bluuebunny/crossref_metadata_2025 huggingface dataset:
Multiple Emitting Amphiphilic Conjugated Polythiophenes‐Coated CdTe QDs for Picogram Detection of Trinitrophenol Explosive and Application Using Chitosan Film and Paper‐Based Sensor Coupled with Smartphone
Authors: Tawfik Salah M. , Sharipov Mirkomil , Kakhkhorov Sarvar , Elmasry Mohamed R. , Lee Yong‐Ill
Published: November 2018

Novel multiple emitting amphiphilic conjugated polythiophene‐coated CdTe quantum dots for picogram level determination of the 2,4,6‐trinitrophenol (TNP) explosive are developed. Four biocompatible sensors, cationic polythiophene nanohybrids (CPTQDs), nonionic polythiophene nanohybrids (NPTQDs), anionic polythiophene nanohybrids (APTQDs), and thiophene copolymer nanohybrids (TCPQDs), are designed using an in situ polymerization method, which shows highly enhanced fluorescence intensity and quantum yield (up to 78%). All sensors are investigated for nitroexplosive detection to provide a remarkable fluorescence quenching for TNP and the quenching efficiency reached 96% in the case of TCPQDs. The fluorescence of the sensors are quenched by TNP through inner filter effect, electrostatic, π−π, and hydrogen bonding interactions. Under optimal conditions, the detection limits of CPTQDs, NPTQDs, APTQDs, and TCPQDs are 2.56, 7.23, 4.12, and 0.56 × 10−9 m, respectively, within 60 s. More importantly, portable, cost effective, and simple to use paper strips and chitosan film are successfully applied to visually detect as little as 2.29 pg of TNP. The possibility of utilizing a smartphone with a color‐scanning APP in the determination of TNP is also established. Moreover, the practical application of the developed sensors for TNP detection in tap and river water samples is described with satisfactory recoveries of 98.02−107.50%.
Early Miocene CO2 estimates from a Neotropical fossil leaf assemblage exceed 400 ppm
Authors: Londoño Liliana , Royer Dana L. , Jaramillo Carlos , Escobar Jaime , Foster David A. , Cárdenas‐Rozo Andrés L. , Wood Aaron
Published: November 2018

Premise of the Study

The global climate during the early Miocene was warmer than the present and preceded the even warmer middle Miocene climatic optimum. The paleo‐CO2 records for this interval suggest paradoxically low concentrations (<450 ppm) that are difficult to reconcile with a warmer‐than‐present global climate.

Methods

In this study, we use a leaf gas‐exchange model to estimate CO2 concentrations using stomatal characteristics of fossil leaves from a late early Miocene Neotropical assemblage from Panama that we date to 18.01 ± 0.17 Ma via 238U/206Pb zircon geochronology. We first validated the model for Neotropical environments by estimating CO2 from canopy leaves of 21 extant species in a natural Panamanian forest and from leaves of seven Neotropical species in greenhouse experiments at 400 and 700 ppm.

Key Results

The results showed that the most probable combined CO2 estimate from the natural forests and 400 ppm experiments is 475 ppm, and for the 700 ppm experiments is 665 ppm. CO2 estimates from the five fossil species exhibit bimodality, with two species most consistent with a low mode (528 ppm) and three with a high mode (912 ppm).

Conclusions

Despite uncertainties, it is very likely (at >95% confidence) that CO2 during the late early Miocene exceeded 400 ppm. These results revise upwards the likely CO2 concentration at this time, more in keeping with a CO2‐forced greenhouse climate.
Integrated automated particle tracking microfluidic enables high‐throughput cell deformability cytometry for red cell disorders
Authors: Guruprasad Puneeth , Mannino Robert G. , Caruso Christina , Zhang Hanqing , Josephson Cassandra D. , Roback John D. , Lam Wilbur A.
Published: November 2018

Investigating individual red blood cells (RBCs) is critical to understanding hematologic diseases, as pathology often originates at the single‐cell level. Many RBC disorders manifest in altered biophysical properties, such as deformability of RBCs. Due to limitations in current biophysical assays, there exists a need for high‐throughput analysis of RBC deformability with single‐cell resolution. To that end, we present a method that pairs a simple in vitro artificial microvasculature network system with an innovative MATLAB‐based automated particle tracking program, allowing for high‐throughput, single‐cell deformability index (sDI) measurements of entire RBC populations. We apply our technology to quantify the sDI of RBCs from healthy volunteers, Sickle cell disease (SCD) patients, a transfusion‐dependent beta thalassemia major patient, and in stored packed RBCs (pRBCs) that undergo storage lesion over 4 weeks. Moreover, our system can also measure cell size for each RBC, thereby enabling 2D analysis of cell deformability vs cell size with single cell resolution akin to flow cytometry. Our results demonstrate the clear existence of distinct biophysical RBC subpopulations with high interpatient variability in SCD as indicated by large magnitude skewness and kurtosis values of distribution, the “shifting” of sDI vs RBC size curves over transfusion cycles in beta thalassemia, and the appearance of low sDI RBC subpopulations within 4 days of pRBC storage. Overall, our system offers an inexpensive, convenient, and high‐throughput method to gauge single RBC deformability and size for any RBC population and has the potential to aid in disease monitoring and transfusion guidelines for various RBC disorders.
Elderly do benefit from induction chemotherapy: High dose mitoxantrone‐based (“5 + 1”) induction chemotherapy regimen in newly diagnosed acute myeloid leukemia
Authors: Saini Neeraj Y. , Cerny Jan , Furtado Vanessa F. , Desmond Angela , Zhou Zheng , Raffel Glen , Puthawala Imran , Bednarik Jayde , Shanahan Lindsey , Miron Patricia M. , Woda Bruce , Ramanathan Muthalagu , Nath Rajneesh
Published: November 2018

