conclusion

In a rat model, mimicking Human metabolic syndrome, imeglimin immediately countered metabolic syndrome‐related cardiac diastolic and vascular dysfunction by reducing oxidative stress/increased NO bioavailability and improving myocardial perfusion and after 90‐day treatment myocardial and kidney structure, effects that are, at least in part, independent from glucose control.
Angiotensin receptor neprilysin inhibition versus individualized RAAS blockade: design and rationale of the PARALLAX trial
Authors: Wachter Rolf , Shah Sanjiv J. , Cowie Martin R. , Szecsödy Peter , Shi Victor , Ibram Ghionul , Zhao Ziqiang , Gong Jianjian , Klebs Sven , Pieske Burkert
Published: April 2020

Aims

Although the effect of the angiotensin receptor blocker neprilysin inhibitor (ARNI) sacubitril/valsartan on heart failure (HF) hospitalizations and cardiovascular death has been evaluated, its effects on functional capacity in patients with HF and ejection fraction (EF) >40% has yet to be determined. In addition, no prior studies have compared sacubitril/valsartan with angiotensin‐converting enzyme inhibitor therapy. We sought to compare the effect of ARNI to background‐medication‐based individualized comparators (BMICs) on N‐terminal pro‐B‐type natriuretic peptide (NT‐proBNP), functional capacity [6 min walk distance (6MWD)], symptoms, and quality of life [Kansas City Cardiomyopathy Questionnaire (KCCQ)] in patients with HF and EF >40% in a randomized clinical trial.

Methods

PARALLAX is a prospective, randomized, controlled, double‐blind multicentre clinical trial in patients with chronic symptomatic HF with EF >40%, New York Heart Association (NYHA) class II–IV symptoms, elevated natriuretic peptides, and evidence of structural heart disease. Eligible patients are randomized to sacubitril/valsartan vs. BMIC for cardiovascular and related co‐morbidities. BMIC includes (i) enalapril, (ii) valsartan, and (iii) placebo depending on the type of medical therapy prior to enrolment. The primary endpoints are the change in plasma NT‐proBNP concentration from baseline to 12 weeks and the change from baseline in 6MWD distance at 24 weeks. The secondary endpoints assess quality of life and symptom burden.

Conclusions

PARALLAX will determine if sacubitril/valsartan compared with standard medical therapy for co‐morbidities improves NT‐proBNP levels, exercise capacity, quality of life, and symptom burden in HF patients with EF >40%.
Radical Anions of Free‐Base Tetraphenyl‐ and Tetrakis(pentafluorophenyl)porphyrins: Effect of Substituents on the Properties and Charge Disproportionation in {Cryptand[2.2.2](Cs+)}(H2TPP·–)
Authors: Konarev Dmitri V. , Kuzmin Aleksey V. , Khasanov Salavat S. , Shestakov Alexander F. , Nazarov Dmitry I. , Otsuka Akihiro , Yamochi Hideki , Kitagawa Hiroshi , Lyubovskaya Rimma N.
Published: April 2020

The new method for the reduction of free‐base porphyrins has been developed and crystalline {cryptand[2.2.2](Cs+)}{H2TPP·–} (1) and {cryptand[2.2.2](Cs+)}{H2T(F5Ph)P·–}·C6H5CH3(2) salts containing porphyrin radical anions [TPP is tetraphenylporphyrin, T(F5Ph)P is tetrakis(pentafluorophenyl)porphyrin] have been obtained. The Cs+cations partially come out of the cryptand cage in {cryptand[2.2.2](Cs+)} approaching close to negatively charged porphyrin surface. As a result, one porphyrin radical anion forms close contacts with two Cs+cations with the Cs···P(plane) distances of 2.83–2.86 Å for1and 3.42 Å for2but another radical anion is positioned rather far from these cations. The salts have effective magnetic moments of 1.63–1.67 µBat 300 K indicating the contribution of oneS= 1/2 spin per radical anion. Salt2shows paramagnetic behaviour indicating the preservation of H2T(F5Ph)P·–down to 2 K. Magnetic moment of1is preserved down 240 K and below this temperature decrease of magnetic moment is observed. This can be attributed to charge disproportionation accompanied by electron transfer between H2TPP·–with different cationic surrounding and the formation of diamagnetic H2TPP0and H2TPP2–. This transfer is a thermally activated process with estimated energy of 200 ± 2 K. The effects of freezing of the disproportionation at low temperatures and shift of the equilibrium to paramagnetic H2TPP·–in magnetic field have been found. EPR spectra of1and2are also presented and discussed.
MCT Oil Coating Improves the Oxidative Stability of Surface Lipids in Corn Extrudates
Authors: Amft Jonas , Bauer Jonas L. , Rostek Jens , Spielvogel Sandra , Döring Frank , Schwarz Karin
Published: April 2020

