bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis, characterization, and cytotoxicity of PCL–PEG–PCL diacrylate and agarose interpenetrating network hydrogels for cartilage tissue engineering
Authors: Su Zih‐Cheng , Lin Shih‐Jie , Chang Yu‐Hsuan , Yeh Wen‐Ling , Chu I‐Ming
Published: June 2020

Hydrogels are suitable biomaterials for cartilage tissue engineering due to the excellent ability to retain water to provide suitable environment for the tissue, however, the insufficient mechanical properties often prevent their wider applications. The objective of this study was to fabricate biocompatible hydrogels with good mechanical performance, high‐water content, and porous microstructure for cartilage regeneration. Photocrosslinked hydrogels are one of the most widely used systems in tissue engineering due to the superior mechanical properties. In this study, block copolymer, poly(ε ‐caprolactone)‐poly(ethylene)‐poly(ε‐caprolactone) diacrylate (PCL–PEG–PCL; PEC), was prepared by ring‐opening polymerization, and PEC hydrogels were made through free radical crosslinking mechanism. Agarose network is chosen as another component of the hydrogels, because of the high‐swelling behavior and cartilage‐like microstructure, which is helpful for chondrocytes growth. Interpenetrating networks (IPN) were fabricated by diffusing PEC into agarose network followed by photo‐crosslinking process. It was noted that incorporating PEC into the agarose network increased the elastic modulus and the compressive failure properties of individual component networks. In addition, high‐swelling ratio and uniform porosity microstructures were found in the IPN hydrogels. IPN and PEC showed low cytotoxicity and good biocompatibility in elution test method. The results suggest promising characteristics of IPN hydrogels as a potential biomaterial for cartilage tissue engineering.
SPEEK‐Tin dioxide proton conducting membranes: Effect of modifying agent of tin dioxide particles surface
Authors: de Aguiar Liz Contino Vianna , de Ramos Filho Florêncio Gomes , Dahmouche Karim , Perez Gerônimo , Archanjo Braulio Soares , Kawaguti Carla Akimi , de Souza Gomes Ailton
Published: June 2020

Proton‐conducting membranes based on sulphonated poly (ether ether ketone) (SPEEK) polymer matrix and tin dioxide have been synthesized. Their local structure has been studied by FTIR and XRD whereas their structural features at nanometer scale has been investigated by Small‐Angle X‐ray Scattering (SAXS) and transmission electron microscopy (TEM). SAXS and TEM results show that incorporation of the inorganic particles in SPEEK promotes dispersion of the hydrophilic sulfonic groups in the polymer matrix, inhibiting the formation of the water‐filled ionic clusters usually observed in hydrated SPEEK membranes. The changes in SPEEK nanostructure are induced by incorporation of particles modified by Tiron that promotes the connectivity between hydrated channels and reduces diffusion of alcohol, as evidenced by permeability measurements. The resulting increase of proton conductivity compared to pristine SPEEK, particularly at medium temperature (80°C), combined to an improved dimensional stability, make this family of membranes very promising for future applications in fuel cell.
Synthesis of hydrogels with a gradient crosslinking structure by electron beam radiation to an aqueous solution of poly(sodium acrylate)
Authors: Dohi Shunsuke , Matsumoto Akikazu
Published: June 2020

Hydrogels were prepared by electron beam (EB) radiation to the aqueous solutions of poly(sodium acrylate) in the presence of potassium and ammonium peroxodisulfates. The effects of EB radiation dose, as well as polymer, and initiator concentrations on the formation of gels, were investigated. On the basis of the storage modulus, loss modulus, and complex viscosity of the isolated gels determined by rheological measurement, the relationship between the radiation conditions and the rheological properties of the gels was discussed. Furthermore, hydrogels with a gradient crosslinking structure in a depth direction were synthesized by controlling EB radiation dose.
Retinal cone photoreceptor distribution in the American black bear (Ursus americanus)
Authors: Heyward Jennifer L. , Reynolds Benjamin D. , Foster Melanie L. , Archibald Kate E. , Stoskopf Michael K. , Mowat Freya M.
Published: June 2020

The distribution of cone photoreceptor subtypes (important for color vision and vision quality) varies widely in different carnivore species, but there have been limited studies on bear (ursid) cone distribution. A previous behavioral study suggests that American black bears (Ursus americanus) are dichromatic, indicating that they possess two cone subtypes, although the retinal distribution of cones is unknown. The purpose of this study was to examine the subtype and topography of cones in American black bear retinas to further predict the nature of their color vision and image resolution. We studied 10 eyes from seven individual legally hunted black bears in northeastern North Carolina. Cryosections and retinal wholemounts were labeled using antibodies targeting two cone opsin subtypes: long/medium (L/M) wavelength sensitive and short (S) wavelength sensitive. Cones in fluorescent microscopy images were counted and density maps were created for retinal wholemounts. The black bear retina contains both cone subtypes and L/M cones outnumber S cones by at least 3:1, a finding confirmed in retinal frozen sections. There are higher concentrations of S cones present than typically seen in other carnivores with some evidence for co‐expression of L/M and S cones. A cone‐dense area centralis is present dorsotemporal to the optic nerve, similar to other carnivores. These results confirm that American black bears are predicted to have a dichromatic vision with high acuity indicated by the presence of a dorsotemporally located area centralis.
Design, synthesis, molecular docking, and anticancer evaluations of 1‐benzylquinazoline‐2,4(1H,3H)‐dione bearing different moieties as VEGFR‐2 inhibitors
Authors: El‐Adl Khaled , El‐Helby Abdel‐Ghany A. , Sakr Helmy , El‐Hddad Sanadelaslam S. A.
Published: June 2020

