bluuebunny/crossref_metadata_2025 huggingface dataset:
Activating Basal Planes of NiPS3 for Hydrogen Evolution by Nonmetal Heteroatom Doping
Authors: Wang Jun , Li Xinzhe , Wei Bin , Sun Rong , Yu Wei , Hoh Hui Ying , Xu Haomin , Li Jing , Ge Xingbo , Chen Zuxin , Su Chenliang , Wang Zhongchang
Published: February 2020

NiPS3, one of the most promising catalysts among transition metal trichalcogenidophosphates (MTPs) in hydrogen evolution reaction (HER) electrocatalysis, is still inhibited by its unsatisfactory activity originating from its semiconducting nature and inert basal plane. Here, it is proposed, for the first time, to engineer the basal surface activity of NiPS3 by nonmetal heteroatom doping, and predict that the degree to which the valance band of NiPS3 is filled dominates not only the electrical conductivity of the catalyst, but also the strength of hydrogen adsorption at its surface. Direct experimental evidence is offered that in all the single nonmetal doping samples, C‐doped NiPS3 exhibits the optimum activity owing to its moderate filled state of valance band and that C, N codoping even shows Pt‐like activity with an ultralow overpotential of 53.2 mV to afford 10 mA cm−2 current density and a high exchange current density of 0.7 mA cm−2 in 1 m KOH. The findings that less valance electrons of dopants than substitutional atoms are of pivotal importance for improving HER activity of NiPS3 catalyst pave the way for readily designing novel MTPs of ever high performance to replace the incumbent Pt‐based catalysts.
Local Defects in Colloidal Quantum Dot Thin Films Measured via Spatially Resolved Multi‐Modal Optoelectronic Spectroscopy
Authors: Lin Yida , Gao Tina , Pan Xiaoyun , Kamenetska Maria , Thon Susanna M.
Published: February 2020

The morphology, chemical composition, and electronic uniformity of thin‐film solution‐processed optoelectronics are believed to greatly affect device performance. Although scanning probe microscopies can address variations on the micrometer scale, the field of view is still limited to well under the typical device area, as well as the size of extrinsic defects introduced during fabrication. Herein, a micrometer‐resolution 2D characterization method with millimeter‐scale field of view is demonstrated, which simultaneously collects photoluminescence spectra, photocurrent transients, and photovoltage transients. This high‐resolution morphology mapping is used to quantify the distribution and strength of the local optoelectronic property variations in colloidal quantum dot solar cells due to film defects, physical damage, and contaminants across nearly the entire test device area, and the extent to which these variations account for overall performance losses. It is found that macroscopic defects have effects that are confined to their localized areas, rarely prove fatal for device performance, and are largely not responsible for device shunting. Moreover, quantitative analysis based on statistical partitioning methods of such data is used to show how defect identification can be automated while identifying variations in underlying properties such as mobilities and recombination strengths and the mechanisms by which they govern device behavior.
Bioinspired Fluffy Fabric with In Situ Grown Carbon Nanotubes for Ultrasensitive Wearable Airflow Sensor
Authors: Wang Haomin , Li Shuo , Wang Yiliang , Wang Huimin , Shen Xinyi , Zhang Mingchao , Lu Haojie , He Maoshuai , Zhang Yingying
Published: February 2020

Recently, electronic skin and smart textiles have attracted considerable attention. Flexible sensors, as a kind of indispensable components of flexible electronics, have been extensively studied. However, wearable airflow sensors capable of monitoring the environment airflow in real time are rarely reported. Herein, by mimicking the spider's fluff, an ultrasensitive and flexible all‐textile airflow sensor based on fabric with in situ grown carbon nanotubes (CNTs) is developed. The fabric decorated with fluffy‐like CNTs possesses exceptionally large contact area, endowing the airflow sensor with superior properties including ultralow detection limit (≈0.05 m s−1), multiangle airflow differential response (0°–90°), and fast response time (≈1.3 s). Besides, the fluffy fabric airflow sensor can be combined with a pristine fabric airflow sensor to realize highly sensitive detection in a wide airflow range (0.05–7.0 m s−1). Its potential applications including transmitting information according to Morse code by blowing the sensors, monitoring increasing and decreasing airflow velocity, and alerting blind people walking outside about potential hazard induced by nearby fast‐moving objects are demonstrated. Furthermore, the airflow sensor can be directly integrated into clothing as stylish designs without sacrificing comfortness. It is believed that the ultrasensitive all‐textile airflow sensor holds great promise for applications in smart textiles and wearable electronics.
Bicyclo[1.1.1]pentyl Sulfoximines: Synthesis and Functionalizations
Authors: Bär Robin M. , Langer Lukas , Nieger Martin , Bräse Stefan
Published: February 2020

Herein we present the first synthesis of bicyclo[1.1.1]pentyl (BCP) sulfoximines from the corresponding sulfides. Both BCPs and sulfoximines are bioisosteres used in medicinal chemistry and therefore desirable motifs. The access to BCP sulfides was enabled by the thiol addition to [1.1.1]propellane as published before. A broad scope with specific limitations was discovered for the sulfoximination. To diversify the sulfoximines, N‐acylations and N‐arylations were performed. As the N‐arylation was low yielding we optimized the copper(I) catalyzed reaction. A wide range of aryl iodides could be deployed and competitive reactions showed that aryl bromides react equally fast. In a scale‐up we prepared a suitable precursor for a BCP drug analogue. In this work several molecular structures could be determined by single‐crystal X‐ray diffraction.