Lipid‐containing extrudates are highly susceptible to lipid oxidation because of their porous structure and high specific surface area. The objective of this study is to investigate the effect of a low‐oxidizable medium‐chain triglycerides (MCT) coating on the oxidative stability. Therefore, cornmeal is extrusion cooked with commercial vegetable oil and various water contents (10–18% on dry matter) and partially coated with 5% w/w MCT oil. Lipid oxidation in the extrudates is examined during storage at +40 °C by measuring hydroperoxide concentrations in different lipid fractions (surface, inner‐surface, and matrix‐incorporated lipids). Hexanal is analyzed using headspace‐gas chromatography. Coating allocation is studied by fatty acid profiles of the lipid fractions, by fluorescence microscopy, and computerized microtomography. Application of an MCT coating leads to lower hydroperoxide concentrations and significantly reduces hexanal formation during storage. In particular, the surface lipids are stabilized. MCT oil diffuse only to small extent inside the extrudates and its effect on lipid oxidation can be attributed to differenct effects: filling surface microcracks, reducing the release of volatiles, and dilution of oxidizable lipids. This effect is strongest in porous extrudates with low feed‐water content.

Practical applications: Inhibition of lipid oxidation of fatty extrudates is of great importance for producers as well as consumers. In this study, we examine whether it is possible to improve the oxidative stability of extrudates by application of a lipid‐based coating. The results of this study suggest that it will be possible in the future to produce extrudates that are protected from oxidation by a thin natural oil film. We expect that especially products such as kibbles could benefit from treatment with a low‐oxidizable lipid‐based coating. In these products, fats are already used in combination with other functional ingredients. The combination of an MCT coating with a palatant or antioxidant is, therefore, an obvious alternative and of high relevance for manufacturers.
Core‐level cybersecurity assurance using cloud‐based adaptive machine learning techniques for manufacturing industry
Authors: Sakthivel Rakesh Kumar , Nagasubramanian Gayathri , Al‐Turjman Fadi , Sankayya Muthuramalingam
Published: April 2020

Cybersecurity is the domain that ensures safeness in both individual system and overall network systems. The classification and learning approaches used in different machine learning (ML) techniques improve the protection of the cyber systems against various attacks. Techniques such as support vector machine (SVM), neural networks (NN), principle component analysis (PCA), and reinforcement learning (RL) are used against various cyber threats. Applying these techniques at the front‐end services (either online or offline) makes less effect than back end process‐level services of any computer system. The proposed work analyzes the benefits of implementing customized ML and deep learning (DL) techniques on the core of the operating system than application level services, which in effect increases the speed and correctness of attack detection. The core (kernel) of the operating system has the capability to extract all internal attributes of process and file systems. The kernel space security activities can be improved by proposed work where the process level attributes classified using ML and DL techniques. The cloud service helps in sharing of the kernel abilities of the system ensuring core level security. The following work uses recurrent NN (RNN), SVM, PCA, and RL for analyzing the system data collected using Process Explorer. This technique finds application in manufacturing domain where the systems are protected from the various attacks to secure the data of the manufacturing company.
Der Erdruhedruckbeiwert K0 von Reibungsböden – Materialgesetz und Bestimmung aus einem Standard‐Triaxialversuch
Authors: Goldscheider Michael
Published: April 2020

Die übliche Formel nach Jáky und ein jüngerer Ansatz für den Erdruhedruckbeiwert K0 werden erläutert und kritisch bewertet. Im vorliegenden Bericht wird aus einem sehr einfachen Materialgesetz für proportionale Verformungs‐ und Spannungspfade, das mit hochgenauen Quaderverformungsversuchen an Sand erhalten wurde, eine Gleichung zur Bestimmung des Ruhedruckbeiwerts als Funktion des Reibungswinkels und des Dilatanzverhältnisses bei triaxialer Kompression entwickelt. Die enthaltenen Materialkonstanten lassen sich mit einem gewöhnlichen D‐Triaxialversuch bestimmen. Die K0‐Werte aus dem vorgestellten Materialgesetz sind deutlich größer als die Werte aus den genannten bestehenden Ansätzen. Die Unterschiede nehmen mit zunehmendem Reibungswinkel und Dilatanzverhältnis zu.
Head and neck virtual medicine in a pandemic era: Lessons from COVID‐19
Authors: Prasad Aman , Carey Ryan M. , Rajasekaran Karthik
Published: April 2020