A novel series of 1‐benzylquinazoline‐2,4(1H,3H)‐dione derivatives, 6a,b to 11a–e, was designed, synthesized, and evaluated for their anticancer activity against HepG2, HCT‐116, and MCF‐7 cells. Compounds 11b, 11e, and 11c were found to be the most potent derivatives of all tested compounds against the HepG2, HCT‐116, and MCF‐7 cancer cell lines, with GI50 = 9.16 ± 0.8, 5.69 ± 0.4, 5.27 ± 0.2 µM, 9.32 ± 0.9, 6.37 ± 0.7, 5.67 ± 0.5 µM, and 9.39 ± 0.5, 6.87 ± 0.7, 5.80 ± 0.4 µM, respectively. These compounds exhibited nearly the same activity as sorafenib against HepG2 and HCT‐116 cells and a higher activity against MCF‐7 cells (GI50 = 9.18 ± 0.6, 5.47 ± 0.3, and 7.26 ± 0.3 µM, respectively). Also, these compounds displayed a lower activity than doxorubicin against HepG2 cells and a higher activity against HCT‐116 and MCF‐7 cells (GI50 = 7.94 ± 0.6, 8.07 ± 0.8, and 6.75 ± 0.4 µM, respectively). The most active antiproliferative derivatives, 6a,b, 8, 9, and 11a–e, were selected to evaluate their enzymatic inhibitory activity against VEGFR‐2. Compounds 11b, 11e, and 11c potently inhibited VEGFR‐2 at IC50 values of 0.12 ± 0.02, 0.12 ± 0.02, and 0.13 ± 0.02 µM, respectively, which are nearly equipotent as sorafenib IC50 value (0.10 ± 0.02 µM). Furthermore, molecular docking studies were performed for all synthesized compounds to assess their binding pattern and affinity toward the VEGFR‐2 active site.
Electrochemical Behaviour of Nb‐Doped Anatase TiO2 Microbeads in an Ionic Liquid Electrolyte
Authors: Lindberg Simon , Cavallo Carmen , Calcagno Giulio , Navarro‐Suárez Adriana M. , Johansson Patrik , Matic Aleksandar
Published: June 2020

TiO2 is a promising material for high‐power battery and supercapacitor applications. However, in general TiO2 suffers from an initial irreversible capacity that limits its use in different applications. A combination of a microbead morphology, Nb‐doping, and the use of an ionic liquid electrolyte is shown to significantly decrease the irreversible capacity loss. A change in the electrochemical response in the first cycles indicates formation of a solid–electrolyte interphase (SEI) or a modification of the structure of the surface layer of the TiO2/Nb microbeads, which apparently stabilises the performance. The change in the response is manifested in an increased charge transfer resistance and the presence of two charge transfer contributions. During prolonged cycling the TiO2/Nb electrode shows an excellent stability over 5000 cycles. Ex situ analysis after cycling shows that the overall microbead morphology is intact and that there are no changes in the crystal structure. However, a decrease in the intensity of the XRD pattern can point to a decrease in size of the nanocrystals building up the microbeads or the formation of amorphous phases.
Regenwürmer als Partner bei der Bodennutzung
Authors: Schrader Stefan , van Capelle Christine , Meyer‐Wolfarth Friederike
Published: June 2020

Regenwürmer sind Leistungsträger innerhalb des Bodennahrungsnetzes und erbringen zahlreiche ökologische Dienstleistungen. So fördern sie Bodenstrukturbildung, Bodengesundheit, Nährstoffverfügbarkeit, Belüftung, Wasserspeicherung sowie Widerstands‐ und Regenerationsfähigkeit von Böden. Dieses große Leistungsspektrum hilft Fruchtbarkeit und Produktivität landwirtschaftlich genutzter Böden nachhaltig zu gewährleisten. Eine Förderung der Regenwürmer durch angepasste, bodenschonende Managementmaßnahmen ist unerlässlich, um die natürlichen Ressourcen der Regenwürmer optimal zu nutzen. Ein synergistisches Zusammenspiel aus Leistungen der Regenwürmer und landwirtschaftlichem Management ist daher ein erfolgversprechender Ansatz, um Bodenfruchtbarkeit und Ertragssicherheit zukünftig nachhaltig zu sichern.
4‐Methylamino antipyrine determination in human plasma by high‐performance liquid chromatography tandem mass spectrometry
Authors: Nikitina Aleksandra , Gildeeva Geliia , Grigoriev Alexander , Sidorova Alla
Published: June 2020

In the present study, a simple and rapid method for metamizole metabolite 4‐methylamino antipyrine (MAA) determination in human plasma was developed, validated and successfully applied to a clinical trial. Chromatographic separation was achieved in HILIC mode on a YMC‐Pack SIL column (100 × 2.0 mm; S‐5 μm, 30 nm), with a mobile phase consisting of acetonitrile, water and formic acid. Protein precipitation of a small plasma volume using acetonitrile was selected for sample preparation. The multiple reaction monitoring transitions in the positive ionization mode were m/z 218.2 → 56.2 for MAA and m/z 221.2 → 56.2 for MAA‐d3 (IS, internal standard). Concentration levels of MAA calibration standards were in the range of 0.100–20 μg/ml. Metamizole conversion into MAA in both water and organic media was investigated, and the level of the conversion in commercially available injection solutions was estimated.
Ethnicity and insurance status predict metastatic disease presentation in prostate, breast, and non‐small cell lung cancer
Authors: Aghdam Nima , McGunigal Mary , Wang Haijun , Repka Michael C. , Mete Mihriye , Fernandez Stephen , Dash Chiranjeev , Al‐Refaie Waddah B. , Unger Keith R.
Published: June 2020

Background

Ethnicity and insurance status have been shown to impact odds of presenting with metastatic cancer, however, the interaction of these two predictors is not well understood. We evaluate the difference in odds of presenting with metastatic disease in minorities compared to white patients despite access to the same insurance across three common cancer types.