An intensive “5 + 1” regimen, which included bolus high dose cytarabine (HiDAC) at 3 g/m2 once daily over 3 hours on days 1‐5 and high dose mitoxantrone (HDM) 80 mg/m2 on day 2, was evaluated in 101 consecutively treated newly diagnosed acute myeloid leukemia (AML) patients at a single center since 2009. The median age was 65 (range 18‐90) years. The 4 and 8‐week mortality in our cohort was 3/101 (2.9%) and 7/99 (7%), respectively. The overall response (complete remission [CR] + CRi) was 76.2% (77/101). The median overall survival (OS) stratified by age group <60, 60‐69 and ≥70 years were 56, 31 and 9 months respectively (log‐rank, P = 0.02). 51.7% (45/84) of patients with intermediate/adverse risk category proceeded to allogeneic stem cell transplants. Among these 84 patients, the percentage of patients able to proceed to transplant in age groups <60, 60‐69, and ≥ 70 years were 75% (18/24), 60.7% (17/28), and 31.2% (10/32), respectively. In conclusion, HDM‐based chemotherapy regimen produces high CR rates, is well tolerated and more patients can undergo curative postremission therapy including stem cell transplant.
Energy, Linear Momentum, and Angular Momentum of Light: What Do We Measure?
Authors: Emile Olivier , Emile Janine
Published: November 2018

The most commonly observed quantity related to light is its power or, equivalently, its energy. It can be either measured with a bolometer, a photodiode, or estimated with the naked eye. Alternatively, people can measure the light impulse or linear momentum. However, linear momentum is characterized by its transfer to matter, and its precise value is, most of the time, of little use. Energy and linear momentum are linked and can be deduced from each other, from a theoretical point of view. Because the linear momentum measurement is more difficult, energy is the most often measured quantity. In every physical process, angular momentum, like energy and linear momentum, is conserved. However, it is independent and cannot be deduced from the energy or the linear momentum. It can only be estimated via its transfer to matter using a torque observation. Nevertheless, experimentally, the torque is found to be proportional to the optical power. This leads to a need for a quantum interpretation of the optical field in terms of photons. Clear experimental evidences and consequences are presented here and debated.
Mechanochemie gasförmiger Reaktanten
Authors: Bolm Carsten , Hernández José G.
Published: November 2018

In den letzten Jahren hat sich die Anwendung von mechanischer Energie auf chemische Systeme wiederholt als vorteilhaft erwiesen, um chemische Umwandlungen in verschiedenen Gebieten der Chemie zu erleichtern. Eine Vielzahl von systematischen Studien belegt heute, dass die Mechanochemie vielversprechende Möglichkeiten eröffnet, die chemische Synthese zu verändern. Nicht nur allein die Fähigkeit, die Herstellung von Produkten zu ermöglichen, die durch bestehende Methoden, wie der reinen thermischen Aktivierung, unzugänglich sind, haben zu einer Anerkennung der Mechanochemie geführt. Man hat auch gemerkt, dass mechanochemische Reaktionen ihre nasschemischen Gegenstücke oft hinsichtlich der Nachhaltigkeit übertreffen. Intuitiv sind die meisten mechanochemischen Reaktionen, die durch Kugelmahlen ausgeführt werden, mit der Umwandlung von Festkörpern und Flüssigkeiten verknüpft. In den letzten Jahren hat allerdings die Anzahl mechanochemischer Reaktionen mit gasförmigen Reaktanten zugenommen. Das Ziel dieses Kurzaufsatzes ist es daher, einerseits einen Überblick über chemische Reaktionen zu geben, die den Gebrauch von gasförmigen Proben in Kugelmühlen beinhalten, und andererseits die Fortschritte der Technologien und Aufbauten der Kugelmühlen aufzuzeigen, die den sicheren Umgang mit gasförmigen Reagenzien unter mechanochemischen Bedingungen ermöglicht haben. Darüber hinaus werden Beispiele für Reaktionen aufgezeigt, die an der Grenzfläche Feststoff/Flüssigkeit/Gas–Gas stattfinden und zu einer signifikanten Verbesserung der Reaktivität oder Selektivität geführt haben. Letztendlich hoffen wir zukünftige Arbeiten anzuregen, um verbleibende Herausforderungen auf dem Gebiet der Mechanochemie anzugehen.
Hydrogen‐Bonded Networks: Molecular Recognition of Cyclic Alcohols in Enantiopure Alleno‐Acetylenic Cage Receptors
Authors: Gropp Cornelius , Husch Tamara , Trapp Nils , Reiher Markus , Diederich François
Published: November 2018

Enantiopure (P)4‐ and (M)4‐alleno‐acetylenic cage (AAC) receptors form circular fourfold hydrogen‐bonding networks in their closed cage conformation. Theoretical studies reveal a preferential clockwise (cw) orientation of the H‐bonding array for (P)4‐configured and counterclockwise (ccw) for (M)4‐configured receptors (ΔEcw−ccw=−2.6 to −3.1 kcal mol−1). Solution and solid‐state studies show how the H‐bonding network of the receptor is expanded upon encapsulation of alcohol‐containing guests. Topologies reminiscent of those found in isolated water clusters are observed: circular fourfold & docking, pentagonal, linear fivefold, and hexagonal boat‐shaped. Expansion of the H‐bonding network together with optimal space occupancy yields very high ligand affinities (ΔG293 K=−9.0 kcal mol−1 for endo‐tropine). The H‐bonding network in the complexes also contributes substantially to the enantioselective complexation of chiral diols, such as (R,R)‐ and (S,S)‐trans‐cyclohexane‐1,2‐diol.
Mechanochemistry of Gaseous Reactants
Authors: Bolm Carsten , Hernández José G.
Published: November 2018