The 2019 novel coronavirus disease (COVID‐19) has presented the world and physicians with a unique public health challenge. In light of its high transmissibility and large burden on the health care system, many hospitals and practices have opted to cancel elective surgeries in order to mobilize resources, ration personal protective equipment and guard patients from the virus. Head and neck cancer physicians are particularly affected by these changes given their scope of practice, complex patient population, and interventional focus. In this viewpoint, we discuss some of the many challenges faced by head and neck surgeons in this climate. Additionally, we outline the utility of telemedicine as a potential strategy for allowing physicians to maintain an effective continuum of care.
A risk score for the early prediction of postpartum bloodstream infections in patients with premature rupture of membranes: A pilot study
Authors: Li Lan , Yan Yunsheng , Qi Haifeng , Qin Jiali , Ren Li , Zhang Yaozong
Published: April 2020

The risk score may be an early predictor of bloodstream infections during the postpartum period in patients with premature rupture of membranes.
The mTORC2 Component Rictor Is Required for Load‐Induced Bone Formation in Late‐Stage Skeletal Cells
Authors: Lewis Karl J , Yi Xin , Wright Christian S , Pemberton Emily Z , Bullock Whitney A , Thompson William R , Robling Alexander G
Published: April 2020

Bone relies on mechanical cues to build and maintain tissue composition and architecture. Our understanding of bone cell mechanotransduction continues to evolve, with a few key signaling pathways emerging as vital. Wnt/β‐catenin, for example, is essential for proper anabolic response to mechanical stimulation. One key complex that regulates β‐catenin activity is the mammalian target of rapamycin complex 2 (mTORc2). mTORc2 is critical for actin cytoskeletal reorganization, an indispensable component in mechanotransduction in certain cell types. In this study, we probed the impact of the mTORc2 signaling pathway in osteocyte mechanotransduction by conditionally deleting the mTORc2 subunit Rictor in Dmp1‐expressing cells of C57BL/6 mice. Conditional deletion of the Rictor was achieved using the Dmp1–Cre driver to recombine Rictor floxed alleles. Rictor mutants exhibited a decrease in skeletal properties, as measured by DXA, μCT, and mechanical testing, compared with Cre‐negative floxed littermate controls. in vivo axial tibia loading conducted in adult mice revealed a deficiency in the osteogenic response to loading among Rictor mutants. Histological measurements of osteocyte morphology indicated fewer, shorter cell processes in Rictor mutants, which might explain the compromised response to mechanical stimulation. In summary, inhibition of the mTORc2 pathway in late osteoblasts/osteocytes leads to decreased bone mass and mechanically induced bone formation. © 2020 The Authors. JBMR Plus published by Wiley Periodicals, Inc. on behalf of American Society for Bone and Mineral Research.
Tools for quantitative analysis: The Al Yergey perspective
Authors: Gale P. Jane , Duncan Mark W.
Published: April 2020

The development of a reliable quantitative method for a specific application requires consideration of several important principles. Although mass spectrometry has become the “gold standard” for sensitive and precise multicomponent quantification, it does not necessarily follow that all quantitative data generated by mass spectrometry are either precise or accurate. Depending on the nature of the sample and the goal of the assay, the endeavor can be challenging. With attention to some critical concerns, valid results can be obtained; without attention to these concerns, results can be misleading and, in some instances, invalid.

For almost 10 years, beginning in 1996, the authors of this article, together with their friend and colleague Al Yergey, taught an American Society for Mass Spectrometry (ASMS) Short Course on the principles of quantitative mass spectrometry. In this Special Feature, we revisit and update some of these principles. We pay special attention to the contributions of Al Yergey to the course that not only enriched our own understanding of quantitative analysis but also had a measurable impact on the entire field of mass spectrometry.
Structural dependence of antidiabetic effect of steviol glycosides and their metabolites on streptozotocin‐induced diabetic mice
Authors: Myint Khaing Zar , Chen Jun‐ming , Zhou Zhuo‐yu , Xia Yong‐mei , Lin Jianguo , Zhang Jue
Published: April 2020

BACKGROUND

Stevia has been proposed as a potential antidiabetic sweetener, mainly based on inconsistent results from stevioside or the plant extract, yet lacking relative experimental evidence from individual steviol glycosides (SGs) and their metabolites.

