bluuebunny/crossref_metadata_2025_split huggingface dataset:
High‐frequency motor rehabilitation in amyotrophic lateral sclerosis: a randomized clinical trial
Authors: Zucchi Elisabetta , Vinceti Marco , Malagoli Carlotta , Fini Nicola , Gessani Annalisa , Fasano Antonio , Rizzi Romana , Sette Elisabetta , Cavazza Stefano , Fiocchi Alena , Buja Sergio , Faccioli Tiziana , Storani Simone , Mandrioli Jessica 
Published: March 2019

AbstractObjectiveExercise may be physically and psychologically important for people with ALS, especially in the earlier stages of the disease, and, as a consequence, current ALS clinical management includes individualized rehabilitation as part of multidisciplinary care because. However, while recent studies focused on which type of exercise is more indicated to ALS patients, there is no evidence at which frequency training sessions should be performed.MethodsWe performed an assessor blinded randomized clinical trial to investigate the superiority of two different frequencies of exercise on rate of progression in ALS. We enrolled 65 patients in two groups: intensive exercise regimen (IER, five sessions/week) versus usual exercise regimen (UER, two sessions/week). The primary aim was to assess if IER decreased disease progression, measured through Amyotrophic Lateral Sclerosis Functional Rating Scale‐Revised, with respect to UER. Secondary aims included assessment of adverse events, tracheostomy‐free survival, motor and respiratory functions, fatigue, quality of life and caregiver burden. Treatment regimen consisted for both groups of the same kind of exercise including aerobic training, endurance training, stretching or assisted active mobilization, differing for frequency of intervention.ResultsNo significant changes in disease progression were found in patients under IER versus UER. At the end of the study, there were no significant differences between the two groups in survival, respiratory function, time to supporting procedures, and quality of life. Adverse events, fatigue, and caregiver burden were not different between the two treatment regimens.ConclusionsDespite some limitations, our trial demonstrated that high‐frequency physical exercise was not superior to UER on ALSFRS‐R scores, motor and respiratory functions, survival, fatigue, and quality of life of ALS patients.
Fused Benzothiadiazole: A Building Block for n‐Type Organic Acceptor to Achieve High‐Performance Organic Solar Cells
Authors: Yuan Jun , Zhang Yunqiang , Zhou Liuyang , Zhang Chujun , Lau Tsz‐Ki , Zhang Guichuan , Lu Xinhui , Yip Hin‐Lap , So Shu Kong , Beaupré Serge , Mainville Mathieu , Johnson Paul A. , Leclerc Mario , Chen Honggang , Peng Hongjian , Li Yongfang , Zou Yingping 
Published: March 2019

AbstractNarrow bandgap n‐type organic semiconductors (n‐OS) have attracted great attention in recent years as acceptors in organic solar cells (OSCs), due to their easily tuned absorption and electronic energy levels in comparison with fullerene acceptors. Herein, a new n‐OS acceptor, Y5, with an electron‐deficient‐core‐based fused structure is designed and synthesized, which exhibits a strong absorption in the 600–900 nm region with an extinction coefficient of 1.24 × 105 cm−1, and an electron mobility of 2.11 × 10−4 cm2 V−1 s−1. By blending Y5 with three types of common medium‐bandgap polymers (J61, PBDB‐T, and TTFQx‐T1) as donors, all devices exhibit high short‐circuit current densities over 20 mA cm−2. As a result, the power conversion efficiency of the Y5‐based OSCs with J61, TTFQx‐T1, and PBDB‐T reaches 11.0%, 13.1%, and 14.1%, respectively. This indicates that Y5 is a universal and highly efficient n‐OS acceptor for applications in organic solar cells.
Functionalized Porous Aromatic Frameworks as High‐Performance Adsorbents for the Rapid Removal of Boric Acid from Water
Authors: Kamcev Jovan , Taylor Mercedes K. , Shin Dong‐Myeong , Jarenwattananon Nanette N. , Colwell Kristen A. , Long Jeffrey R. 
Published: March 2019