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Copper‐Catalyzed Selective Pyrrole Functionalization by Carbene Transfer Reaction
Authors: Rodríguez Anabel M. , Molina Francisco , Díaz‐Requejo M. Mar , Pérez Pedro J.
Published: February 2020

1H‐Pyrroles can be directly functionalized by means of the incorporation of carbene groups from diazo compounds, in a process catalyzed by TpxCu complexes (Tpx=hydrotrispyrazolylborate ligand). The reactions take place with a complete selectivity toward the formal insertion of the carbene into the Cα−H bond, leading to alkylated pyrroles, with no modification of the Cβ−H, N−H or C=C bonds of the pyrrole unit. Alkyl substituents at C‐ring as well as alkyl, aryl, allyl or alkyne substitution at N atom are tolerated, the strategy affording 20 new pyrrole derivatives. The observance of partial deuteration at the methylene group when the reaction is carried out with added D2O serves to discard the direct insertion of the carbene group into the Csp2−H bond, the alternative electrophilic attack to the pyrrole ring being feasible.

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Iodine Mediated Base‐Controlled Regio‐Selective Annulation of 2‐(Pyridin‐2‐yl)acetate Derivatives with Acrylic Esters for the Synthesis of Indolizines
Authors: Fang Youlai , Li Fei , Yang Yuzhu , Liu Xiaolan , Pan Weidong
Published: February 2020

An iodine mediated base‐controlled reaction between 2‐(pyridin‐2‐yl)acetate derivatives and acrylic esters has been developed for the selective synthesis of 1,3‐disubstituted indolizines and 1,2‐disubstituted indolizines. A single‐pot reaction of 2‐(pyridin‐2‐yl)acetate derivatives and acrylic esters in the presence of CsOAc delivers 1,3‐disubstitued indolizines, while KHCO3 promotes the formation of C3‐iodo indolizines, which could be further de‐iodinated in the presence of copper powder, affording 1,2‐disubstituted indolizines via a sequential stepwise fashion. A plausible reaction mechanism involving radical process has been proposed for this reaction. Pd‐catalzyed reaction of C3‐iodo indolizines with aryl boronic acids has been described.

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Porous PEI Coating for Copper Ion Storage and Its Controlled Electrochemical Release
Authors: Elmas Sait , Gedefaw Desta A. , Larsson Mikael , Ying Yanting , Cavallaro Alex , Andersson Gunther G. , Nydén Magnus , Andersson Mats R.
Published: February 2020

The use of copper‐based chemicals to prevent biological growth has been widely practiced in the past. However, leaching of the copper has increased concentrations in ports and marinas, posing a risk to marine life and the environment. It is therefore timely to develop a sustainable antibiofouling coating that could replace conventional copper‐based paints. Herein, the use of cross‐linked polyethylene imine (PEI) coated on conducting carbon cloth electrodes as a material that can absorb copper from seawater and allow for controlled electrochemical release of copper as a biocide to prevent biofouling is proposed. The results show that the porous coating can store and release copper ions over multiple cycles by passing only 1 mA cm−2 current density through the electrode in artificial seawater. This could enable a closed‐cycle, copper‐based antifouling coating, i.e., a coating that uses the well‐established biocidal activity of copper, but without any net release to the ocean.
Robust High‐Capacitance Polymer Gate Dielectrics for Stable Low‐Voltage Organic Field‐Effect Transistor Sensors
Authors: Rahmanudin Aiman , Tate Daniel J. , Marcial‐Hernandez Raymundo , Bull Nicholas , Garlapati Suresh K. , Zamhuri Adibah , Khan Raja U. , Faraji Sheida , Gollu Sankara R. , Persaud Krishna. C. , Turner Michael L.
Published: February 2020

Organic field‐effect transistors (OFETs) have shown great promise for use as chemical sensors for applications that range from the monitoring of food spoilage to the determination of air quality and the diagnosis of disease. However, for these devices to be truly useful, they must deliver reliable and stable low‐voltage operation over extended timescales. An important element to address this challenge is the development of a high‐capacitance gate dielectric that delivers excellent insulation with robust chemical resistance against the solution processing of organic semiconductors (OSC). The development of a bilayer gate dielectric containing a high‐k fluoropolymer relaxor ferroelectric layer modified at the OSC/dielectric interface with a photo‐crosslinked chemically resistant low‐k methacrylate‐based copolymer buffer layer is reported. Bottom‐gate OFET chemical sensors using this bilayer dielectric operate at low‐voltage with exceptional operational stability. They deliver reliable sensing performance over multiple cycles of ammonia exposure (2 to 50 ppm) with an estimated limit‐of‐detection below 1 ppm.
Response of agronomic crops to planting date and double‐cropping with wheat
Authors: Hare Andrew T. , Jordan David L. , Edmisten Keith L. , Leon Ramon G. , Post Angela R. , Vann Rachel , Dunphy E. James , Heiniger Ronnie , Collins Guy , Washburn Derek
Published: February 2020