In recent years, the application of mechanical energy to chemical systems has repeatedly proven beneficial to facilitate chemical transformations in various areas in chemistry. Today, a systematic body of evidence indicates that mechanochemistry holds great promise to become a game‐changer in chemical synthesis. Not only does mechanochemistry permit access to products that are inaccessible by established means (e.g. purely thermal activation), mechanochemical reactions often outperform their solution‐based counterparts in terms of sustainability. Most mechanochemical reactions carried out by ball milling techniques involve transformations of solids and liquids, but the number of mechanochemical reactions with gaseous reactants is increasing. The aim of this Minireview is to provide an overview of recent chemical reactions involving gaseous samples by ball milling techniques and to highlight advances in ball milling technology for the safe handling of gaseous reagents. Examples of reactions proceeding at the interface of solid–/liquid–/gas–gas systems that led to significant improvements in reactivity or selectivity will also be highlighted.
GC‐MS metabolite profiling for specific detection of dwarf somaclonal variation in banana plants
Authors: Cevallos‐Cevallos Juan M. , Jines Cristina , Maridueña‐Zavala María G. , Molina‐Miranda María J. , Ochoa Daniel E. , Flores‐Cedeno José A.
Published: November 2018

Premise of the Study

The production of banana (Musa spp.; Musaceae) plants is affected by various types of somaclonal variations (SV), including dwarfism. However, methods for specific detection of SV are still scarce. To overcome this, a metabolite‐based method for detection of dwarf variants was evaluated.

Methods

The gas chromatography–mass spectrometry (GC‐MS) metabolite profile of dwarf banana variants was investigated and compared to that of normal‐healthy (N) and cucumber mosaic virus (CMV)–infected plants using principal components analysis and partial least squares discriminant analysis (PLS‐DA).

Results

Significant differences among the sample groups were observed in 82 metabolites. Rhamnose was exclusively present in dwarf plants but allothreonine and trehalose were present in all but SV samples. Cellobiose was only detected in N plants, while 45 other metabolites, including methyl‐glucopyranoside, allopyranose, lactose, phenylalanine, and l‐lysine were detected in all but CMV‐infected samples. PLS‐DA models were able to detect SV, CMV, and N plants with 100% accuracy and specificity.

Discussion

The GC‐MS metabolite profile can be used for the rapid, specific detection of SV at early plant production stages. This is the first metabolite‐based characterization and detection of somaclonal variation in plants.
The contribution of gustatory input to larval acceptance and female oviposition choice of potential host plants in Papilio hospiton (Géné)
Authors: Sollai Giorgia , Crnjar Roberto
Published: November 2018

The Lepidopteran Papilio hospiton uses only plants belonging to the Apiaceae and the Rutaceae families as hosts. Both adult females and larvae are equipped with gustatory receptor neurons (GRNs) capable of detecting sugars, bitters and salts, thus providing information for evaluating the chemical composition of the plant. Since the activation of these neurons may affect insect behavior, the aim of this study were: (a) to study the gustatory sensitivity of both females and larvae to the sap of two Apiaceae,
Foeniculum vulgare (fennel) and
Daucus carota (carrot), that are not used as host plants; (b) to cross‐compare the spike activity evoked from these two plants with that evoked by
Ferula communis (ferula), the host plant preferred by ovipositing females of
P. hospiton and where the larvae perform best; (c) finally, to confirm that the gustatory system can provide the central nervous system with the necessary information to evaluate differences between plant saps. The results show that: (a) fennel and carrot both evoke a higher neural activity from the bitter‐sensitive neurons and lower from the sugar‐sensitive neurons with respect to ferula, in both adult females and larvae; (b) on the basis of the different patterns of neural activity generated in tarsal, lateral and medial sensilla by fennel and carrot versus ferula, both adult and larvae possess enough information to discriminate among these plants; (c) adult females of
P. hospiton lay eggs where the larvae have the greatest growth success and this confirms the importance of taste sensitivity in host plants selection.
An Aluminum/Graphite Battery with Ultra‐High Rate Capability
Authors: Elia Giuseppe A. , Kyeremateng Neil A. , Marquardt Krystan , Hahn Robert
Published: November 2018

A high‐performance Al/graphite battery has been investigated, employing a natural graphite cathode (NG) and 1‐ethyl‐3‐methylimidazolium chloride (EMIMCl):AlCl3 as electrolyte. The employed graphite is characterized by excellent reversibility as revealed by electrochemical tests and ex‐situ XRD. The Al/EMIMCl:AlCl3/NG battery showed extraordinary performance in terms of rate capability, and cycle life. The cell delivered a capacity of 110 mAh g−1 at lower current values, retaining 90 % and 60 % of the capacity employing a current of 20 A g−1 and 50 A g−1, respectively (i. e., a complete charge‐discharge cycle in 35 and 9 seconds, respectively). Furthermore, the cycling test performed using a current of 20 A g−1 revealed an extremely long calendar life of half million of cycles. The practical applicability of the investigated Al/graphite system has been ascertained; this involved estimating the energy efficiency as a function of current rate and carefully calculating the practical energy densities that can be obtained from the system.
An alternative model of researching educational practice: A pedagogic–stereoscopic point of view
Authors: Saeverot Herner , Kvam Vegard
Published: November 2018