Methods

Using the National Cancer Database, a multilevel logistic regression model that estimated the odds of metastatic disease was fit, adjusting for covariates including year of diagnosis, ethnicity, insurance, income, and region. We included adults diagnosed with metastatic prostate, non–small cell lung cancer (NSCLC), and breast cancer from 2004 to 2015.

Results

The study cohort consisted of 1 191 241 prostate cancer (PCa), 1 310 986 breast cancer (BCa), and 1 183 029 NSCLC patients. Private insurance was the most protective factor against metastatic presentation. Odds of presenting with metastatic disease were 0.190 [95% CI, 0.182‐0.198], 0.616 [95% CI, 0.602‐0.630], and 0.270 [95% CI, 0.260‐0.279] for PCa, NSCLC, and BCa compared to uninsured patients, respectively. Private insurance provided the most significant benefit to non‐Hispanic White PCa patients with 81% reduction in odds of metastatic presentation and conferred the least benefit to African‐American NSCLC patients at 30.4% reduction in odds of metastatic presentation.

Conclusions

Insurance status provided the single most protective effect against metastatic presentation. This benefit varied for minorities despite similar insurance. Reducing metastatic disease presentation rates requires addressing social barriers to care independent of insurance.
Criminal career duration: Predictability from self‐reports and official records
Authors: Ahonen Lia , FitzGerald Douglas , Klingensmith Kaylee , Farrington David P.
Published: June 2020

Criminal career duration has not been well investigated. There are very few longitudinal data sets that last long enough and enough subjects to investigate criminal career duration, and especially the characteristics and risk profiles of especially life course persistent offenders. The aim of the study was to describe the predictability of criminal career duration based on both official records and self‐reports of offending, and to put the results in the context of the Moffitt theory of “adolescent limited” and “life course persistent” offenders. The Pittsburgh Youth Study (n = 1517) is a seminal longitudinal study based on a community sample of high‐risk boys from the city of Pittsburgh. Data was used from the oldest sample of boys in the PYS (N = 506). The participants were first assessed on average at age 12, and data was used up until age 36 for self‐reported offending, and age 40 for police charges. The analyses were conducted on moderate and serious violence and moderate and serious theft. Career duration was based on self‐reports and official charges in combination. The results show the extent to which commonly accepted and well validated risk factors predict criminal career duration with a special focus on individuals showing high rate/persistent offending in adolescence. Results show more pathways of delinquent development than have previously been described by Moffitt, (Psychological Review, 1993, 100(4), 674–701). Results also show that there is limited predictability of delinquency and offending over time. In addition, results show that only a small number of risk factors distinguish high and low rate adolescent offenders who become continuous offenders. Examples are peer factors. Implications for policy making and intervention science are discussed.
Intraoperative detection of second inferior vena cava during para‐aortic lymphadenectomy for advanced‐staged ovarian cancer: Lessons to be learned
Authors: Petousis Stamatios , Margioula‐Siarkou Chrysoula , Navarro Beatriz , Mavromatidis George , Dinas Konstantinos , Guyon Frederic
Published: June 2020

As the presence of second inferior vena cava may alter the extent of para‐aortic lymphadenectomy, early preoperative imaging diagnosis is of great significance to avoid intraoperative difficulties.
Transient swallowing‐induced atrial tachycardia in a patient with genotyped hypertrophic cardiomyopathy
Authors: Fujino Noboru , Hayashi Kenshi , Sakata Kenji , Tada Hayato , Nakanishi Chiaki , Tsuda Toyonobu , Nomura Akihiro , Yoshida Shohei , Sakamoto Yuichiro , Kato Takeshi , Furusho Hiroshi , Kawashiri Masa‐aki , Takamura Masayuki
Published: June 2020

Most cases of swallowing‐induced atrial tachycardia require radiofrequency catheter ablation for a permanent cure; however, the arrhythmia subsided after temporary prescription of verapamil in a patient with genotyped hypertrophic cardiomyopathy.
Imidazolium‐Functionalized Cationic Covalent Triazine Frameworks Stabilized Copper Nanoparticles for Enhanced CO2 Electroreduction
Authors: Mao Min‐Jie , Zhang Meng‐Di , Meng Dong‐Li , Chen Jian‐Xin , He Chang , Huang Yuan‐Biao , Cao Rong
Published: June 2020

