bluuebunny/crossref_metadata_2025_split huggingface dataset:
Large‐Area Aminated‐Graphdiyne Thin Films for Direct Methanol Fuel Cells
Authors: Wang Fan , Zuo Zicheng , Li Liang , Li Kuo , He Feng , Jiang Zhongqing , Li Yuliang 
Published: September 2019

AbstractA two‐dimensional (2D) carbon nanofilm with uniform artificial nanopores is an ideal material to ultimately suppress the fuel permeation in the proton exchange membrane fuel cells. Graphdiyne has great mechanical strength, high dimensional stability, and controllable nanopores, and has good prospects to play this crucial role. It is found that graphdiyne nanofilm with amino groups and natural nanopores can be easily prepared with high integrity. The aminated graphdiyne has good compatibility with the Nafion matrix owing to the acid–base interaction between them. The excellent comprehensive properties of graphdiyne in selectivity, dimensional stability, and integrity effectively improve the power performance and stability of fuel cells at wide temperature. Our results can be developed into a universal method that can easily realize the selective separation of ions and small molecules, and open a new way for the emerging applications in green energy.
Crosslinking Allosteric Sites on the Nucleosome
Authors: Batchelor Lucinda K. , De Falco Louis , von Erlach Thibaud , Sharma Deepti , Adhireksan Zenita , Roethlisberger Ursula , Davey Curt A. , Dyson Paul J. 
Published: September 2019

AbstractTargeting defined histone protein sites in chromatin is an emerging therapeutic approach that can potentially be enhanced by allosteric effects within the nucleosome. Here we characterized a novel hetero‐bimetallic compound with a design based on a nucleosomal allostery effect observed earlier for two unrelated drugs—the RuII antimetastasis/antitumor RAPTA‐T and the AuI anti‐arthritic auranofin. The RuII moiety binds specifically to two H2A glutamate residues on the nucleosome acidic patch, allosterically triggering a cascade of structural changes that promote binding of the AuI moiety to selective histidine residues on H3, resulting in cross‐linking sites that are over 35 Å distant. By tethering the H2A‐H2B dimers to the H3‐H4 tetramer, the hetero‐bimetallic compound significantly increases stability of the nucleosome, illustrating its utility as a site‐selective cross‐linking agent.
A Mesoporous Nanorattle‐Structured Pd@PtRu Electrocatalyst
Authors: Li Chunjie , Yu Hongjie , Liu Songliang , Xu You , Wang Ziqiang , Li Xiaonian , Wang Liang , Wang Hongjing 
Published: September 2019

AbstractPt‐based nanomaterials play important roles in the catalytic process toward oxygen reduction reaction (ORR). Rationally regulating the composition and morphology of the catalysts could enhance the catalytic performance effectively. In this work, an effective method is presented to synthesize Pd@ mesoporous PtRu nanorattles (Pd@mPtRu NRs) containing a Pd core and a mesoporous PtRu shell. Owing to the unique structure and PtRu alloy composition, the prepared Pd@mPtRu NRs exhibit an enhanced catalytic performance and durability toward ORR relative to mesoporous PtRu hollow nanoparticles (mPtRu HNs) and commercial Pt/C. The proposed approach may provide a general way to synthesize Pt‐based yolk‐shell structures with different compositions.
Duplex‐forming Oligonucleotide of Triazole‐linked RNA
Authors: Fujino Tomoko , Suzuki Takeru , Ooi Tsugumi , Ikemoto Koki , Isobe Hiroyuki 
Published: September 2019

AbstractAn oligonucleotide of triazole‐linked RNA (TLRNA) was synthesized by performing consecutive copper‐catalyzed azide‐alkyne cycloaddition reactions for elongation. The reaction conditions that had been optimized for the synthesis of 3‐mer TLRNA were found to be inappropriate for longer oligonucleotides, and the conditions were reoptimized for the solid‐phase synthesis of an 11‐mer TLRNA oligonucleotide. Duplex formation of the 11‐mer TLRNA oligonucleotide was examined with the complementary oligonucleotide of natural RNA to reveal the effects of the 2′‐OH groups on the duplex stability.
Controlled Synthesis of CuCo2S4@Ni(OH)2 Hybrid Nanorod Arrays for Water Splitting at an Ultralow Cell Voltage of 1.47 V
Authors: Du Xiaoqiang , Fu Jianpeng , Zhang Xiaoshuang 
Published: September 2019