Planting date can affect crop yield and is an important management decision for practitioners. Although wheat (Triticum aestivumL.) and soybean [Glycine max(L.) Merr.] can be effectively double‐cropped in North Carolina, if commodity prices and projected economic returns are higher for crops other than soybean, growers might consider a nontraditional, double‐crop system. Direct comparisons of major agronomic crops with different planting dates or in a double‐crop system with wheat are limited in North Carolina. Therefore, research was conducted in North Carolina from 2013 through 2017 to determine yield potential of corn (Zea maysL.), cotton (Gossypium hirsutumL.), grain sorghum [Sorghum bicolor(L.) Moench], peanut (Arachis hypogaeaL.), and soybean planted at two dates within the recommended planting window for full‐season production versus planting these crops after wheat harvest. The experimental design was a split plot, with summer crop serving as the whole plot unit and planting date within a crop serving as the subplot unit. Yield of corn, cotton, grain sorghum, peanut, and soybean in full‐season production exceeded that of double‐cropping with wheat in 5, 5, 2, 4, and 5 yr out of 5 yr of the study, respectively. Estimated economic returns were generated using the 10‐yr average (2008–2017) summer crop prices with the 10‐yr average wheat price. When considering all possible combinations of years and crops (n = 25), in only 20% of the possible combinations was the economic return of the double‐cropping system greater than economic return of full‐season crop production when compared with at least one of the planting dates within the traditional planting window.
Impact of minimal residual negativity using next generation flow cytometry on outcomes in light chain amyloidosis
Authors: Sidana Surbhi , Muchtar Eli , Sidiqi M. Hasib , Jevremovic Dragan , Dispenzieri Angela , Gonsalves Wilson , Buadi Francis , Lacy Martha Q. , Hayman Suzanne R. , Kourelis Taxiarchis , Kapoor Prashant , Go Ronald S. , Warsame Rahma , Leung Nelson , Rajkumar S. Vincent , Kyle Robert A. , Gertz Morie A. , Kumar Shaji K.
Published: February 2020

We evaluated bone marrow minimal residual disease (MRD) negativity in 44 patients with light chain (AL) amyloidosis using next generation flow cytometry (sensitivity ≥1 × 10−5; median events analyzed: 8.7 million, range: 4.8 to 9.7 million). All patients underwent MRD testing in 2 years from start of therapy (median: 7 months). The overall MRD negative rate was 64% (n = 28). The MRD‐negative rate after one‐line of therapy was 71% (20/28). And, MRD negative rates were higher with stem‐cell transplant as first‐line therapy (86%, 18/21) vs chemotherapy alone as first‐line treatment (29%, 2/7), P = .005. The MRD negative rate amongst patients in complete response was 75% (15/20), and in very good partial response, 50% (11/22). There were two patients in partial response/rising light chains (with renal dysfunction) who were MRD negative. There were no differences in baseline characteristics of MRD negative vs MRD positive patients, except younger age amongst MRD‐negative patients. Patients with MRD negativity were more likely to have achieved cardiac response at the time of MRD assessment, 67% (8/12) vs 22% (2/7), P = .04. Renal response rates were similar in both groups. Progression free survival was assessed in the 42 patients achieving CR or VGPR. After median follow‐up of 14 months, the estimated 1‐year progression free survival in MRD negative vs MRD positive patients was 100% (26 patients, 0 events) vs 64% (16 patients, five events), P = .006, respectively. MRD assessment should be explored as a surrogate endpoint in clinical trials and MRD risk‐adapted trials may help optimize treatment in AL amyloidosis.
Joy and Challenges of Alkynylation of Arenes and Heteroarenes through Double C−H Functionalizations
Authors: Panda Biswajit
Published: February 2020

A significant number of reactions have appeared in the literature regarding direct oxidative cross‐coupling of arenes and heteroarenes with terminal alkynes achieved through functionalization of C(SP2)−H and C(SP)−H bonds to provide the corresponding alkynylated products. The delights and difficulties of the direct alkynylation have been discussed thoroughly to enlighten this growing area. More emphasis is given to the successful implementation and improvement of various protocols for this transformation. Wherever necessary, the uniqueness of the methods has been shown by highlighting the substrate scope, selectivity, yields along with mechanistic consideration.
Do functional traits offset the effects of fragmentation? The case of large‐bodied diurnal lemur species
Authors: Eppley Timothy M. , Santini Luca , Tinsman Jen C. , Donati Giuseppe
Published: February 2020

Primates worldwide are faced with increasing threats making them more vulnerable to extinction. Anthropogenic disturbances, such as habitat degradation and fragmentation, are among the main concerns, and in Madagascar, these issues have become widespread. As this situation continues to worsen, we sought to understand how fragmentation affects primate distribution throughout the island. Further, because species may exhibit different sensitivity to fragmentation, we also aimed to estimate the role of functional traits in mitigating their response. We collated data from 32 large‐bodied lemur species ranges, consisting of species from the families Lemuridae (five genera) and Indriidae (two genera). We fitted Generalized Linear Models to determine the role of habitat fragmentation characteristics, for example, forest cover, patch size, edge density, and landscape configuration, as well as the protected area (PA) network, on the species relative probability of presence. We then assessed how the influence of functional traits (dietary guild, home range size) mitigate the response of species to these habitat metrics. Habitat area had a strong positive effect for many species, and there were significantly negative effects of fragmentation on the distribution of many lemur species. In addition, there was a positive influence of PAs on many lemur species’ distribution. Functional trait classifications showed that lemurs of all dietary guilds are negatively affected by fragmentation; however, folivore‐frugivores show greater flexibility/variability in terms of habitat area and landscape complexity compared to nearly exclusive folivores and frugivores. Furthermore, species of all home range sizes showed a negative response to fragmentation, while habitat area had an increasingly positive effect as home range increased in size. Overall, the general trends for the majority of lemur species are dire and point to the need for immediate actions on a multitude of fronts, most importantly landscape‐level reforestation efforts.
Visible‐Light Photocatalysis of Asymmetric [2+2] Cycloaddition in Cage‐Confined Nanospace Merging Chirality with Triplet‐State Photosensitization
Authors: Guo Jing , Fan Yan‐Zhong , Lu Yu‐Lin , Zheng Shao‐Ping , Su Cheng‐Yong
Published: February 2020