The highly selective production of reduced multicarbon products with long‐term durability for CO2 electroreduction reaction (CO2RR) using clean and renewable electricity is currently a major challenge. Copper nanoparticles (Cu NPs) are exceptionally advantageous for CO2RR to yield multielectron transfer chemical products such as ethylene and ethanol. However, Cu NPs for CO2RR generally require high overpotential to produce multiple electron transfer C2+ products with poor stability. Herein, an imidazolium‐functionalized covalent triazine framework (ICTF) stabilized Cu NPs (Cu/ICTF) for the enhanced CO2RR to produce ethylene is reported. The imidazolium groups in the cationic ICTF not only can enhance CO2 capture capacity and lower the energetic barrier to activate CO2, but also the in situ formed N‐heterocyclic carbenes (NHC) could stabilize Cu NPs to prevent their deactivation. Thus, the Cu/ICTF demonstrated higher selectivity (35 %) for the electroreduction of CO2 to ethylene with larger partial current density of ethylene (4.14 mA cm−2) over the unmodified neutral CTF stabilized Cu NPs (Cu/CTF) with 29 % Faradaic efficiency (FE) of ethylene and current density of 3.69 mA cm−2. Moreover, the active sites could be stabilized by the in situ produced NHC in ICTF and the current density and C2H4 FE of Cu/ICTF50 were almost maintained after 10 h continuous electrolysis experiment, while the C2H4 FE of Cu/CTF50 were lost ca. 42 % of its original value after 7 h. This strategy provides a facile approach to stabilize active sites for CO2RR and may bring new inspiration to apply in energy storage and conversion.
Mild and Selective Carbon Dioxide Hydroboration to Methoxyboranes Catalyzed by Mn(I) PNP Pincer Complexes
Authors: Kostera Sylwia , Peruzzini Maurizio , Kirchner Karl , Gonsalvi Luca
Published: June 2020

Well‐defined Mn(I)‐PNP pincer‐type complexes were tested as non‐precious transition metal catalysts for the selective reduction of CO2 to boryl‐protected MeOH in the presence of hydroboranes (HBpin, 9‐BBN) and borates as Lewis acids (LA) additives. The best performance was obtained under mild reaction conditions (1 bar CO2, 60 °C) in the presence of the hydridocarbonyl complex [MnH(PNPNH–iPr)(CO)2] and B(OPh)3 as co‐catalyst. Preliminary mechanistic studies suggest that the initial activation step may occur by cationization of the metal center by the strong LA, and that both metal‐catalyzed and metal‐free steps are present in the overall catalytic system.
Cycloaddition Reactions of Epoxides and CO2 by the Novel Imidazolium‐Functionalized Metalloporphyrins: Optimization and Analysis using Response Surface Methodology
Authors: Li Zhonglu , Su Zhenping , Xu Wenhua , Shi Qing , Yi Jiajia , Bai Caihe , Wang Ning , Li Jun
Published: June 2020

The production of cyclic carbonates using CO2 and epoxides has received great attention due to 100 % atom utilization. Herein, novel imidazolium‐containing metalloporphyrins were synthesized as bifunctional catalysts for the cycloaddition reactions of epoxides and CO2. The reaction conditions were optimized and analyzed with the response surface methodology. Under the optimum condition using Zn‐porphyrin 1 as the catalyst, the turnover number (TON) and turnover number frequency (TOF) for the cycloaddition of CO2 and ECH were 11,629 and 1,735, respectively. In addition, analysis of the RSM indicated that the CO2 pressure had only a small impact on the yield. Based on this conclusion, the catalytic activity of 1 was further evaluated under mild conditions. Regardless of whether the CO2 pressure is high or ambient, this Zn‐porphyrin exhibited an excellent performance with a high turnover number frequency.
Stable overall water splitting in an asymmetric acid/alkaline electrolyzer comprising a bipolar membrane sandwiched by bifunctional cobalt‐nickel phosphide nanowire electrodes
Authors: Xu Junyuan , Amorim Isilda , Li Yue , Li Junjie , Yu Zhipeng , Zhang Bingsen , Araujo Ana , Zhang Nan , Liu Lifeng
Published: June 2020

Water splitting has been proposed to be a promising approach to producing clean hydrogen fuel. The two half‐reactions of water splitting, that is, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), take place kinetically fast in solutions with completely different pH values. Enabling HER and OER to simultaneously occur under kinetically favorable conditions while using exclusively low‐cost, earth‐abundant electrocatalysts is highly desirable but remains a challenge. Herein, we demonstrate that using a bipolar membrane (BPM) we can accomplish HER in a strongly acidic solution and OER in a strongly basic solution, with bifunctional self‐supported cobalt‐nickel phosphide nanowire electrodes to catalyze both reactions. Such asymmetric acid/alkaline water electrolysis can be achieved at 1.567 V to deliver a current density of 10 mA/cm2 with ca. 100% Faradaic efficiency. Moreover, using an “irregular” BPM with unintentional crossover the voltage needed to afford 10 mA/cm2 can be reduced to 0.847 V, due to the assistance of electrochemical neutralization between acid and alkaline. Furthermore, we show that BPM‐based asymmetric water electrolysis can be accomplished in a circulated single‐cell electrolyzer delivering 10 mA/cm2 at 1.550 V and splitting water very stably for at least 25 hours, and that water electrolysis is enabled by a solar panel operating at 0.908 V (@13 mA/cm2), using an “irregular” BPM. BPM‐based asymmetric water electrolysis is a promising alternative to conventional proton and anion exchange membrane water electrolysis.
A “Push–Pull” Stabilized Phosphinidene Supported by a Phosphine‐Functionalized β‐Diketiminato Ligand
Authors: Bestgen Sebastian , Mehta Meera , Johnstone Timothy C. , Roesky Peter W. , Goicoechea Jose M.
Published: June 2020