AbstractDeveloping environmentally friendly and highly active water splitting catalysts would be of great significance for clean energy conversion and utilization processes. Heterogeneous CuCo2S4@Ni(OH)2 nanorod arrays with abundant oxygen vacancy firstly have been designed through a controllable hydrothermal and electrodeposition method. The synergies and open structures of the particular hierarchical structure together with the abundant oxygen vacancies offer more surface reactive centers, which can promote the electron transfer rate and reduce the activation energy of intermediate species. The CuCo2S4@Ni(OH)2–20 min nanorod arrays are considered as an excellent and robust electrocatalyst for the proton reduction under an alkaline condition with an extraordinary low overpotential of 117 mV at 10 mA cm−2. The CuCo2S4@Ni(OH)2–20 min heterostructures electrode is also stable and robust for the water oxidation reaction, needing an overpotential of only 250 mV to obtain 100 mA cm−2. Therefore, an alkaline electrolyzer was designed using CuCo2S4@Ni(OH)2–20 min nanorod arrays as bifunctional electrocatalyst, which can complete overall water splitting at a cell voltage of 1.47 V with 10 mA cm−2, suggesting a promising combination of the same material for efficient overall water splitting device. The cell voltage of 1.47 V, to our knowledge, is among the lowest values of the published support catalysts for electrocatalytic water splitting up to now.
Efficient production of S‐adenosyl‐l‐methionine from dl‐methionine in metabolic engineered Saccharomyces cerevisiae
Authors: Liu Wei , Tang Dandan , Shi Rui , Lian Jiazhang , Huang Lei , Cai Jin , Xu Zhinan 
Published: September 2019

AbstractS‐Adenosyl‐l‐methionine (SAM) is an important small molecule compound widely used in treating various diseases. Although l‐methionine is generally used, the low‐cost dl‐methionine is more suitable as the substrate for industrial production of SAM. However, d‐methionine is inefficient for SAM formation due to the substrate‐specificity of SAM synthetase. In order to increase the utilization efficiency of dl‐methionine, intracellular conversion of d‐methionine to l‐methionine was investigated in the type strain Saccharomyces cerevisiae BY4741 and an industrial strain S. cerevisiae HDL. Firstly, via disruption of HPA3 encoding d‐amino acid‐N‐acetyltransferase, d‐methionine was accumulated in vivo and no N‐acetyl‐d‐methionine production was observed. Further, codon‐optimized d‐amino acid oxidase (DAAO) gene from Trigonopsis variabilis (Genbank MK280686) and l‐phenylalanine dehydrogenase gene (l‐PheDH) from Rhodococcus jostii (Genbank MK280687) were introduced to convert d‐methionine to l‐methionine, SAM concentration and content was increased by 110% and 72.1% in BY4741 (plasmid borne) and increased by 38.2% and 34.1% in HDL (genome integrated), by feeding 0.5 g/L d‐methionine. Using the recently developed CRISPR tools, the DAAO and l‐PheDH expression cassettes were integrated into the HPA3 and SAH1 loci while SAM2 expression was integrated into the SPE2 and GLC3 loci of HDL, and the resultant strain HDL‐R2 accumulated 289% and 192% more SAM concentration and content, respectively, by feeding 0.5 g/L dl‐methionine. Further, in a 10 L fed‐batch fermentation process, 10.3 g/L SAM were accumulated with the SAM content of 242 mg/g dry cell weight by feeding 16 g/L dl‐methionine. The strategies used here provided a promising approach to enhance SAM production using low‐cost dl‐methionine.
Biosynthesis of the human milk oligosaccharide 3‐fucosyllactose in metabolically engineered Escherichia coli via the salvage pathway through increasing GTP synthesis and β‐galactosidase modification
Authors: Choi Yun Hee , Park Bum Seok , Seo Joo‐Hyun , Kim Byung‐Gee 
Published: September 2019