While teachers and practitioners are increasingly expected to conduct research on their own practice, there is a lot of educational research that is not directly involved in practice. This often leads to unilateral research perspectives on educational practice. Therefore, this article calls for an alternative model of researching educational practice, summarised through the term ‘pedagogical science’. We argue that practical and normative theories that seek to improve educational practice should be combined with theories that aim to describe and explain. It is further argued that the combination of such perspectives and theories, a so‐called stereoscopic point of view, can allow for a thorough and holistic investigation of educational practice. As part of this argumentation, the article addresses critical questions of various theoretical models of educational research, models that are being used in Scandinavian, European and Anglo‐American research on educational practice. With reference to interdisciplinary models of educational research, such as educational sciences, learning sciences and Bildungswissenschaften, there are trends in which pedagogy is marginalised. Thus, the second argument of the article calls for placing pedagogy at the centre of knowledge production in a broad sense, after which pedagogy is made into a source of knowledge for pedagogical science, which sets forth to test and provide empirical support for pedagogy‐based knowledge.
Absorption and distribution of lupeol in CD‐1 mice evaluated by UPLC–APCI+–MS/MS
Authors: Cháirez‐Ramírez Manuel Humberto , Gallegos‐Infante Jose Alberto , Moreno‐Jiménez Martha Rocio , González‐Laredo Ruben Francisco , Rocha‐Guzmán Nuria Elizabeth
Published: November 2018

Lupeol is a dietary triterpene that shows limited water solubility, which affects its bioavailability. It is well known that poor oral bioavailability is one of the major causes of therapeutic variability. Lupeol has been reported to have multiple biological activities; however, there are no reports about its bioavailability. Therefore, the objective of this research was to evaluate the systemic bioavailability of lupeol. An experimental strategy with three groups of female CD‐1 strain mice was proposed (control, olive oil and lupeol in olive oil), at six experimental times (0.5, 2, 4, 8, 12 and 24 h) with four animals per experimental point. Mice were sacrificed for organs, urine, feces and blood collection. Lupeol was extracted from samples and analyzed by UPLC–APCI+–MS/MS, obtaining the pharmacokinetics parameters time to peak concentration 6.444 ± 0.851 h and peak concentration 8.071 ± 2.930 μg/mL. Study of direct digestion and absorption in various organs showed important concentrations of lupeol at earlier post‐administration times (stomach, 137.25 ± 19.94 ng/mg and small intestine, 99.00 ± 12.99 ng/mg). The main excretion route was fecal, with a peak at 12 h post‐administration (163.28 ± 9.83 μg/mg). Absorption of lupeol by the animals was better than expected despite its nonpolar nature (extent of absorption F = 0.645 ± 0.0581).
Design Principles for Cationic, Astrocyte‐Targeted Probes
Authors: Preston Alyssa N. , Farr Joshua D. , Tan Kevin C. , Cervasio Danielle A. , Butkus Lauren R. , Laughlin Scott T.
Published: November 2018

The brain's astrocytes play key roles in normal and pathological brain processes. Targeting small molecules to astrocytes in the presence of the many other cell types in the brain will provide useful tools for their visualization and manipulation. Herein, we explore the functional consequences of synthetic modifications to a recently described astrocyte marker composed of a bright rhodamine‐based fluorophore and an astrocyte‐targeting moiety. We altered the nature of the targeting moiety to probe the dependence of astrocyte targeting on hydrophobicity, charge, and pKa when exposed to astrocytes and neurons isolated from the mouse cortex. We found that an overall molecular charge of +2 and a targeting moiety with a heterocyclic aromatic amine are important requirements for specific and robust astrocyte labeling. These results provide a basis for engineering astrocyte‐targeted molecular tools with unique properties, including metabolite sensing or optogenetic control.
Hybrid transcatheter tricuspid valve‐in‐valve placement of an Edwards Sapien XT valve in palliated hypoplastic left heart syndrome
Authors: Ho Andrew B. , Kaarne Markku , Mullen Michael , Hayes Nicholas
Published: November 2018

Tricuspid regurgitation in the context of hypoplastic left heart syndrome (HLHS) carries a significant burden of both mortality and morbidity. We report successful hybrid trans‐atrial implantation of an Edwards Sapien XT valve into a dysfunctional bioprosthetic valve in the tricuspid position of a 9‐year‐old patient with HLHS. There was an immediate fall in the Fontan pressures combined with significant clinical improvement and the valve continues to function well nearly 3 years post implant. To the best of our knowledge, this is the first described implantation of a transcatheter valve in this specific position and anatomy.
Isolated pan‐pontine posterior reversible encephalopathy syndrome in a patient with uncontrolled hypertension
Authors: Gowan Jacqueline Marie , Liu Antonio
Published: November 2018

Key Clinical Message

Recognition of central variant PRES is key to avoiding detrimental treatment. The pons may be the most vulnerable area in central PRES, and delayed presentation may result in greater damage. CSF reporting may lead to eventual recognition of a common profile, and possible aid in future diagnosis.
Rhomboid blepharoplasty and cryotherapy for the treatment of a squamous cell carcinoma on the lower eyelid in a horse
Authors: Jeanes Emily C. , Koll‐Hampp Sarah , Dawson Charlotte , Dunkel Bettina , Tetas Pont Roser
Published: November 2018

Key Clinical Message

A rhomboid blepharoplasty can be used to achieve functional and cosmetic eyelid reconstruction at the medial canthus in the horse. Combination of a rhomboid blepharoplasty with cryotherapy is a treatment option for eyelid ocular squamous cell carcinomas.
Adult renal sarcoma: A rare case of recurrence 13 years after initial resection
Authors: Alameddine Mahmoud , Zheng Ian , Yusufali Ali , Mackrides Nicholas , Ciancio Gaetano
Published: November 2018

Key Clinical Message

Renal sarcoma is a rare and aggressive malignancy without proper guidelines for treatment. Due to the aggressiveness of this disease and the potential for recurrence, we believe that extensive surgical resection with healthy margins may be the best option to treat this condition during both initial resection and resection of the recurrent lesion. Clinical follow‐up is also important to monitor for tumor recurrence.
Congenital glucose‐galactose malabsorption: A case report with a novel SLC5A1 mutation
Authors: Al‐lawama Manar , Albaramki Jumana , Altamimi Mutaz , El‐Shanti Hatem
Published: November 2018