Although the photodimerization of acenaphthylene (ACE) has been known for 100 years, the asymmetric cycloaddition of its 1‐substituted derivatives is unknown. Herein, we report a supramolecular photochirogenic approach in which a homochiral and photoactive Δ/Λ‐[Pd6(RuL3)8]28+ metal–organic cage (Δ/Λ‐MOC‐16) is used as a supramolecular reactor for the enantioselective exited‐state photocatalysis of 1‐Br‐ACE. Owing to preorganization of the substrates by the supramolecular cage, stereochemical control of the triplet state, and nanospace transfer of energy and chirality, the cycloaddition of ACE proceeded with high selectivity for the formation of anti over syn stereoisomers, whereas the regio‐, stereo‐, and enantioselective cycloaddition of unsymmetrical 1‐Br‐ACE showed effective enantiodifferentiation of a pair of anti head‐to‐head stereoisomers. The enzyme‐mimicking photocatalysis was verified by catalytic turnover, rate enhancement, and competing‐guest inhibition experiments.
Multiple‐State Emissions from Neat, Single‐Component Molecular Solids: Suppression of Kasha's Rule
Authors: Wu Ya‐Hang , Xiao Hongyan , Chen Bin , Weiss Richard G. , Chen Yu‐Zhe , Tung Chen‐Ho , Wu Li‐Zhu
Published: February 2020

Three rigid and structurally simple heterocyclic stilbene derivatives, (E)‐3H,3′H‐[1,1′‐biisobenzofuranylidene]‐3,3′‐dione, (E)‐3‐(3‐oxobenzo[c] thiophen‐1(3H)‐ylidene)isobenzofuran‐1(3H)‐one, and (E)‐3H,3′H‐[1,1′‐bibenzo[c] thiophenylidene]‐3,3′‐dione, are found to fluoresce in their neat solid phases, from upper (S2) and lowest (S1) singlet excited states, even at room temperature in air. Photophysical studies, single‐crystal structures, and theoretical calculations indicate that large energy gaps between S2 and S1 states (T2 and T1 states) as well as an abundance of intra and intermolecular hydrogen bonds suppress internal conversions of the upper excited states in the solids and make possible the fluorescence from S2 excited states (phosphorescence from T2 excited states). These results, including unprecedented fluorescence quantum yields (2.3–9.6 %) from the S2 states in the neat solids, establish a unique molecular skeleton for achieving multi‐colored emissions from upper excited states by “suppressing” Kasha's rule.
The Structure of Water Bonded to Phosphate Groups at the Electrified Zwitterionic Phospholipid Membranes/Aqueous Interface
Authors: Li Shanshan , Wu Lie , Zhang Xiaofei , Jiang Xiue
Published: February 2020

Gaining insight into the water structure at the electrified phospholipid membranes/aqueous interface is vital and essential for elucidating the mechanism of many biochemical reactions, but still remains a formidable challenge. Herein, based on the superiority of surface enhanced infrared absorption (SEIRA) spectroscopy combined with electrochemistry in interfacial analysis, the evolution of local water structure at the zwitterionic phospholipid membranes/aqueous interface with an external electric field is revealed by means of ion perturbation. The strongly hydrogen‐bonded water directly bonded to the phosphate groups (PO2−) has a strong mechanical strength to resist potential perturbations, and that portion of water greatly affects the electrostatic properties of the phospholipid membranes. This study innovates the basic understanding of electric double layer (EDL) at the membranes/aqueous interface.
Adsorption Properties of Hydrated Cr3+ Ions on Schiff‐base Covalent Organic Frameworks: A DFT Study
Authors: Wei Dongli , Zhang Anrui , Ai Yuejie , Wang Xiangke
Published: February 2020

Considering the superior physiochemical property, increasing efforts have been devoted to exploiting the covalent organic frameworks (COFs) materials on the environmental remediation of heavy metal ions. Water pollution caused by Cr3+ metal ions is of special concern for scientists and engineers. Notwithstanding all the former efforts made, it is surprising that very little is known about the interaction mechanisms between the hydrated Cr3+ metal ions and COF materials. In present context, density functional theory (DFT) method is used to elucidate geometric and electronic properties with the purpose of putting into theoretical perspective the application values and interaction mechanisms for COF materials on Cr3+ capture. The results showed that all the five selected Schiff‐base COFs materials displayed good adsorption performance on Cr3+ removal while the phenazine‐linked and imine‐COFs possessed the most favorable adsorption capacity due to the optimal chemical units and frameworks. The hydration effect was found to play a two‐side role in the adsorption process and interaction mechanisms, involving coordination, hydrogen bonds, as well as weak non‐covalent interactions, have been illuminated to explain the observed different adsorption behaviors. This study provides a general guidance for the design and selection of efficient COF materials as high‐capacity Cr3+ adsorbents.
Shear stress computation in a millimeter thin flat panel photobioreactor: Numerical design validated by experiments
Authors: Jiang Wenbiao , Levasseur Wendie , Casalinho Joel , Martin Thierry , Puel François , Perré Patrick , Pozzobon Victor
Published: February 2020

Flat panels are the most spread type of photobioreactors for studying light effects on a microalgae culture. Their low thickness, usually between 1 and 3 cm, aims at ensuring light homogeneity across the culture. Yet because optical density has to remain very low, studies are still limited to low cell density cultures. To alleviate this problem, even thinner photobioreactors can be designed. Nevertheless, thin flat panel reactors are very prone to induce high shear stress. This work aimed at designing a new millimeter thin panel photobioreactor to study light effects on Chlorella and Scenedesmus genera. We proposed a numerical workflow that is capable of assessing the shear stress intensity in such a reactor. The numerical predictions were validated at three different levels: 2D preliminary simulations were able to reproduce bubble commonly known behaviors; close to the nozzle, the predictions were successfully confronted to shadowgraphy experimental reference; at the mini bioreactor scale, experimental and numerical mixing were found to be close. After these throughout validations, shear stress intensity in the photobioreactor was calculated over 1000 Lagrangian tracers. The experienced shear stress was agglomerated at the population level. From the computed shear stress, it was possible to choose the minimal reactor thickness that would not hinder cell growth.
A Bayesian spatiotemporal statistical analysis of out‐of‐hospital cardiac arrests
Authors: Peluso Stefano , Mira Antonietta , Rue Håvard , Tierney Nicholas John , Benvenuti Claudio , Cianella Roberto , Caputo Maria Luce , Auricchio Angelo
Published: February 2020