Abstract3‐Fucosyllactose (3‐FL) is one of the major fucosylated oligosaccharides in human milk. Along with 2′‐fucosyllactose (2′‐FL), it is known for its prebiotic, immunomodulator, neonatal brain development, and antimicrobial function. Whereas the biological production of 2′‐FL has been widely studied and made significant progress over the years, the biological production of 3‐FL has been hampered by the low activity and insoluble expression of α‐1,3‐fucosyltransferase (FutA), relatively low abundance in human milk oligosaccharides compared with 2′‐FL, and lower digestibility of 3‐FL than 2′‐FL by bifidobacteria. In this study, we report the gram‐scale production of 3‐FL using E. coli BL21(DE3). We previously generated the FutA quadruple mutant (mFutA) with four site mutations at S46F, A128N, H129E, Y132I, and its specific activity was increased by nearly 15 times compared with that of wild‐type FutA owing to the increase in kcat and the decrease in Km. We overexpressed mFutA in its maximum expression level, which was achieved by the optimization of yeast extract concentration in culture media. We also overexpressed L‐fucokinase/GDP‐
L‐fucose pyrophosphorylase to increase the supply of GDP‐fucose in the cytoplasm. To increase the mass of recombinant whole‐cell catalysts, the host E. coli BW25113 was switched to E. coli BL21(DE3) because of the lower acetate accumulation of E. coli BL21(DE3) than that of E. coli BW25113. Finally, the lactose operon was modified by partially deleting the sequence of LacZ (lacZΔm15) for better utilization of D‐lactose. Production using the lacZΔm15 mutant yielded 3‐FL concentration of 4.6 g/L with the productivity of 0.076 g·L−1·hr−1 and the specific 3‐FL yield of 0.5 g/g dry cell weight.
Myocardial tissue salvage is correlated with ischemic border region temperature at reperfusion
Authors: Merrill Thomas L. , Mitchell Jennifer E. , Merrill Denise R. , Gorman Joseph H. , Gorman Robert C. , Gillespie Matthew J. 
Published: September 2019

AbstractObjectivesOur pilot study investigated the association between region‐specific myocardial tissue temperature and tissue salvage using a novel tri‐lumen cooling catheter to provide rapid localized cooling directly to the heart in an open‐chest porcine model of ischemia–reperfusion.BackgroundTherapeutic hypothermia remains a promising strategy to limit reperfusion injury following myocardial ischemia.MethodsLarge swine underwent 60 min of coronary occlusion followed by 3 hr of reperfusion. Prior to inducing ischemia, six temperature probes were placed directly on the heart, monitoring myocardial temperatures in different locations. Hemodynamic parameters and core temperature were also collected. Approximately 15 min prior to reperfusion, the cooling catheter was inserted via femoral artery and the distal tip advanced proximal to the occluded coronary vessel under fluoroscopic guidance. Autologous blood was pulled from the animal via femoral sheath and delivered through the central lumen of the cooling catheter, delivering at 50 ml/min, 27°C at the distal tip. Cooling was continued for an additional 25 min after reperfusion followed by a 5‐min controlled rewarming. Hearts were excised and assessed for infarct size per area at risk.ResultsAlthough cooling catheter performance was consistent throughout the study (38 W), the resulting tissue cooling was not. Our results show a correlation between myocardial tissue salvage and ischemic border region (IBR) temperature at the time of reperfusion (R2 = 0.59, p = 0.027). IBR tissue is the tissue located at the boundary between healthy and ischemic tissues.ConclusionsOur findings suggest that localized, rapid, short‐term myocardial tissue cooling has the potential to limit reperfusion injury in humans.
Various Techniques for Preparation of Thin‐Film Composite Mixed‐Matrix Membranes for CO2 Separation
Authors: Fauzan Nur Aqilah Bt , Mannan Hafiz Abdul , Nasir Rizwan , Mohshim Dzeti Farhah Bt , Mukhtar Hilmi 
Published: September 2019

AbstractThe application of thin‐film composite mixed‐matrix membranes (TFC‐MMMs) for gas separation is widely considered as an efficient separation technology. The principal methods for the preparation of TFC‐MMMs are dip‐coating, phase inversion, and interfacial polymerization comprising different types of support layers. These methods influence the CO2 permeation over the selective and support layers. A comprehensive review is provided for capturing new details of progress achieved in developing TFC‐MMMs with detailed performance of gas separation in the previous few years. Various preparation techniques of TFC‐MMMs and their effect on the gas separation performance of the prepared membranes are described.
Regioisomeric BODIPY Benzodithiophene Dyads and Triads with Tunable Red Emission as Ratiometric Temperature and Viscosity Sensors
Authors: Aswathy P. R. , Sharma Sushil , Tripathi Narendra Pratap , Sengupta Sanchita 
Published: September 2019