The use of a bis(diphenyl)phosphine functionalized β‐diketiminato ligand, [HC{(CH3)C}2{(ortho‐[P(C6H5)2]2C6H4)N}2]− (PNac), as a support for germanium(II) and tin(II) chloride and phosphaketene compounds, is described. The conformational flexibility and hemilability of this unique ligand provide a versatile coordination environment that can accommodate the electronic needs of the ligated elements. For example, chloride abstraction from [(PNac)ECl] (E=Ge, Sn) affords the cationic germyliumylidene and stannyliumylidene species [(PNac)E]+ in which the pendant phosphine arms associate more strongly with the Lewis acidic main group element centers, providing further electronic stabilization. In a similar fashion, chemical decarbonylation of the germanium phosphaketene [(PNac)Ge(PCO)] with tris(pentafluorophenyl)borane affords a “push–pull” stabilized phosphinidene in which one of the phosphine groups of the ligand backbone associates with the low valent phosphinidene center.
In Situ Construction of Pt–Ni NF@Ni‐MOF‐74 for Selective Hydrogenation of p‐Nitrostyrene by Ammonia Borane
Authors: Xu Jinhui , Zhu Junjiang , Liu Yu , Long Yan , Feng Jing , Yang Xiangguang , Zhang Yibo , Song Shuyan , Zhang Hongjie
Published: June 2020

Pt–Ni nanoframes (Pt–Ni NFs) exhibit outstanding catalytic properties for several reactions owing to the large numbers of exposed surface active sites, but its stability and selectivity need to be improved. Herein, an in situ method for construction of a core–shell structured Pt‐Ni NF@Ni‐MOF‐74 is reported using Pt–Ni rhombic dodecahedral as self‐sacrificial template. The obtained sample exhibits not only 100 % conversion for the selective hydrogenation of p‐nitrostyrene to p‐aminostyrene conducted at room temperature, but also good selectivity (92 %) and high stability (no activity loss after fifteen runs) during the reaction. This is attributed to the Ni‐MOF‐74 shell in situ formed in the preparation process, which can stabilize the evolved Pt–Ni NF and donate electrons to the Pt metals that facilitate the preferential adsorption of electrophilic NO2 group. This study opens up new vistas for the design of highly active, selective, and stable noble‐metal‐containing materials for selective hydrogenation reactions.
Total Synthesis of Anti‐MRSA Active Diorcinols and Analogues
Authors: Boehlich G. Jacob , de Vries Jessica , Geismar Olivia , Gudzuhn Mirja , Streit Wolfgang R. , Wicha Sebastian G. , Schützenmeister Nina
Published: June 2020

Diorcinols and related prenylated diaryl ethers were reported to exhibit activity against methicillin‐resistant clinical isolates of Staphylococcus aureus (MRSA). Within these lines, we report the first total synthesis of diorcinol D, I, J, the proposed structure of verticilatin and recently isolated antibacterial diaryl ether by using an efficient and highly divergent synthetic strategy. These total syntheses furnish the diaryl ethers in only five to seven steps employing a Pd‐catalyzed diaryl ether coupling as the key step. The total synthesis led to the structural revision of the natural product verticilatin, which has been isolated from a plant pathogenic fungus. Furthermore, these structures were tested in order to determine their antibacterial activities against different MRSA strains as well as further Gram‐positive and ‐negative bacteria.
Chemistry inside a Porphyrin Skeleton: Platinacyclopentadiene from Tellurophene
Authors: Pacholska‐Dudziak Ewa , Vetter Grzegorz , Góratowska Aleksandra , Białońska Agata , Latos‐Grażyński Lechosław
Published: June 2020

Platinum(II) binds to 21,23‐ditelluraporphyrin forming a side‐on complex, which can be easily transformed into an aromatic metallaporphyrin, that is, 21‐platina‐23‐telluraporphyrin, with a platinacyclopentadiene unit built in the porphyrin skeleton in place of one pyrrole ring. The central platinum(II) ion with a CCNTe square‐planar coordination sphere can be oxidized to platinum(IV) by chlorine, bromine, methyl iodide or allyl chloride to yield octahedral complexes. All platinatelluraporphyrins show dynamic behavior involving the platinum ion coordination sphere fluxionality and the porphyrin skeleton deformation, both in‐plane and out‐of‐plane, as demonstrated by 1H NMR spectroscopy.
Bioenergie – Chancen für die Zukunft
Authors: Bley Thomas
Published: June 2020

Welche Möglichkeiten bietet die Nutzung von Biomasse zur Energiegewinnung? Biomasse kann durch biotechnologische Verfahren in gasförmige (Methan) und flüssige (Ethanol) Energieträger umgewandelt, gespeichert und transportiert werden. Es wird unter anderem konstatiert, dass es sinnvoller wäre, diese Energieträger direkt für die Mobilität zu nutzen und nicht über den Umweg der Verstromung. Das Potenzial von Bioenergie wird exemplarisch an den drei Ländern Deutschland, Thailand und Kenia dargestellt. Die Nutzung der Bioenergien kann einen Beitrag zur Reduzierung der CO2‐Emissionen und zur Stabilisierung der Energieversorgung leisten.
Inhibition of neural stem cell aging through the transient induction of reprogramming factors
Authors: Han Min Ji , Lee Won Ji , Choi Joonhyuk , Hong Yean Ju , Uhm Sang Jun , Choi Youngsok , Do Jeong Tae
Published: June 2020

Adult stem cells age during long‐term in vitro culture, and neural stem cells (NSCs), which can self‐renew and differentiate into neurons and glial cells, also display reduced differentiation potential after repeated passaging. However, the mechanistic details underlying this process remain unclear. In this study, we found that long‐term in vitro culture of NSCs resulted in aging‐related upregulation of inflammatory‐ and endoplasmic reticulum (ER) stress‐related genes, including the proinflammatory cytokines interleukin (IL)1β and IL6, the senescence‐associated enzyme matrix metallopeptidase 13 (MMP13), and the ER stress‐responsive transcription factor activating transcription factor 4 (ATF4) and C/EBP homologous protein (CHOP). However, the cyclic and transient induction of four reprogramming factors (POU domain, class 5, transcription factor 1, also known as octamer‐binding transcription factor 4; SRY [sex determining region Y]‐box 2; Kruppel‐like factor 4; and myelocytomatosis oncogene; collectively referred to as OSKM) can inhibit NSC aging, as indicated by the decreased expression of the inflammatory and ER stress‐related genes. We used ROSA‐4F NSCs, which express OSKM from only one allele, to minimize the potential for full reprogramming or tumor formation during NSC rejuvenation. We expect that this novel rejuvenation method will enhance the potential of NSCs as a clinical approach to the treatment of neurological diseases.
Oxidative Originators of Graphene Barrier Coating Grown on Surfaces
Authors: Yuan Aiheng , Guan Ran , Luo Birong
Published: June 2020