AbstractThis study demonstrates that functionalized, highly porous polymers are promising for the adsorptive capture of boric acid, a neutral contaminant that is difficult to remove from seawater using conventional reverse osmosis membranes. Appending N‐methyl‐d‐glucamine (NMDG) to the pore walls of high‐surface‐area porous aromatic frameworks (PAFs) yields the adsorbents PAF‐1‐NMDG and P2‐NMDG in a simple two‐step synthesis. The boron‐selective PAFs demonstrate adsorption capacities that are up to 70% higher than those of a commercial boron‐selective resin, Amberlite IRA743, and markedly faster adsorption rates, owing to their higher NMDG loadings and greater porosities relative to the resin. Remarkably, PAF‐1‐NMDG is able to reduce the boron concentration in synthetic seawater from 2.91 to <0.5 ppm in less than 3 min at an adsorbent loading of only 0.3 mg mL−1. The boron adsorption rate constants of both frameworks, determined via a pseudo‐second‐order rate model, represent the highest values reported in the literature—in most cases orders of magnitude higher than those of other boron‐selective adsorbents. The frameworks can also be readily regenerated via mild acid/base treatment and maintain constant boron adsorption capacities for at least 10 regeneration cycles. These results highlight the numerous advantages of PAFs over traditional porous polymers in water treatment applications.
Magneto‐Optical Metamaterials: Nonreciprocal Transmission and Faraday Effect Enhancement
Authors: Fan Bo , Nasir Mazhar E. , Nicholls Luke H. , Zayats Anatoly V. , Podolskiy Viktor A. 
Published: March 2019

AbstractMagneto‐optical effects are at the heart of modern technologies providing opportunities for polarization control in laser physics and optical communications, metrology, and in high‐density data storage. Here a new type of a hyperbolic magneto‐optical metamaterial based on Au–Ni nanorod arrays is developed. The metamaterial exhibits an enhanced magneto‐optical response with large rotation of the polarization plane and nonreciprocal light transmission. The effective medium model that incorporates both plasmonic and magneto‐optical phenomena in complex multicomponent nanorod media is proposed and validated. The experimental and theoretical results indicate that the magneto‐optical response of the nanostructured metamaterial is drastically enhanced and spectrally modified with respect to bulk ferromagnetic media due to interplay between strong anisotropy and magnetic field induced polarization rotation.
Room Temperature Broadband Polariton Lasing from a Dye‐Filled Microcavity
Authors: Sannikov Denis , Yagafarov Timur , Georgiou Kyriacos , Zasedatelev Anton , Baranikov Anton , Gai Lizhi , Shen Zhen , Lidzey David , Lagoudakis Pavlos 
Published: March 2019

AbstractA material system is proposed to generate polariton lasing at room temperature over a broad spectral range. The system developed is based on a boron‐dipyrromethene fluorescent dye (BODIPY‐G1) that is dispersed into a polystyrene matrix and used as the active layer of a strongly coupled microcavity. It is shown that the BODIPY‐G1 exciton polaritons undergo nonlinear emission over a broad range of exciton–cavity mode detuning in the green‐yellow portion of the visible spectrum, with polariton lasing achieved over a spectral range spanning 33 nm. The recorded linewidth of ≈0.1 nm corresponds to a condensate coherence lifetime of ≈1 ps. It is proposed that similar effects can be anticipated using a range of molecular dyes in the BODIPY family; a result that paves the way for tunable polariton devices over the visible and near‐infrared spectral region.
Approaching the Intrinsic Lifetime and Modulating a Graphene Plasmonic Resonance at a Few Hundred GHz
Authors: Ye Tong , Wang Bo , Wang Chun , Li Zhiyuan , Zhang Zhenwei , Jin Kuijuan , Wang Li , Yin Yan 
Published: March 2019

AbstractGraphene‐based metamaterials exhibit large tunability, low insertion loss, and high field confinement compared with metal‐based structures. Graphene‐based metamaterials may find numerous applications in optical modulators, optoelectronic devices, and chemical sensors in the few‐hundred‐GHz and low‐THz regime, constituting a new frontier as electronics and wireless communication continuously push further to higher frequencies. However, the main challenge is overcoming loss in graphene‐based resonant applications. Here, a low‐loss graphene plasmonic resonant modulator is demonstrated that operates at a few hundred GHz and 1 THz. The modulation depth is in excess of 35% with two layers of graphene. Numerical simulations show good agreement with the experimental results and reveal 100–200 fs lifetimes, which are approaching the intrinsic lifetime of the graphene plasmon due to the suppression of loss from phonon and edge scattering. The above values are the closest to electronic frequencies and represent the longest plasmon lifetime and largest modulation depth in graphene plasmon resonance devices reported so far.
Hydroxyl Assisted Rhodium Catalyst Supported on Goethite Nanoflower for Chemoselective Catalytic Transfer Hydrogenation of Fully Converted Nitrostyrenes
Authors: Hu Zenan , Ai Yongjian , Liu Lei , Zhou Junjie , Zhang Gang , Liu Hongqi , Liu Xiangyu , Liu Zhibo , Hu Jianshe , Sun Hong‐bin , Liang Qionglin 
Published: March 2019