AbstractRegioisomeric acceptor‐donor (AD) molecular rotors (p‐AD, m‐AD and m‐ADA) were synthesized and characterized, wherein dyads p‐AD and m‐AD, and triad m‐ADA contained 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) and benzodithiophene (BDT) as electron‐acceptor and electron‐donor, respectively. In all the compounds, the donor and acceptor moieties are electronically decoupled by a phenyl spacer, either through a para coupling or through a meta coupling. The dyad counterparts p‐AD and m‐AD showed distinct photophysical characteristics in which dyad p‐AD showed TICT band at ca. 654 nm characterized by a Stokes shift of ca. 150 nm and prominent solvatochromism. However, meta regioisomeric triad m‐ADA showed well‐defined aggregation in solution. Notably, because of the temperature‐tunable and solvent‐viscosity‐dependent emission, efficient ratiometric temperature sensing with positive and negative temperature coefficients and viscosity sensing was observed for all compounds. Interestingly, the fluorescence of dyad m‐AD (in 10/90 v/v THF/water) revealed a near‐white light emission with CIE chromaticity coordinates (x, y) of (0.32, 0.29). Furthermore, the fluorescence emission of p‐AD in THF at 0 °C also showed a near‐white light emission with chromaticity coordinates (x, y) of (0.34, 0.27). Such multifunctional rotors with readily tunable emission in the red region and prominent temperature‐ and viscosity‐sensing abilities are promising for sensing and bioimaging applications.
Luminescent Mono‐, Di‐, and Triradicals: Bridging Polychlorinated Triarylmethyl Radicals by Triarylamines and Triarylboranes
Authors: Hattori Yohei , Michail Evripidis , Schmiedel Alexander , Moos Michael , Holzapfel Marco , Krummenacher Ivo , Braunschweig Holger , Müller Ulrich , Pflaum Jens , Lambert Christoph 
Published: September 2019

AbstractUp to three polychlorinated pyridyldiphenylmethyl radicals bridged by a triphenylamine carrying electron withdrawing (CN), neutral (Me), or donating (OMe) groups were synthesized and analogous radicals bridged by tris(2,6‐dimethylphenyl)borane were prepared for comparison. All compounds were as stable as common closed‐shell organic compounds and showed significant fluorescence upon excitation. Electronic, magnetic, absorption, and emission properties were examined in detail, and experimental results were interpreted using DFT calculations. Oxidation potentials, absorption and emission energies could be tuned depending on the electron density of the bridges. The triphenylamine bridges mediated intramolecular weak antiferromagnetic interactions between the radical spins, and the energy difference between the high spin and low spin states was determined by temperature dependent ESR spectroscopy and DFT calculations. The fluorescent properties of all radicals were examined in detail and revealed no difference for high and low spin states which facilitates application of these dyes in two‐photon absorption spectroscopy and OLED devices.
Synthesis and Characterisation of Hierarchically Structured Titanium Silicalite‐1 Zeolites with Large Intracrystalline Macropores
Authors: Weissenberger Tobias , Leonhardt Rainer , Zubiri Benjamin Apeleo , Pitínová‐Štekrová Martina , Sheppard Thomas L. , Reiprich Bastian , Bauer Jürgen , Dotzel Ralf , Kahnt Maik , Schropp Andreas , Schroer Christian G. , Grunwaldt Jan‐Dierk , Casci John L. , Čejka Jiří , Spiecker Erdmann , Schwieger Wilhelm 
Published: September 2019

AbstractThe successful synthesis of hierarchically structured titanium silicalite‐1 (TS‐1) with large intracrystalline macropores by steam‐assisted crystallisation of mesoporous silica particles is reported. The macropore topology was imaged in 3D by using electron tomography and synchrotron radiation‐based ptychographic X‐ray computed tomography, revealing interconnected macropores within the crystals accounting for about 30 % of the particle volume. The study of the macropore formation mechanism revealed that the mesoporous silica particles act as a sacrificial macropore template during the synthesis. Silicon‐to‐titanium ratio of the macroporous TS‐1 samples was successfully tuned from 100 to 44. The hierarchically structured TS‐1 exhibited high activity in the liquid phase epoxidation of 2‐octene with hydrogen peroxide. The hierarchically structured TS‐1 surpassed a conventional nano‐sized TS‐1 sample in terms of alkene conversion and showed comparable selectivity to the epoxide. The flexible synthesis route described here can be used to prepare hierarchical zeolites with improved mass transport properties for other selective oxidation reactions.
Excited‐State Dynamics of Non‐Luminescent and Luminescent π‐Radicals
Authors: Teki Yoshio 
Published: September 2019