Graphene coating has been proposed to be a promising oxidation barrier for metals because of its chemical inertia and physical impermeability. Nevertheless, chemical vapor deposition (CVD)‐grown graphene on metal surfaces results in many structural defects and growth imperfections, which would serve as oxidative originators and favor a substantial galvanic corrosion at such interfaces in the long term. On this basis, oxidative originators including graphene structural defects and CVD growth imperfections of graphene on copper have been reviewed from the perspective of CVD growth of graphene. The associated oxidation processes and long‐term corrosion mechanisms as a protective coating for Cu are discussed. Finally, the remaining challenges and potential improvement of graphene and graphene‐like materials grown on surfaces as a barrier coating are outlooked. We aim to providing comprehensive knowledge about the relationship between various graphene defects/growth imperfections and the oxidation/corrosion mechanisms as a protective coating, seeking a roadmap to promote the development of cheap, powerful and effective barrier technologies based on such ultrathin two‐dimensional materials.
Changes in Electron Structure of the Triple Bond in Substituted Acetylene and Diacetylene Derivatives
Authors: Jabłoński Mirosław , Krygowski Tadeusz M.
Published: June 2020

The substituent effect is usually considered by means of various Hammett‐like substituent constants and is most often related to aromatic systems. Unlike this, we present results of our research on the influence of 27 substituents spanning a wide range of electronic properties, from strongly electron‐withdrawing to strongly electron‐donating, on the electron structure of X‐substituted acetylenes and diacetylenes – thus the systems which until now have practically not been subject of any deeper studies. It is shown that the interaction through triple bond(s) is associated with a significant advantage of resonance effects and that the substituent effect transmitted by the C≡C−C≡C unit is about half of that transmitted by the C≡C unit alone. Substituent X mainly affects the closest carbon atom by means of proximity effect, hence changes of charge on this atom do not follow any substituent constants. The effect on further carbon atoms is much smaller. The presence of the C≡C−C≡C unit withdraws more charge from X than a triple bond alone, and hinders communication between X and the terminal H atom. Comparison of substituent effects to those present in X‐substituted benzene derivatives shows that the electronic properties of the terminal hydrogen atom in acetylenes and diacetylenes are most similar to the electronic properties of ortho and para hydrogen atoms in X‐substituted benzene derivatives.
Scalable Fabrication of Biophotoelectrodes by Means of Automated Airbrush Spray‐Coating
Authors: Bobrowski Tim , Conzuelo Felipe , Ruff Adrian , Hartmann Volker , Frank Anna , Erichsen Thomas , Nowaczyk Marc M. , Schuhmann Wolfgang
Published: June 2020

The fabrication and electrochemical evaluation of transparent photoelectrodes consisting of Photosystem I (PSI) or Photosystem II (PSII) is described, which are embedded and electrically wired by a redox polymer. The fabrication process is performed by an automated airbrush‐type spray coating system, which ensures controlled and scalable electrode preparation. As proof of concept, electrodes with a surface area of up to 25 cm2 were prepared. The macro‐porous structure of the indium tin oxide electrodes allows a high loading of the photoactive protein complexes leading to enhanced photocurrents, which are essential for potentially technologically relevant solar‐powered devices. In addition, we show that unpurified crude PSII extracts, which can be provided in comparatively high yields for electrode modification, are suitable for photoelectrode fabrication with comparable photocurrent densities.
Dual blockade of EGFR and VEGFR pathways: Results from a pilot study evaluating apatinib plus gefitinib as a first‐line treatment for advanced EGFR‐mutant non‐small cell lung cancer
Authors: Zhang Zhonghan , Zhang Yang , Luo Fan , Ma Yuxiang , Fang Wenfeng , Zhan Jing , Li Su , Yang Yunpeng , Zhao Yuanyuan , Hong Shaodong , Zhou Ting , Zhang Yaxiong , Zhao Shen , Huang Yan , Zhao Hongyun , Zhang Li
Published: June 2020

Background

Dual blockade of both EGFR and VEGFR pathways in EGFR‐mutant NSCLC have shown enhanced antitumor efficacy versus EGFR‐TKIs alone. Apatinib is an orally effective VEGFR‐2 tyrosine kinase inhibitor (TKI). This pilot study aims to evaluate the tolerability, pharmacokinetic profile, and antitumor activity of apatinib plus gefitinib as a therapy for EGFR‐mutant advanced NSCLC.

Methods

Advanced non‐squamous NSCLC participants harbored with the EGFR 19 deletion or the 21 L858R point mutation were included. There were two cohorts: Cohort A: apatinib 500 mg + gefitinib 250 mg. Cohort B: apatinib 250 mg + gefitinib 250 mg. The primary endpoint was safety profile. Other endpoints consisted of PK analysis, objective response rate (ORR), and progression‐free survival (PFS). Exploratory analysis was conducted using next‐generation sequencing of plasma circulating‐tumor DNA.