RESULTS

The results systematically revealed that the typical SGs and their final metabolite (steviol) presented an antidiabetic effect on streptozotocin (STZ) diabetic mice in all assayed antidiabetic aspects. In general, the performance strength of the samples followed the sequence steviol > steviol glucosyl ester > steviolbioside > rubusoside > stevioside > rebaudioside A, which is opposite to their sweetness strength order, and generally in accordance with the glucosyl group numbers in their molecules. This may imply that the antidiabetic effect of the SGs might be achieved through steviol, which presented antidiabetic performance similar to that of metformin with a dose of 1/20 that of metformin. Moreover, the 18F‐fluorodeoxyglucose traced micro‐PET experiment revealed that stevioside and steviol could increase the uptake of glucose in the myocardium and brain of the diabetic mice within 60 min, and decrease the accumulation of glucose in the liver and kidney.

CONCLUSIONS

The SGs and steviol presented an antidiabetic effect on STZ diabetic mice in all assayed aspects, with an induction time to start the effect of the SGs. Stevioside and steviol could increase uptake of glucose in the myocardium and brain of the diabetic mice, and decrease accumulation of glucose in the liver and kidney. The performance strength of the SGs is generally in accordance with glucosyl group numbers in their molecules.
Orbital metastases from breast cancer: A single institution case series
Authors: Sindoni Alessandro , Fama' Fausto , Vinciguerra Paolo , Dionigi Gianlorenzo , Manara Sofia Ada Assunta Maria , Gaeta Roberto , Gioffre'‐Florio Maria , Di Maria Alessandra
Published: April 2020

Background and Objectives

Among orbital tumors, metastatic lesions have a prevalence of 1% to 13%; on the other hand, breast cancer is the most common malignancy causing orbital metastases. The aim of this study is to present our experience dealing with orbital metastases caused by breast cancer, to assess characteristics and clinic‐pathological data of patients suffering from this rare occurrence and to find indexes related with their prognosis and survival.

Methods

Records of 28 patients diagnosed with orbital metastases from breast cancer at the Department of Ophthalmology, Humanitas Clinical and Research Centre of Milano over a 27‐year period (1992‐2018) were retrieved and analyzed.

Results

Mean patients' age at breast cancer diagnosis was 56.29 ± 14.63 years. Mean time interval between breast cancer diagnosis and orbital metastasis occurrence was 5 ± 4.17 years. All lesions were estrogen receptor‐positive; 79% of patients harbored progesterone receptor‐positive lesions. Interestingly, the majority of deceased patients presented orbital lesions with MIB‐1 index >50% (P = .0265) and had concomitant lung metastases (P = .0452).

Conclusions

The occurrence of orbital metastasis from breast cancer represents a challenging finding. Patients' clinical picture can include exophthalmos, edema, tumefaction, proptosis and/or diplopia. Significant symptomatic improvement can be achieved through surgery and other adjuvant treatments, such as radiation therapy and chemotherapy.
Quantitative Inflammation Assessment for Crohn Disease Using Ultrasensitive Ultrasound Microvessel Imaging
Authors: Gong Ping , Song Pengfei , Kolbe Amy B. , Sheedy Shannon P. , Huang Chengwu , Ling Wenwu , Yu Yue , Zhou Chenyun , Lok U Wai , Tang Shanshan , Bruining David H. , Knudsen John M. , Chen Shigao
Published: April 2020

Objectives

Crohn disease (CD) is a chronic inflammation in the digestive tract that affects millions of Americans. Bowel vascularity has important diagnostic information because inflammation is associated with blood flow changes. We recently developed an ultrasensitive ultrasound microvessel imaging (UMI) technique with high vessel sensitivity. This study aimed to evaluate the feasibility of UMI to assist CD detection and staging.

Methods

Ultrasound microvessel imaging was performed on 76 bowel wall segments from 48 symptomatic patients with CD. Clinically indicated computed tomographic/magnetic resonance enterography was used as the reference standard. The vessel‐length ratio (VLR, the number of vessel pixels in the bowel wall segment normalized to the segment length) was derived in both conventional color flow imaging (CFI) and UMI to quantitatively stage disease activity. Receiver operating characteristic curves were then analyzed between different disease groups.