Key Clinical Message

A three‐day‐old newborn girl presented with decreased feeding and dehydration. She was sick and in shock. She had renal impairment and hypernatremia. With the resumption of breast feeding, she developed watery stools and hypernatremia. Glucose‐Galactose Malabsorption was suspected and confirmed by the presence of a likely pathogenic homozygous variant in SLC5A1.
Variable phenotypic expression of Apert syndrome in monozygotic twins
Authors: Dap Matthieu , Bach‐Segura Pascale , Bertholdt Charline , Menzies Didier , Masutti Jean‐Pierre , Klein Olivier , Perdriolle‐Galet Estelle , Lambert Laetitia , Morel Olivier
Published: November 2018

Key Clinical Message

Apert syndrome in monozygotic twins can lead to different phenotypic expression of the disease in the two fetuses. Apert syndrome can be associated with congenital left diaphragmatic hernia and cleft palate.
Oral maxillary exostosis
Authors: Limongelli Luisa , Tempesta Angela , Capodiferro Saverio , Maiorano Eugenio , Favia Gianfranco
Published: November 2018

Key Clinical Message

Oral maxillary exostoses are proliferating bone lesions with an unknown etiology occurring on the cortical plates both in the maxilla and in the mandible of young individuals, showing a typical slow but continuous enlargement. No treatment is usually required unless they create esthetic or functional limitations during follow‐up; the biopsy is needed only for doubtful lesions. Furthermore, it is mandatory to collect an accurate familiar history of patients affected by exostosis, especially when occurring with atypical clinical presentation, in order to exclude or prevent potentially associated systemic diseases.
Tuning the Catalytic Activity and Substrate Specificity of Peptide‐Nanoparticle Conjugates
Authors: Mikolajczak Dorian J. , Scholz Jonas , Koksch Beate
Published: November 2018

The immobilization of cysteine‐containing peptides onto the surface of gold nanoparticles (Pep‐Au‐MPCs) emerged as a promising strategy towards the development of artificial enzymes. In this context we studied the effect the location of the catalytic unit within the peptide‐monolayer relative to the nanoparticle surface has on the esterolytic activity and substrate specificity of three Pep‐Au‐MPCs, that only differ in the position of the catalytic unit (surface proximal, intermediate, surface distal). Rates of ester hydrolysis were found to correlate with the hydrophobicity of the substrate and the position of the catalytic unit. Highly hydrophobic ester substrates are cleaved more efficiently surface proximal, whereas less hydrophobic substrates showed higher rates of hydrolysis in the intermediate region of the monolayer. Our studies reveal the importance the position of the catalytic center has on the catalytic activity and substrate specificity of peptide‐nanoparticle conjugates.
Ruthenium Catalyzed Reductive Transformation of Itaconic Acid and Ammonia Into 3‐ and 4‐Methyl‐pyrrolidone
Authors: Louven Yannik , Schute Kai , Palkovits Regina
Published: November 2018

The reductive transformation of biogenic carboxylic acids and ammonia presents a promising route to access pyrrolidones as N‐containing bio‐based fine chemicals. Herein, we report the first approach to convert itaconic acid to N‐unsubstituted pyrrolidones. The reaction was carried out in low amounts of water as solvent with hydrogen as reduction agent and ammonia as nitrogen source. A Ru/C catalyst was found to be highly active for this reaction. Furthermore, a coherent reaction network could be proposed. Catalyst recycling and variation of substrates demonstrate both the robustness and broad scope of the presented catalytic system.
Preparative separation of four isomers of synthetic anisodamine by HPLC and diastereomer crystallization
Authors: Wu Tong , Zhu Jiu‐Xin , Wei Qian , Li Ping , Wang Li‐Bo , Huang Jian , Wang Jin‐Hui , Tang Li‐Ke , Wu Li‐Jun , Li Chang , Han Wei‐Na
Published: November 2018

Anisodamine (654‐1), a well‐known cholinergic antagonist, is marketed as synthetic anisodamine (mixture of four isomers, 654‐2) in China. To preparative resolution and comparison of the bioactivities of the four isomers of synthetic anisodamine, current work explores an economic and effective separation method by using preparative high performance liquid chromatography (HPLC) and diastereomer crystallization. Their absolute configurations were established by single‐crystal X‐ray diffraction and circular dichroism method. The purities of each isomer were more than 95%. Among them, 654‐2‐A2 (6R, 2′S configuration) exhibited better effect on cabachol preconditioned small intestine tension more than 654‐2 and other isomers. The direct separation method without using HPLC was tried as well, which was still on progress. This is the first report of the method for preparative separation of four isomers of synthetic anisodamine which could be used for large‐scale production in industry.
Gray‐Box Modeling for the Optimization of Chemical Processes
Authors: Asprion Norbert , Böttcher Roger , Pack Robert , Stavrou Marina‐Eleni , Höller Johannes , Schwientek Jan , Bortz Michael
Published: November 2018

The availability of predictive models for chemical processes is the basic prerequisite for offline process optimization. In cases where a predictive model is missing for a process unit within a larger process flowsheet, measured operating data of the process can be used to set up such models combining physical knowledge and process data. In this contribution, the creation and integration of such gray‐box models within the framework of a flowsheet simulator is presented. Results of optimization using different gray‐box models are shown for a virtual cumene process.
News from Microprocess Engineering
Authors: Pietrek Philip , Deschner Benedikt J. , Navarrete Alexander
Published: November 2018

Mit einem Fokusthema „Flexible Production #FlexProd” stellte die ACHEMA in diesem Jahr Anlagenkonzepte für eine digitalisierte, agile und adaptive Prozessindustrie zum allgemeinen Industrietrend Industrie 4.0 in den Vordergrund. Eine tragende Säule dieses Fokusthemas war der Flow Chemistry Pavillion. Dieser Ausstellungsteil bündelte auf einer weitläufigen Ausstellungsfläche innovative Aussteller zur kontinuierlichen Produktion samt Präsentations‐ und Diskussionsbereich. Die aktuellen Trends und Produkte aus der Mikroverfahrenstechnik werden vorgestellt, die die Zukunft der Mikroverfahrenstechnik bahnen sollen.
Population‐based data registries suggest novel insight into malignancy and metabolism
Authors: Meydan Chanan
Published: November 2018