Results

Between July 2016 and April 2017, 13 of NSCLC patients were recruited. Six patients were pooled in Cohort A, while seven patients were in Cohort B. Adverse events (AEs) were tolerable (mostly grade 1–2) and the treatment‐related AEs were similar in both cohorts: rash (100% vs 71.4%), diarrhea (66.7% vs 71.4%), hypertension (66.7% vs 71.4%), proteinuria (66.7% vs 42.9%), and hand‐foot skin reaction (33.3% vs 28.6%). The area under plasma concentration‐time curve for the steady state of apatinib was 2864.73 ± 2605.54 ng mL–1 h–1 in Cohort A and 2445.09 ± 1550.89 ng mL–1 h–1 in Cohort B. Of the 11 patients evaluable for efficacy, Cohort A achieved an ORR of 80.0% and reached a median PFS of 19.2 months, while it was 83.3% and 13.4 months in Cohort B. Patients without a concomitant mutation at baseline had a prolonged PFS tendency (20.99 months v 13.21 months, P = .0624). The EGFR‐T790M mutation remained the dominant resistance mechanism.

Conclusion

Apatinib (500 mg) plus gefitinib (250 mg) showed a tolerable safety profile and encouraging antitumor activity for advanced EGFR‐mutant NSCLC in the first‐line setting. Phase III trials of apatinib (500 mg) plus gefitinib (250 mg) are warranted.

Trial registration

Clinicaltrials.gov, NCT02824458, date of registration June 23, 2016.
Life‐Saving Microscopy Method for Amyotrophic Lateral Sclerosis Patients
Authors: Schubert Walter
Published: June 2020

The submission describes in the form of a communication recent experiences with a promising new therapeutic approach for amyotrophic lateral sclerosis (ALS). This approach is based on imaging cycler microscopy that led to the discovery of ALS specific cells in the blood, which invade the pyramidal system (lateral corticospinal tract) of ALS patients, where they compress motor axons. The depletion of these cells leads to remission of clinical symptoms and demonstrates the important role of these cells in ALS. The therapy will be offered to ALS patients in licensed and certified centers (in progress). © 2020 International Society for Advancement of Cytometry
Disentangling landscape and local drivers of ground‐dwelling beetle community assembly in an urban ecosystem
Authors: Perry Kayla I. , Hoekstra Nicole C. , Delgado de la flor Yvan A. , Gardiner Mary M.
Published: June 2020

Community assembly is the process by which local communities are organized and maintained from the regional species pool. Understanding processes of insect assembly are of interest in “shrinking” cities where vacant land has become abundant as a result of protracted economic decline and population loss. Vacant land represents a viable conservation space for insects such as beetles that contribute to ecosystem services including pest suppression, decomposition, and nutrient cycling. However, the inherent heterogeneity of cities may pose challenges for beetle dispersal from source populations, while quality of the urban environment may constrain establishment. The objective of this study was to investigate the constraints to ground‐dwelling beetle community assembly in vacant lots and pocket prairies of Cleveland, Ohio using a functional trait‐based approach. Functional traits with a strong predictive capacity for ecological functions were measured on beetle species collected via pitfall traps. Assembly of beetle communities was primarily constrained by dispersal limitations to colonization. Over 93% of species found within treatments were capable of flight, and functional diversity of beetle communities was higher across all treatments than expected by chance. Once beetles colonized, successful establishment was influenced by heavy metal contamination and mowing frequency, with these disturbances shaping communities based on body size, antennae length, and origin. Colonization of dispersal‐limited species could be facilitated by increasing connectivity among greenspaces in cities, while establishment could be enhanced by managing local environmental conditions. Understanding how insect communities are structured in urban ecosystems provides context for observed patterns of biodiversity, advances conservation efforts, and fosters ecosystem services.
Isolated LLC converter for PEV charging for wide‐range voltage gain using six‐switch bridge
Authors: Kinoshita Yuki , Haga Hitoshi
Published: June 2020

This paper proposes a dual LLC converter based on a six‐switch bridge to charge deeply depleted plug‐in electric vehicle onboard battery packs. The primary‐side switch network comprises an input series or parallel, and two types of transformer‐independent modes. Thus, there are four operation modes. In the input series mode, normalized voltage gains are scaled to 0.5; therefore, a low output voltage can be obtained. In addition, in the input parallel mode, the normalized voltage gains are scaled to 2.0. These four modes operate at the resonant frequency at the switching frequency. Therefore, the efficiency performance can be optimized over a wide output voltage range. The validity of the proposed system is confirmed with a 1‐kW prototype.
MDSC subtypes and CD39 expression on CD8+ T cells predict the efficacy of anti‐PD‐1 immunotherapy in patients with advanced NSCLC
Authors: Koh Jiae , Kim Youjin , Lee Kyoung Young , Hur Joon Young , Kim Mi Soon , Kim Boram , Cho Hee Jin , Lee Yeong Chan , Bae Yeon Hee , Ku Bo Mi , Sun Jong‐Mu , Lee Se‐Hoon , Ahn Jin Seok , Park Keunchil , Ahn Myung‐Ju
Published: June 2020