We propose a Bayesian spatiotemporal statistical model for predicting out‐of‐hospital cardiac arrests (OHCAs). Risk maps for Ticino, adjusted for demographic covariates, are built for explaining and forecasting the spatial distribution of OHCAs and their temporal dynamics. The occurrence intensity of the OHCA event in each area of interest, and the cardiac risk‐based clustering of municipalities are efficiently estimated, through a statistical model that decomposes OHCA intensity into overall intensity, demographic fixed effects, spatially structured and unstructured random effects, time polynomial dependence, and spatiotemporal random effect. In the studied geography, time evolution and dependence on demographic features are robust over different categories of OHCAs, but with variability in their spatial and spatiotemporal structure. Two main OHCA incidence‐based clusters of municipalities are identified.
Analysis of chemometric models applied to Raman spectroscopy for monitoring key metabolites of cell culture
Authors: Rafferty Carl , Johnson Kjell , O'Mahony Jim , Burgoyne Barbara , Rea Rosemary , Balss Karin M.
Published: February 2020

The Food and Drug Administration (FDA) initiative of Process Analytical Technology (PAT) encourages the monitoring of biopharmaceutical manufacturing processes by innovative solutions. Raman spectroscopy and the chemometric modeling tool partial least squares (PLS) have been applied to this aim for monitoring cell culture process variables. This study compares the chemometric modeling methods of Support Vector Machine radial (SVMr), Random Forests (RF), and Cubist to the commonly used linear PLS model for predicting cell culture components—glucose, lactate, and ammonia. This research is performed to assess whether the use of PLS as standard practice is justified for chemometric modeling of Raman spectroscopy and cell culture data. Model development data from five small‐scale bioreactors (2 × 1 L and 3 × 5 L) using two Chinese hamster ovary (CHO) cell lines were used to predict against a manufacturing scale bioreactor (2,000 L). Analysis demonstrated that Cubist predictive models were better for average performance over PLS, SVMr, and RF for glucose, lactate, and ammonia. The root mean square error of prediction (RMSEP) of Cubist modeling was acceptable for the process concentration ranges of glucose (1.437 mM), lactate (2.0 mM), and ammonia (0.819 mM). Interpretation of variable importance (VI) results theorizes the potential advantages of Cubist modeling in avoiding interference of Raman spectral peaks. Predictors/Raman wavenumbers (cm−1) of interest for individual variables are X1139–X1141 for glucose, X846–X849 for lactate, and X2941–X2943 for ammonia. These results demonstrate that other beneficial chemometric models are available for use in monitoring cell culture with Raman spectroscopy.
Digital manufacturing course framework for senior aircraft manufacturing engineering undergraduates
Authors: Liu Hao , Jin Xia
Published: February 2020

Digital manufacture is a necessary part of modern aircraft construction. It has grown from its application in traditional structural part milling to be incorporated into the majority of aircraft manufacturing processes. Consequently, there is an emerging need for innovation in digital manufacturing courses to remain current with these rapid changes in the aircraft industry. This study focused on developing a new digital curriculum including computer‐aided design, computer‐aided manufacture, computer‐aided engineering, computer numerical control, virtual assembly, and product data management. The study included a literature survey on digital manufacturing course designs in which the limitations to traditional teaching activities with respect to digital manufacture were identified. A trend survey of aircraft manufacturing technologies was also presented to determine the aircraft industry's expectations for their new employees. A new digital curriculum design was presented that incorporated both existing digital manufacturing fundamental theories and practical tools into the course content. Finally, evaluations were successfully conducted to verify the effectiveness of our new digital curriculum.
Mobile devices use in analyzing the engineering students attitude towards programming by using a fuzzy logic technique
Authors: Ozdemir Ali , Balbal Kadriye Filiz , Senel Berat Can
Published: February 2020

The aim of this study is to use mobile devices in the determination of engineering students' attitudes towards programming by using a fuzzy logic technique. First of all, a mobile game that is played by engineering students is developed to make learning programming more enjoyable. After that, the proposed fuzzy logic‐based attitude determination system which runs on mobile devices comes into play. Student answers and gives points between 1 and 5 to the survey questions which are presented by the developed mobile application. These points are first evaluated in the fuzzification step by using membership functions and then the fuzzied input is given to the rule base step. To get crisp output value, fuzzied output is defuzzified at the last step of the fuzzy logic‐based system. Hence the attitude of the student towards programming is inferenced. The developed system is carried out with 100 first‐grade students of the software engineering department. Frequency, mean, standard deviation, normality, t test, and analysis of variance (ANOVA) analyses are performed with the obtained data. Results show that the proposed fuzzy logic‐based system performs much better than the classical approach. As a result of Article Reliability Analysis of the Attitude Scale Towards Mobile Learning, the scale is found highly reliable. A significant difference is found in favor of fuzzy logic‐based attitude score among classical logic‐based attitude scores as a result of the paired‐samples t test. The results of t test and ANOVA tests according to gender, mother, and father education levels are found not statistically significant.
A new prognostic score for disease progression and mortality in patients with newly diagnosed primary CNS lymphoma
Authors: Liu Chia‐Jen , Lin Shinn‐Yn , Yang Ching‐Fen , Yeh Chiu‐Mei , Kuan Ai‐Seon , Wang Hao‐Yuan , Tsai Chun‐Kuang , Gau Jyh‐Pyng , Hsiao Liang‐Tsai , Chen Po‐Min , Liu Yao‐Chung , Hong Ying‐Chung , Ko Po‐Shen , Liu Jin‐Hwang , Lin Chia‐Hsin
Published: February 2020

Background

Although various prognostic models for primary central nervous system lymphoma (PCNSL) have been developed, there is no consensus regarding the optimal prognostic index. We aimed to evaluate potential prognostic factors and construct a novel predictive model for PCNSL patients.