Malignancy and the metabolic syndrome are key challenges in modern health care. Population‐based data registries are potent enablers for research into possible associations between them, providing primers for further studies, including the elucidation of molecular and cellular mechanisms underlying such links.
Adolescent overweight and obesity and the risk for pancreatic cancer among men and women: a nationwide study of 1.79 million Israeli adolescents
Authors: Levi Zohar , Rottenberg Yakir , Twig Gilad , Katz Lior , Leiba Adi , Derazne Estela , Tzur Dorit , Eizenstein Sapir , Keinan‐Boker Lital , Afek Arnon , Kark Jeremy Dan
Published: November 2018

Background

There is growing concern regarding the impact of adolescent obesity on adult health. The objective of this study was to evaluate the association between body mass index (BMI) in late adolescence and the incidence of pancreatic cancer during adulthood.

Methods

The authors analyzed a cohort of 1087,358 Israeli Jewish men and 707,212 Jewish women who underwent a compulsory physical examination between ages 16 and 19 years from 1967 to 2002. Pancreatic cancer incidence through December 31, 2012 was identified by linkage to the national cancer registry. Multivariable‐adjusted Cox regression was used to estimate hazard ratios (HRs) for pancreatic cancer according to the US Centers for Disease Control and Prevention (CDC) BMI percentiles at baseline.

Results

Over a median 23 year follow‐up, 551 incident cases of pancreatic cancer cases occurred (423 men; 128 women). Compared with normal weight (5th to‐<85th percentile), obesity (≥95th percentile) was associated with an increased risk of cancer among both men (HR, 3.67; 95% confidence interval [CI], 2.52‐5.34) and women (HR, 4.07; 95% CI, 1.78‐9.29). Among men, compared with low‐normal BMI (≥5th to <25th percentile), high‐normal BMI (≥75th to <85th percentile) and overweight (85th to 95th percentile) also were associated with a higher risk for cancer(high‐normal BMI: HR, 1.49; 95% CI, 1.05‐2.13; overweight: HR, 1.97; 95% CI, 1.39‐2.80). The estimated population‐attributable fraction because of overweight and obesity was 10.9% (95% CI, 6.1%‐15.6%).

Conclusions

Men and women who were obese or overweight as adolescents are at an increased risk for subsequent pancreatic cancer.
Marked interspecific differences in the neuroanatomy of the male olfactory system of honey bees (genus Apis)
Authors: Bastin Florian , Couto Antoine , Larcher Virginie , Phiancharoen Mananya , Koeniger Gudrun , Koeniger Nikolaus , Sandoz Jean‐Christophe
Published: November 2018

All honey bee species (genus Apis) display a striking mating behavior with the formation of male (drone) congregations, in which virgin queens mate with many drones. Bees' mating behavior relies on olfactory communication involving queen—but also drone pheromones. To explore the evolution of olfactory communication in Apis, we analyzed the neuroanatomical organization of the antennal lobe (primary olfactory center) in the drones of five species from the three main lineages (open‐air nesting species: dwarf honey bees Apis florea and giant honey bees Apis dorsata; cavity‐nesting species: Apis mellifera, Apis kochevnikovi, and Apis cerana) and from three populations of A. cerana (Borneo, Thailand, and Japan). In addition to differences in the overall number of morphological units, the glomeruli, our data reveal marked differences in the number and position of macroglomeruli, enlarged units putatively dedicated to sex pheromone processing. Dwarf and giant honey bee species possess two macroglomeruli while cavity‐nesting bees present three or four macroglomeruli, suggesting an increase in the complexity of sex communication during evolution in the genus Apis. The three A. cerana populations showed differing absolute numbers of glomeruli but the same three macroglomeruli. Overall, we identified six different macroglomeruli in the genus Apis. One of these (called MGb), which is dedicated to the detection of the major queen compound 9‐ODA in A. mellifera, was conserved in all species. We discuss the implications of these results for our understanding of sex communication in honey bees and propose a putative scenario of antennal lobe evolution in the Apis genus.
Revisiting the Origin of Bacterial Bioluminescence: QM/MM Study on Oxygenation Reaction of Reduced Flavin in Protein
Authors: Luo Yanling , Liu Ya‐Jun
Published: November 2018

Bacterial bioluminescence is initiated by the oxygenation reaction of reduced flavin mononucleotide in luciferase. This enzymatic oxygenation occurs in a wide range of biological processes including cellular redox metabolism, biocatalysis, biosynthesis and homeostasis. However, little is known about the mechanism of the enzymatic reaction between singlet reduced flavin and triplet oxygen. To explore the enigmatic oxygenation, for the first time, the reaction of reduced flavin anion with oxygen was studied in bacterial luciferase by a combined quantum mechanics and molecular mechanics method as well as molecular dynamics simulation. The calculated results demonstrate that the reaction proceeds via a proton‐coupled electron transfer (PCET) pathway, and the essential αHis44 acts as a catalytic acid to provide the proton. The currently proposed PCET mechanism clearly describes the initial steps of bacterial bioluminescence, and could be suitable for the other flavin oxygenation reactions in enzymes.
α‐ and β‐Lapachone Isomerization in Acidic Media: Insights from Experimental and Implicit/Explicit Solvation Approaches
Authors: Delarmelina Maicon , Nicoletti Caroline D. , de Moraes Marcela C. , Futuro Debora O. , Bühl Michael , de C. da Silva Fernando , Ferreira Vitor F. , de M. Carneiro José W.
Published: November 2018