The major suppressive immune cells in tumor sites are myeloid derived suppressor cells (MDSCs), tumor‐associated macrophages (TAMs), and Treg cells, and the major roles of these suppressive immune cells include hindering T‐cell activities and supporting tumor progression and survival. In this study, we analyzed the pattern of circulating MDSC subtypes in patients with non‐small cell lung cancer (NSCLC) whether those suppressive immune cells hinder T‐cell activities leading to poor clinical outcomes. First, we verified PMN‐MDSCs, monocytic‐MDSCs (M‐MDSCs), and Treg cells increased according to the stages of NSCLC, and MDSCs effectively suppressed T‐cell activities and induced T‐cell exhaustion. The analysis of NSCLC patients treated with anti‐PD‐1 immunotherapy demonstrated that low PMN‐MDSCs, M‐MDSCs, and CD39+CD8+ T cells as an individual and all together were associated with longer progression free survival and overall survival, suggesting PMN‐MDSCs, M‐MDSCs, and CD39+CD8+ T cells frequencies in peripheral blood might be useful as potential predictive and prognostic biomarkers.
Using directed graphs to define viewpoints to keep a metamodel, an architecture framework and views using different modeling languages consistent
Authors: Plum Nic
Published: June 2020

Keeping an architecture description of a complex system consistent is difficult. View content is specified by viewpoints which draw upon an underlying metamodel. Viewpoints need to define consistency rules. This becomes increasingly hard as the metamodel size and the number of viewpoints increase. Use of an architecture description language (ADL) such as the Unified Modeling Language (UML) complicates this further because its metamodel may not be able to implement the triples in the AD metamodel and therefore one or more views requiring use of an additional ADL. Even for an architecture framework with a small footprint, such as TRAK, it is a time‐consuming and error‐prone process to keep the metamodel, viewpoint definitions, and implementation consistent. To tackle these TRAK has been modeled by creating views against five viewpoints. These viewpoints can be used to define a metamodel, define the viewpoints for an architecture framework, assess the implementation using one or more ADLs, and record model changes over time. The viewpoint definitions and views are wholly graph‐based and provide a mechanism to define allowed and minimum view content. Views and viewpoints can be read as simple assertions requiring no technical knowledge and support query and analysis. The viewpoint definitions have been validated against a model of TRAK held in a Neo4J graph database. This showed that the TRAK metamodel contains c 750 triples not 500 as had been previously thought. It also identified metamodel elements missing from one of the UML profiles. Example views are provided together with CYPHER queries.
Seasonal insect migrations: massive, influential, and overlooked
Authors: Satterfield Dara A , Sillett T Scott , Chapman Jason W , Altizer Sonia , Marra Peter P
Published: June 2020

During seasonal changes around the globe, trillions of insects are on the move. Many insect populations, including butterflies, moths, hoverflies, and dragonflies, make repeated seasonal migrations each year. It is only during the past century that biologists have come to accept the concept of insect migration, and new research using radar, citizen science, and stable isotopes has revealed unexpected insights about this phenomenon. Drawing on these findings, we demonstrate how seasonal insect movements are both massive and ecologically influential, with consequences for food webs, nutrient transport, pollination, and infectious disease. Responding to environmental changes, some mobile insect populations are declining or shifting the timing and extent of their journeys. We suggest research and policy priorities for investigating and protecting insect migrations. Outcomes from such work could transform strategies for agricultural pest control and wildlife conservation, and could help preserve the ecological functions performed by migratory insects.
Development of an improved divergence‐free‐condition compensated coupled framework to solve flow problems with time‐varying geometries
Authors: Chiu Pao‐Hsiung , Poh Hee Joo
Published: June 2020

In this article a coupled version of the improved divergence‐free‐condition compensated method will be proposed to simulate time‐varying geometries by direct forcing immersed boundary method. The proposed method can be seen as a quasi‐multi‐moment framework due to the fact that the momentum equations are discretized by both cell‐centered and cell‐face velocity. For simulating time‐varying geometries, a semi‐implicit iterative method is proposed for calculating the direct forcing terms. Treatments for suppressing spurious force oscillations, calculating drag/lift forces, and evaluating velocity and pressure for freshly cells will also be addressed. In order to show the applicability and accuracy, analytical as well as benchmark problems will be investigated by the present framework and compared with other numerical and experimental results.
Using of an Electrochemical Compressor for Hydrogen Recirculation in Fuel Cell Vehicles
Authors: Wiebe W. , v. Unwerth T. , Schmitz S.
Published: June 2020

The automotive industry sees hydrogen‐powered fuel cell (FC) drives as a promising option with a high range and short refueling time. Current research aims to increase the profitability of the fuel cell system by reducing hydrogen consumption. This study suggests the use of an electrochemical hydrogen compressor (EHC) for hydrogen recirculation. Compared to mechanical compressors, the EHC is very efficient due to the almost isothermal conditions and due to its modular structure, can only take up a minimal amount of space in vehicles. In addition, gas separation and purification of the hydrogen takes place in an EHC, which is a significant advantage over the standard recirculation with a blower or a jet pump. The high purity of the hydrogen at the cathode outlet of the EHC, also increased partial pressure of the hydrogen at the fuel cell inlet and its efficiency. The study carried out shows that replacing the blower with the EHC reduces the hydrogen loss by purging by up to ∼95% and the efficiency of the FC system could be further improved. Thus, the EHC has a great potential for recycling hydrogen in FC systems in the automotive industry and is a great alternative to the current blower.
Enhancing managerial equity incentives with moving average payoffs
Authors: Tian Yisong S.
Published: June 2020

Prior research suggests that Asian stock options provide stronger managerial equity incentives than traditional stock options do, holding the cost of the option grant constant. Although this is true on the grant date, it is not over the life of the option grant. Very little of the initial advantage remains after 2 years because Asian stock options have diminishing incentive effects over time. A simple solution is to replace averaging over the option's life with averaging over a moving window. We show that moving average options do not have the diminishing incentive problem and are effective in preventing managerial gaming.