AbstractRecently, the potential use of organic π‐radicals and related spin systems has been expanded to modern technological applications. The unique excited‐state dynamics of organic π‐radicals can be useful to improve the stability of photochemically unstable organic compounds, make the polarization transfer applicable to information technology, and achieve effective up‐conversion of interest for luminescence bioimaging, among others. Furthermore, highly luminescent stable π‐radicals have been recently reported, which are especially interesting for application in organic light‐emitting devices owing to their potential to provide an internal quantum efficiency of 100 %. Thus, the excited‐state nature of stable π‐radicals as well as the control of their excited‐state spin dynamics are emerging topics both in terms of fundamental science and related technological applications. In this minireview, we focus on the excited‐state dynamics of both photostable non(weakly)‐luminescent and luminescent π‐radicals, which are opposites of each other. In particular, we cover the following topics: 1) effective generation of high‐spin photoexcited states and control of the excited‐state dynamics by using non‐luminescent π‐radicals, 2) unique excited‐state dynamics of luminescent π‐radicals and radical excimers, and 3) applications utilizing excited‐state dynamics of π‐radicals.
Palladium‐Catalyzed C8‐Arylation of Naphthalenes through C−H Activation: A Combined Experimental and Computational Study
Authors: Garrec Julian , Cordier Marie , Frison Gilles , Prévost Sébastien 
Published: September 2019

AbstractHerein, a direct C8‐arylation reaction of 1‐amidonaphthalenes is described. By using diaryliodonium salts as arylating agents, the palladium‐catalyzed C−H activation reaction showed perfect C8 regioselectivity and a wide functional group tolerance. In most cases, the desired polyaromatic compounds were isolated in good to excellent yields. To explain the observed regioselectivity, DFT calculations were performed and highlighted the crucial role of the amide directing group. Finally, the utility of this method is showcased by the synthesis of benzanthrone derivatives.
Highly Stable and Inert Complexation of Indium(III) by Reinforced Cyclam Dipicolinate and a Bifunctional Derivative for Bead Encoding in Mass Cytometry
Authors: Grenier Laura , Beyler Maryline , Platas‐Iglesias Carlos , Closson Taunia , Gómez David Esteban , Seferos Dwight S. , Liu Peng , Ornatsky Olga I. , Baranov Vladimir , Tripier Raphaël 
Published: September 2019

AbstractH2cb‐te2pa, a cross‐bridged cyclam functionalized by two picolinate arms, was used for the formation of an incredible inert InIII chelate. The inertness of the complex was evaluated by UV/Vis experiments in several competitive media and was highlighted by the comparison with [In(dota)]− and [In(dtpa)]2− (H4dota = 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid, H5dtpa = diethylenetriamine pentaacetic acid), which are currently used in biological applications. For the first time, a bifunctional analogue of H2cb‐te2pa was prepared by C‐functionalization to keep its coordination properties intact. However, this strategy leads to the formation of two diastereoisomers as evidenced and studied by NMR experiments and DFT calculations. Kinetic studies proved nevertheless that both isomers of the complex are equally inert. They were therefore used without distinction for their covalent grafting on polystyrene beads. The so‐called metal‐encoded beads were tested for imaging mass cytometry. The detection of 115In allows the generation of images with high quality, proving the great potential of the bifunctional [In(cb‐te2pa)]+ derivatives for single‐cell analysis by mass cytometry.
Hue, chroma, and lightness preference in Chinese adults: Age and gender differences
Authors: Zhang Yujing , Liu Pingping , Han Buxin , Xiang Yang , Li Liqin 
Published: September 2019

AbstractRecent studies have shown cultural differences in color preference. However, the color preference of people in China, which was found to have its own pattern, was yet to be studied in depth. The current study investigated color preference and the associated age and gender differences in an adult national sample (N = 1290) to provide a culture‐specific characteristic of color perception. Participants rated how much they liked each of 31 colors (four chroma‐lightness levels of red, orange, yellow, green, cyan, blue, and purple, plus three achromatic colors). We found a unique saturated color preference pattern characterized by red, cyan, and blue being preferred the most and orange as the least preferred chromatic color. The “red preference” phenomenon was observed in Chinese adults. Light colors were preferred the most in terms of chroma‐lightness level, followed by saturated, muted, and dark colors. The results of a principal component analysis of the 28 chromatic colors showed that blue‐green‐like colors (cool colors) constituted the largest proportion of color preference. The preference for orange and several dark colors increased with age, while that for bluish colors, purple, yellow, white, black, and light colors decreased. In terms of gender, women liked cyan, white, pink, and light colors and disliked red, orange, and dark colors more than men did. Our findings provide new empirical evidence about the color preference of Chinese and may offer some insight into the study of color preference and lay the foundations for future theoretical and practical research.