Combined experimental and mixed implicit/explicit solvation approaches were employed to gain insights into the origin of switchable regioselectivity of acid‐catalyzed lapachol cyclization and α‐/β‐lapachone isomerization. It was found that solvating species under distinct experimental conditions stabilized α‐ and β‐lapachone differently, thus altering the identity of the thermodynamic product. The energy profile for lapachol cyclization revealed that this process can occur with low free‐energy barriers (lower than 8.0 kcal mol−1). For α/β isomerization in a dilute medium, the computed enthalpic barriers are 15.1 kcal mol−1 (α→β) and 14.2 kcal mol−1 (β→α). These barriers are lowered in concentrated medium to 11.5 and 12.6 kcal mol−1, respectively. Experimental determination of isomers ratio was quantified by HPLC and NMR measurements. These findings provide insights into the chemical behavior of lapachol and lapachone derivatives in more complex environments.
BrdU incorporation in multiparameter flow cytometry: A new cell cycle assessment approach in multiple myeloma
Authors: Requirand Guilhem , Robert Nicolas , Boireau Stéphanie , Vincent Laure , Seckinger Anja , Bouhya Salaheddine , Ceballos Patrice , Cartron Guillaume , Hose Dirk , Klein Bernard , Moreaux Jérôme
Published: November 2018

Background

Mutiple myeloma (MM) is a neoplasia characterized by the accumulation of malignant plasma cells (PC) in the bone marrow. Although proliferation markers have been studied in MM, none of the current staging systems include them. Moreover, approaches used to analyze proliferation do not separate MM cells (MMCs) from normal PC.

Methods

In this study, we combined multiparameter flow cytometry and BrdU incorporation or Ki67 staining to analyze MM cell proliferation in 44 monoclonal gammopathy of undetermined significance (MGUS), 153 newly diagnosed MM patients and 69 MM patients at relapse. The prognostic value of proliferation assessment was analyzed in 60 newly diagnosed patients treated with high‐dose chemotherapy supported by autologous hematopoietic stem cell transplantation.

Results

The median number of proliferating malignant PC significantly increases during MM disease progression. MM patients with a percentage of proliferating MMCs greater than 1.42% using BrdU/DAPI or greater than 1.1% using ki67/DAPI, are associated with a significantly shorter event free survival compared with patients with a lower percentage of proliferating MMCs.

Conclusions

Combination of flow cytometry with BrdU or ki67/DAPI staining could become a standard for the determination of MM cell proliferation. Furthermore, in the context of new effective myeloma treatment options, assessment of MM cell proliferation may be valuable, in clinical trials, to identify novel agents that could significantly affect the small proliferative compartment of MM cells. © 2018 International Clinical Cytometry Society.
Variation in three community features across habitat types and scales within a 15‐ha subtropical evergreen‐deciduous broadleaved mixed forest dynamics plot in China
Authors: Feng Guang , Li Jun‐Qing , Zang Run‐Guo , Ding Yi , Ai Xun‐Ru , Yao Lan
Published: November 2018

The evergreen and deciduous broadleaved mixed forests (EDBMFs) belong to one of the ecosystems most sensitive to environmental change, however, little is known about the environmental determinants for their plant diversity and forest structure at different habitat types and spatial scales. Here, we used data from a 15‐ha (300 × 500 m) forest dynamic plot (FDP) of an old‐growth EDBMF to examine the patterns and determinants of the three community features (stem abundance, rarefied species richness and basal area [BA]) in three habitat types (ridge, hillside and foothill) and at three spatial scales (20 × 20 m, 50 × 50 m, and 100 × 100 m). We found that the three community features significantly changed with habitat type, but only one of them (rarefied richness) changed with scale. Among spatial scales, the principle environmental factors that widely affected community features were pH, soil organic matter, and total phosphorus, while these effects only taken place at certain habitat. Variations in the three community features explained by soil conditions were generally greater than those explained by topographical conditions. With changes in habitat type, the proportion of variations explained by environmental conditions was 31%–53%, 8%–25%, and 18%–26% for abundance, rarefied richness, and BA, respectively. With increasing spatial scale, the variations explained by environmental conditions were 44%–75% for abundance, 28%–95% for rarefied richness, and 18%–86% for BA. Our study demonstrated that environmental factors had great impacts on the plant diversity and forest structure in the EDBMFs, especially the soil factors such as pH. In addition, the importance of the environmental determinants on these community features was highly related to the spatial scale.
A unified concept of dominance applicable at both community and species scales
Authors: Ma Zhanshan (Sam) , Ellison Aaron M.
Published: November 2018

Dominance and evenness can be two sides of the same coin or opposite ends of a spectrum. Although evenness and diversity are community‐level concepts, dominance can be applied at both community and species scales. Nevertheless, there is not a metric applicable at both these scales that are unified with a single mathematical framework in the existing literature. Here, by extending Lloyd's meaning crowding concept from the population to community scale, we propose a dominance concept and associated metrics that are applicable at both scales. Such metrics can act as proxies for diversity in diversity–stability and diversity–ecosystem service analyses or for population abundance in species interaction network analysis and population stability analysis, with advantages in cross‐scale and unified analyses. Our concept of dominance includes three measures (metrics) that link communities and species. The metrics have the same mathematical form, but different interpretations at the community and species scales. Our community‐level metric is a function of Simpson's () diversity index, for which we present a rigorous mathematical proof. Our species‐level metrics quantify the difference between community dominance and the dominance of a virtual community whose mean population size, per species, equals the population size of the focal species. We demonstrate the use of these metrics using data from a longitudinal study of the human vaginal microbiome and provide new insights relevant for microbiome stability and disease etiology at the community scale. The new metrics also can be used for species dominance network (SDN) analysis at the species scale. Since the species dominance is a function of both species (population) abundance and community dominance, it has an advantage of capturing both community‐scale global and species‐scale local information, which becomes even more evident when it is used to construct SDNs. These results demonstrate the significance and applications of our unified dominance concept and metrics.
The Reactivity of FeII and CoII Disulfide Compounds with Dihydrogen Peroxide
Authors: Jiang Feng , Siegler Maxime A. , Bouwman Elisabeth
Published: November 2018