Methods

We enrolled newly diagnosed PCNSL patients between 2003 and 2015. The primary endpoint was progression‐free survival (PFS), and the secondary endpoint was overall survival (OS). The prognostic factors identified using multivariate Cox proportional hazards models were used to develop a predictive model. We subsequently validated the prognostic model in an independent cohort. We also evaluated the validity of the existing scores: the International Extranodal Lymphoma Study Group (IELSG), the Nottingham/Barcelona (NB), and the Memorial Sloan‐Kettering Cancer Center models (MSKCC).

Results

We identified 101 patients with newly diagnosed PCNSL at our center. Multivariate analysis showed that age ≥80, deep brain lesions, and ECOG ≥2 were independent risk factors of PFS. Assigning one point for each factor, we constructed a novel prognostic model, the Taipei Score, with four distinct risk groups (0‐3 points). The performances of the Taipei Score in discriminating both PFS and OS in the training cohort were significant, and the score was validated in the external validation cohort. The IELSG, NB and MSKCC models had insufficient discriminative ability for either PFS or OS in both cohorts.

Conclusion

The Taipei Score is a simple model that discriminates PFS and OS for PCNSL patients. The score may offer disease risk stratification and facilitate clinical decision‐making.
Paving the Way for Practical Use of Sugar‐Binding Natural Products as Lectin Mimics in Glycobiological Research
Authors: Nakagawa Yu
Published: February 2020

Pradimicins (PRMs) constitute an exceptional class of natural products that show Ca2+‐dependent recognition of d‐mannose (Man). In addition to therapeutic uses as antifungal drugs, the application of PRMs as lectin mimics for glycobiological research has been attracting considerable interest, since the emerging biological roles of Man‐containing glycans have been highlighted. However, only a few attempts have been made to use PRMs for glycobiological purposes. The limited use of PRMs is primarily due to the early assumption that the readily modifiable carboxyl group of PRMs is involved in Ca2+ binding, and thus, not available to prepare research tools. Recently, this assumption has been disproved by structural elucidation of the Ca2+ complex of PRMs, which paves the way for designing carboxyl group modified derivatives of PRMs for research use. This article outlines studies related to Ca2+‐mediated Man binding of PRMs and discusses their application for glycobiology.
Hydroconversion of Perhydrophenanthrene over Bifunctional Pt/H‐USY Zeolite Catalyst
Authors: Brito Larissa , Pirngruber Gerhard D. , Guillon Emmanuelle , Albrieux Florian , Martens Johan A.
Published: February 2020

In petroleum refining, middle distillates are produced via hydroisomerization/hydrocracking processes using bifunctional catalysts often containing ultrastable Y (USY) zeolite. Petroleum fractions serving as feedstock for hydrocracking processes contain a majority of (poly)cyclic hydrocarbon molecules. Few studies on reaction mechanisms of hydrocracking of such polycyclic compounds are available. In this study the tricyclic phenanthrene molecule was used as model compound. Phenanthrene was hydrogenated on a Pt/alumina pre‐catalyst to perhydrophenanthrene, and subsequently hydrocracked over Pt/H‐USY zeolite. The feed consisted of 3 wt.% phenanthrene dissolved in n‐heptane. The reaction was performed at 280 °C and 60 bar, with a molar H2 to total hydrocarbon ratio of 7 mol/mol. The reaction products were analyzed using GCxGC‐FID/MS. This detailed analysis enabled identification of the reaction scheme involving skeletal isomerization, ring opening and fragmentation. New mechanistic insight is gained on relative reactivities of bridged and non‐bridged tricyclic naphthenes. Preferential hydrocracking routes were identified. The study provides insight in the products to be expected from polycyclic hydrocarbon isomerization and hydrocracking.
Approaching Dissolved Species in Ammonoacidic GaN Crystal Growth: A Combined Solution NMR and Computational Study
Authors: Becker Peter , Wonglakhon Tanakorn , Zahn Dirk , Gudat Dietrich , Niewa Rainer
Published: February 2020

Solutions of gallium trihalides GaX3 (X=F, Cl, Br, I) and their ammoniates in liquid ammonia were studied at ambient temperature under autogenous pressure by multinuclear (71Ga, 35Cl, 81Br) NMR spectroscopy. To unravel the role of pH, the analyses were done both in absence and in presence of ammonium halides, which are employed as mineralizers during ammonoacidic gallium nitride crystal growth. While gallium trifluoride and its ammoniate were found to be too sparingly soluble to give rise to a NMR signal, the spectra of solutions of the heavier halides reveal the presence of a single gallium‐containing species in all cases. DFT calculations and molecular dynamics simulations suggest the identification of this species as consisting of a [Ga(NH3)6]3+ cation and up to six surrounding halide anions, resulting in an overall trend towards negative complex charge. Quantitative 71Ga NMR studies on saturated solutions of GaCl3 containing various amounts of additional NH4Cl revealed a near linear increase of GaCl3 solubility with mineralizer concentration of about 0.023 mol GaCl3 per mol NH4Cl at room temperature. These findings reflect the importance of Coulombic shielding for the inhibition of oligomerization and precipitation processes and help to rationalize both the low solubility of gallium halides in neutral ammonia solution and, in turn, the proliferating effect of the mineralizer during ammonoacidic gallium nitride formation.
Photocatalytic CO2 Reduction under Visible‐Light Irradiation by Ruthenium CNC Pincer Complexes
Authors: Arikawa Yasuhiro , Tabata Itoe , Miura Yukari , Tajiri Hiroki , Seto Yudai , Horiuchi Shinnosuke , Sakuda Eri , Umakoshi Keisuke
Published: February 2020