Results

The VLR‐CFI and VLR‐UMI detected similar correlations between vascularization and disease activity: severe inflammation had a higher VLR than normal/mildly inflamed bowels (P < .05). No significant difference was found between quiescent and mild CD due to the small sample size. The VLR‐CFI had more difficulties in distinguishing quiescent versus mild CD compared to the VLR‐UMI. After combining the VLR‐UMI with thickness, in the receiver operating characteristic curve analysis, the areas under the curves (AUCs) improved to AUC1 = 0.996 for active versus quiescent CD, AUC2 = 0.978 for quiescent versus mild CD, and AUC3 = 0.931 for mild versus severe CD, respectively, compared to those using thickness alone (AUC1 = 0.968; P = .04; AUC2 = 0.919; P = .16; AUC3 = 0.857; P = .01).

Conclusions

Ultrasound microvessel imaging offers a safe and cost‐effective tool for CD diagnosis and staging, which may potentially assist disease activity classification and therapy efficacy evaluation.
From Dimeric to Octameric Metallo‐Supramolecular Macrocycles Based on Sterically Congested Ligand–assisted Self‐Assembly with Zn(II), Cd(II), and Fe(II)
Authors: Guan Shengwen , Yu Hao , Zhang Zhe , Jiang Xin , Shi Junjuan , Lu Tong , Wang Chunyu , Wang Pingshan , Wang Ming
Published: April 2020

Two sterically congested 2,2′:6′,2″‐terpyridine‐based ligands LA and LB, composed of asymmetrically contiguous terpyridine units, are designed and synthesized for metallo‐supramolecular architectures. The significant advantage of this design is that the terpyridines in these ligands have different chemical environments and show a selective coordination ability with each other. For ditopic ligand LA, the self‐assembly with Zn(II), Cd(II), and Fe(II) gave the rhombic dimers, which have the same sets of terpyridine signals as ligand LA. The self‐assembly behavior of tritopic ligand LB with Cd(II) and Zn(II) are observed for discrete tetramers under thermodynamic control, whereas ligand LB and Fe(II) are assembled to generate a mixture of tetramer, hexamer, and octamer, which are successfully isolated using regular chromatographic separation. Moreover, the sterically congested ligands and metal ions formed stable intermediates to drive the formation of discrete structures, which is also proved by mixing LB and Cd(II) with a precise stoichiometric ratio of 1:1. These supramolecular complexes are thoroughly characterized by NMR spectroscopy, electrospray ionization‐mass spectrometry, and 2D traveling‐wave ion mobility‐mass spectrometry. This conceptually new design of sterically congested ligands provides a novel strategy for precisely controlled supramolecular complexes with diverse architectures.
Pedicled perforator‐based flaps: Risk factor analysis, outcomes evaluation and decisional algorithm based on 130 consecutive reconstructions
Authors: Brunetti Beniamino , Barone Mauro , Tenna Stefania , Salzillo Rosa , Segreto Francesco , Persichetti Paolo
Published: April 2020

Introduction

Pedicled perforator flaps are widely used for soft tissue reconstruction, but evidence in literature about risk factors associated with complications is still controvert. The aim of this study is to evaluate risk factors and outcomes associated with pedicled perforator‐based flaps harvested at different anatomical sites.

Patients and methods

Seventy‐one propeller and 59 V‐Y advancement flaps were performed to reconstruct defects of the face (24 cases), trunk (47 cases), and extremities (59 cases). Mean defect and flap area were 32.43 and 43.2 cm2, respectively. The average age recorded was 66 years. We statistically analyzed whether patient and flap‐related variables had an impact on flap vascular complications rate. Patients were asked to rate on a 5‐point Likert scale the aesthetic and functional outcomes of the surgery.

Results

Overall flap complications rate was 23.07%. Coronary heart disease was an independent risk factor for flap complications (p = .010), while hypertension was associated with a lower complication rate (p = .010). The increasing degree of pedicle rotation had a significant impact on the development of flap vascular complications (p = .008). Mean patients' aesthetic and functional ratings were 4.23 of 5 and 4.37 of 5, respectively.

Conclusions

We found a positive correlation between both coronary heart disease and increasing degree of pedicle rotation and complications. Other factors tested were not significantly associated with complications. Patients were overall satisfied with both the aesthetic and functional outcomes of the procedure. The decisional algorithm hereby suggested yields a 93.1% overall success rate and we believe it could be of help to plastic surgeons approaching soft tissue defects.