The reactivity of two metal disulfide compounds [MII2(L1SSL1)Cl4] {M = Fe and Co, L1SSL1 = di‐2‐[bis(2‐pyridylmethyl)amino]ethyl disulfide} with dihydrogen peroxide has been investigated. Reaction of the iron(II) disulfide compound [FeII2(L1SSL1)Cl4] with H2O2 results in the formation of the mononuclear iron(III) sulfonate compound [FeIII(L1SO3)Cl2]. The crystal structure combined with EPR spectroscopy confirms that a high‐spin (S = 5/2) iron(III) center was generated, which is coordinated by three nitrogen donors and one oxygen atom of the sulfonate group of the tetradentate ligand, and two chloride ions in an octahedral geometry. In contrast, reaction of compound [CoII2(L1SSL1)Cl4] with H2O2 yielded the mononuclear cobalt(III) sulfinate compound [CoIII(L1SO2)Cl2]. The crystal structure and NMR spectroscopy show that in this case a low‐spin (S = 0) cobalt(III) center was obtained, which is coordinated by three nitrogen donors and one sulfur atom of the sulfinate group of the tetradentate ligand and two chloride ions in an octahedral geometry.
Construction of Crystalline One‐Dimensional Infinite Argentophilic Silver Alkynyl Assemblies and their Luminescence Properties
Authors: Yang Yang , Zhang Shan‐Shan , Zhao Quan‐Qin , Wang Xing‐Po , Tung Chen‐Ho , Sun Di
Published: November 2018

Four crystalline one‐dimensional (1‐D) silver alkynyl assemblies, namely, [Ag11(tBuC≡C)7(CH3COO)4]n (1), [Ag21(tBuC≡C)11(PhCOO)10]n (2), [Ag16(m‐F‐PhC≡C)12(CF3COO)4(CH3CN)4]n (3) and [Cl@Ag14(PhC≡C)10(CF3SO3)3]n (4). have been obtained by reacting polymeric [AgC≡CR]n with silver salts under mild solvothermal conditions. Compound 1 and 3 are coordination polymer of irregular silver alkynyl clusters. Compound 2 consists of well‐defined parallel Ag3 triangles columns. Compound 4 is chains of chloride templated cage‐like silver clusters. Compound 2–4 show temperature‐sensitive luminescent behaviors. Amongst, compound 2 and 3 display dual‐emissive characteristic at low temperature. By correlating the structures and properties of four silver compounds, we found that the non‐emissive behavior of compound 1 could be tentatively assigned to the absence of any aryl groups on the ligands.
Halide‐Substituted Phosphacyclohexadienyl Iron Complexes: Covalent Structures vs. Ion Pairs
Authors: Hoidn Christian M. , Leitl Julia , Ziegler Christoph G. P. , Shenderovich Ilya G. , Wolf Robert
Published: November 2018

The coordination chemistry of phosphinines (phosphabenzenes) has been intensively investigated over the last decades, but metal complexes of halophosphinines and related halide‐substituted phosphacyclohexadienyls have remained scarce. Here, we describe the synthesis of a series of complexes [Cp*Fe(1‐F‐PC5Ph3H2)] (2‐F, Cp* = C5Me5), [Cp*Fe(1‐Cl‐PC5Ph3H2)] (2‐Cl), [Cp*Fe(PC5Ph3H2)]Br (2‐Br) and [Cp*Fe(PC5Ph3H2)]I (2‐I), which were obtained by reacting the previously reported 2,4,6‐triphenylphosphinine iron complex [K([18]crown‐6)(thf)2] [Cp*Fe(PC5Ph3H2)] (1) with electrophilic halogenating agents. To the best of our knowledge, 2‐F and 2‐Cl are the first π‐coordinated λ3‐halophosphacyclohexadienyl complexes with covalent P–X bonds (X = halogen). In the solid state 2‐Br and 2‐I show ionic structures with [Cp*Fe(PC5Ph3H2)]+ cations and separated X– anions. Anion exchange of I– in 2‐I for [BArF4]– {ArF = 3,5‐(CF3)2C6H3} affords [Cp*Fe(PC5Ph3H2)][BArF4] (2‐[BArF4]), which also displays an ionic structure. These new complexes were further characterized by solid‐state and solution 31P NMR spectroscopy, UV/Vis spectroscopy, elemental analyses, electrical conductivity measurements in solution, and DFT calculations. The resulting data indicate that 2‐F retains its covalent P–F bond in THF, fluorobenzene, and acetonitrile solution, while the remaining 2‐X complexes containing heavier halogen atoms (X = Cl, Br, and I) apparently form ion pairs in such solvents.
Visible‐Light Promoted Stereoselective Arylselanyl Functionalization of Alkynes
Authors: Weber Andressa C. H. , Coelho Felipe L. , Affeldt Ricardo F. , Schneider Paulo H.
Published: November 2018

Functionalization of double bonds with arylselenium groups found in the literature, commonly uses high temperatures in the presence of metal catalysts, reducing agents or other additives. In this context, this work presents a series of bis‐arylselanyl olefins synthesized by photoinduced reaction without heating or additives. Since the absorption range of the diselenide comprises the UV/Visible region of spectra, a mixture of arylacetylene and diaryl diselenide in dichloromethane was irradiated with white light from compact (household) fluorescent lamp. The optimized procedure allows preparation of E‐olefins due to radical addition followed by photoisomerization with low cost and low environmental impact.