Photocatalytic CO2 reduction using a ruthenium photosensitizer, a sacrificial reagent 1,3‐dimethyl‐2‐(o‐hydroxyphenyl)‐2,3‐dihydro‐1H‐benzo[d]imidazole (BI(OH)H), and a ruthenium catalyst were carried out. The catalysts contain a pincer ligand, 2,6‐bis(alkylimidazol‐2‐ylidene)pyridine (CNC) and a bipyridine (bpy). The photocatalytic reaction system resulted in HCOOH as a main product (selectivity 70–80 %), with a small amount of CO, and H2. Comparative experiments (a coordinated ligand (NCMe vs. CO) and substituents (tBu vs. Me) of the CNC ligand in the catalyst) were performed. The turnover number (TONHCOOH) of carbonyl‐ligated catalysts are higher than those of acetonitrile‐ligated catalysts, and the carbonyl catalyst with the smaller substituents (Me) reached TONHCOOH=5634 (24 h), which is the best performance among the experiments.
Untersuchung des dynamischen Prozessverhaltens bei Betriebsstörungen im Bereich der chemischen Absorption
Authors: Bothe Mike , Fedorov Alexander , Frei Herrmann , Lutters Nicole , Kenig Eugeny Y.
Published: February 2020

Die Kenntnis des dynamischen Prozessverhaltens im Bereich der chemischen Absorption ist für die Vermeidung von Stör‐ und Notfallsituationen unerlässlich. Daher wurde in dieser Arbeit ein Rate‐based‐Modell zur dynamischen Simulation entwickelt und validiert. Als Beispiel wurde die reaktive Absorption von Kohlenstoffdioxid mit wässriger Monoethanolaminlösung modelliert. Anschließend wurden mit diesem Modell Sprungantworten für Änderungen einzelner Eintrittsgrößen in einer Absorptionskolonne im industriellen Maßstab simuliert. Mithilfe dieser Sprungantworten können schnelle vereinfachte Modelle entwickelt werden, die zur Vorbeugung von Störfällen in Echtzeit verwendet werden können.
Modellierung der Oberflächenstruktur von Nadelfilz‐Filtermedien zur Simulation der kuchenbildenden Staubfiltration
Authors: Zhang Qian , Horst David , Schmidt Eberhard
Published: February 2020

Die charakteristischen, filtrationsrelevanten Merkmale der Oberfläche von verschiedenen Nadelfilz‐Filtermedien werden mit einigen neu eingeführten Kenngrößen quantitativ beschrieben. Diese Kenngrößen ermöglichen eine günstige Konstruktion von Filtermedienmodellen, die als Ersatz der realen Filtermediengeometrie für Simulationsrechnungen bezüglich des Staubkuchenaufbaus verwendet werden. Vielfältige Filtermedienmodelle können durch Variation dieser Kenngrößen erzeugt werden, was eine systematische Studie über den Zusammenhang zwischen der Oberflächenstruktur eines Nadelfilz‐Filtermediums und dessen Betriebsverhalten ermöglicht.
Comparative analysis of taxol‐derived fluorescent probes to assess microtubule networks in a complex live three‐dimensional tissue
Authors: Logan Gregory , McCartney Brooke
Published: February 2020

Drosophila oogenesis is an excellent in vivo model for investigating cytoskeletal dynamics because of the rapid cytoskeletal remodeling that occurs at the end of stage 10; however, there are few robust tools for detecting microtubules in live complex tissues. The recent development of membrane permeable taxol‐based fluorescent probes to label microtubules is significant technical progress, but the effectiveness of these probes and the potential stabilizing effects of the taxol derivative have not been well characterized in vivo. Here, we compared three commercially available taxol‐derived microtubule labels to determine their efficacy and potential artifacts. We found that all three probes labeled microtubules with differences in permeability, brightness, and signal to noise ratio. Like taxol, however, all of the probes disrupted the F‐actin cytoskeleton at higher concentrations. We also found that the efflux pump inhibitor, verapamil, increased the intensity of the label and modestly increased the severity of the F‐actin defects. Of the three probes, Tubulin Tracker (ThermoScientific) was the most permeable and was brightest, with the highest signal to noise ratio. Furthermore, washing out the probe after a 30‐min incubation significantly reduced the F‐actin artifacts without compromising signal brightness.
Synthesis, Molecular Docking, and Preliminary Evaluation of 2‐(1,2,3‐Triazoyl)benzaldehydes As Multifunctional Agents for the Treatment of Alzheimer's Disease
Authors: Costa Gabriel P. , Baldinotti Rodolfo S. M. , Fronza Mariana G. , Nascimento José Edmilson R. , Dias Ítalo F. C. , Sonego Mariana Souza , Seixas Fabiana Kömmling , Collares Tiago , Perin Gelson , Jacob Raquel G. , Savegnago Lucielli , Alves Diego
Published: February 2020

We described here our results on the use of thiourea as a ligand in the copper catalysed azide‐alkyne cycloaddition (CuAAC) of 2‐azidobenzaldehyde with alkynes. Reactions were performed reacting 2‐azidobenzaldehyde with a range of terminal alkynes using 10 mol % of copper iodide as a catalyst, 20 mol % of thiourea as a ligand, triethylamine as base, DMSO as solvent at 100 °C under nitrogen atmosphere. The corresponding 2‐(1H‐1,2,3‐triazoyl)‐benzaldehydes (2‐TBH) were obtained in moderated to excellent yields and according our experiments, the use of thiourea decreases the formation of side products. The obtained compounds were screened for their binding affinity with multiple therapeutic targets of AD by molecular docking: β‐secretase (BACE), glycogen synthase kinase (GSK‐3β) and acetylcholinesterase (AChE). The three compounds with highest affinity, 5 a (2‐(4‐phenyl‐1H‐1,2,3‐triazol‐1‐yl)benzaldehyde), 5 b (2‐(4‐(p‐tolyl)‐1H‐1,2,3‐triazol‐1‐yl)benzaldehyde), and 5 d (2‐(4‐(4‐(tert‐butyl)phenyl)‐1H‐1,2,3‐triazol‐1‐yl)benzaldehyde) were selected and evaluated on its antioxidant effect, in view of select the most promising one to perform the in vivo validation. Due the antioxidant potential ally to the affinity with BACE, GSK‐3β and AChE, compound 5 b was evaluated in a mouse model of AD induced by intracerebroventricular injection of streptozotocin (STZ). Our results indicate that 5 b (1 mg/kg) treatment during 20 days is able to reverse the cognitive and memory impairment induced by STZ trough the modulation of AChE activity, amyloid cascade and GSK‐3β expression.
Germline alterations in patients with biliary tract cancers: A spectrum of significant and previously underappreciated findings
Authors: Maynard Hannah , Stadler Zsofia K. , Berger Michael F. , Solit David B. , Ly Michele , Lowery Maeve A. , Mandelker Diana , Zhang Liying , Jordan Emmett , El Dika Imane , Kemel Yelena , Ladanyi Marc , Robson Mark E. , O’Reilly Eileen M. , Abou‐Alfa Ghassan K.
Published: February 2020

Background

With limited information on germline mutations in biliary tract cancers, this study performed somatic and germline testing for patients at Memorial Sloan Kettering Cancer Center with known biliary tract carcinoma with the aim of determining the frequency and range of pathogenic germline alterations (PGAs).

Methods

Patients with biliary tract carcinoma were consented for somatic tumor and matched blood testing of up to 468 genes via the Memorial Sloan Kettering Cancer Center Integrated Mutation Profiling of Actionable Cancer Targets next‐generation sequencing platform. A germline variant analysis was performed on a panel of up to 88 genes associated with an increased predisposition for cancer. Demographic and diagnostic details were collected.

Results

Germline mutations were tested in 131 patients. Intrahepatic cholangiocarcinoma was the most common cancer (63.4%), and it was followed by gallbladder adenocarcinoma (16.8%), extrahepatic cholangiocarcinoma (16%), and otherwise unspecified biliary tract cancer (3.8%). Known and likely PGAs were present in 21 patients (16.0%), with 9.9% harboring a PGA in a high/moderate‐penetrance cancer predisposition gene. Among high‐penetrance cancer susceptibility genes, PGAs were most commonly observed in BRCA1 and BRCA2 (33.3%), which made up 5.3% of the entire cohort, and they were followed by PALB2, BAP1, and PMS2. Mutations in ATM, MITF, and NBN, moderate‐penetrance cancer susceptibility genes, were identified in 1 patient each. There was no observed difference in the types of mutations among the subtypes of biliary tract cancer.

Conclusions

The frequency of PGAs found was comparable to existing data on the prevalence of germline mutations in other solid tumor types with matched tumor analysis. This provides support for the role of the BRCA1/2, ATM, and BAP1 genes in biliary tract cancer susceptibility.
Gas‐Phase Conformational Map of the Amino Acid Isovaline
Authors: Neeman E. M. , León I. , Alonso E. R. , Mata S. , Alonso J. L.
Published: February 2020

Four conformers of the non‐proteinogenic α‐amino acid isovaline, vaporized by laser ablation, are characterized by Fourier‐transform microwave techniques in a supersonic expansion. The comparison between the experimental rotational and 14N nuclear quadrupole coupling constants and the ab initio calculated ones provides conclusive evidence for the identification of the conformers. The most stable species is stabilized by an N−H⋅⋅⋅O =C intramolecular hydrogen bond and a cis‐COOH interaction, whereas the higher‐energy conformers exhibit an N⋅⋅⋅H−O intramolecular hydrogen bond and trans‐COOH, as in other aliphatic amino acids. The spectroscopic data herein reported can be used for the astrophysical purpose in a possible detection of isovaline in space.
Studying Structural and Optical Properties of TiO2–SnO2 Core–Shell Synthesized by Sol–Gel Route
Authors: Bitaraf Mehrnaz , Ghazi Mohammad E. , Izadifard Morteza
Published: February 2020

Herein, the TiO2–SnO2 core–shell structures with the core‐to‐shell molar ratios of 5:0.5, 5:0.67, and 5:1 are synthesized by the sol–gel route, and then the structural and optical properties of the synthesized samples are investigated. In order to characterize the samples, the XRD, Raman, FESEM, and TEM techniques are used for their structural verification, while the UV–visible and photoluminescence spectra are used for their optical characterization. The XRD results obtained showed that the annealed TiO2 sample has an anatase tetragonal structure and that the core–shell samples contain the diffraction peaks of both the core TiO2 and the shell SnO2. The XRD results obtained are supported by Raman spectroscopy. The TEM images obtained show evidence of the formation of the composite (core–shell) nanostructure in the samples. The optical investigation shows that the band gaps of the core–shell samples are indirect, like the TiO2 core itself, and increase with an increase in the core‐to‐shell molar ratio. These results also show that the synthesized core–shell samples are suitable candidates for use in optoelectronic devices.