AbstractControl of chemoselectivity is a special challenge for the reduction of nitroarenes bearing one or more unsaturated groups. Here, we report a flower‐like Rh/α‐FeOOH catalyst for the chemoselective hydrogenation of nitrostyrene to vinylaniline over full conversion, which benefits the new functionalized aminostyrene because the multisubstituted aminostyrenes are usually commercially unavailable. This catalyst does not only show desirable selectivity for the vinylanilines, but also exhibits the inertness to various other reducible groups over wide reaction duration. The catalytic selectivity for the reduction of the nitro group towards vinyl group was investigated by the control experiments and FT‐IR analysis. We have found that the abundant hydroxyl groups in the α‐FeOOH may contribute to the improvement of catalytic activity and selectivity. Furthermore, the catalyst exhibits excellent stability and keeps its catalytic performance even after 6 cycles.magnified image
Loop Swapping as a Potent Approach to Increase Ene Reductase Activity with Nicotinamide Adenine Dinucleotide (NADH)
Authors: Mähler Christoph , Kratzl Franziska , Vogel Melina , Vinnenberg Stefan , Weuster‐Botz Dirk , Castiglione Kathrin 
Published: March 2019

AbstractThe asymmetric reduction of alkenes is a widely used transformation in industry. Ene reductases (ERs) are (βα)8‐barrel folded enzymes capable of catalyzing this hydrogenation reaction. At the expense of nicotinamide coenzymes, ERs can reduce a wide range of electron‐deficient alkenes in an anti‐specific manner and with high regio‐ and stereoselectivities. However, a cost‐effective industrial use of these enzymes is hampered, since most ERs prefer nicotinamide adenine dinucleotide phosphate (NADPH) to the more stable and less expensive non‐phosphorylated nicotinamide adenine dinucleotide (NADH) as coenzyme. Here, we demonstrate an approach to both modify the biocatalysts coenzyme selectivity and strongly increase the activity and affinity with NADH. By swapping loop regions of the cyanobacterial NostocER1 for the corresponding regions of two NADH‐favoring ERs, a strong alteration of the biocatalyst's coenzyme binding was achieved. This made possible a transfer of the respective donor‐ER kinetic parameters to NostocER1. Additionally, outperformance of both donors in terms of activity was achieved through combinatorial swapping of loops of both species. These findings demonstrate the high potential of loop swapping as protein engineering approach to selectively optimize the coenzyme binding of ERs.magnified image
One‐Pot Cascade Synthesis of (3S)‐Hydroxyketones Catalyzed by Transketolase via Hydroxypyruvate Generated in Situ from d‐Serine by d‐Amino Acid Oxidase
Authors: L'enfant Mélanie , Bruna Felipe , Lorillière Marion , Ocal Nazim , Fessner Wolf‐Dieter , Pollegioni Loredano , Charmantray Franck , Hecquet Laurence 
Published: March 2019

AbstractWe described an efficient in situ generation of hydroxypyruvate from d‐serine catalyzed by a d‐amino acid oxidase from Rhodotorula gracilis. This strategy revealed an interesting alternative to the conventional chemical synthesis of hydroxypyruvate starting from toxic bromopyruvate or to the enzymatic transamination from l‐serine requiring an additional substrate as amino acceptor. Hydroxypyruvate thus produced was used as donor substrate of transketolases from Escherichia coli or from Geobacillus stearothermophilus catalyzing the stereoselective formation of a carbon−carbon bond. The enzymatic cascade reaction was performed in one‐pot in the presence of d‐serine and appropriate aldehydes for the synthesis of valuable (3S)‐hydroxyketones, which were obtained with high enantio‐ and diastereoselectivity and in good yield. The efficiency of the process was based on the irreversibility of both reactions allowing complete conversion of d‐serine and aldehydes.magnified image
Co (II) Boron Imidazolate Framework with Rigid Auxiliary Linkers for Stable Electrocatalytic Oxygen Evolution Reaction
Authors: Wen Tian , Zheng Yao , Zhang Jian , Davey Kenneth , Qiao Shi‐Zhang 
Published: March 2019

AbstractMetal–organic frameworks (MOFs) have significant potential for practical application in catalysis. However, many MOFs are shown to be sensitive to aqueous solution. This severely limits application of MOFs in electrocatalytic operations for energy production and storage. Here, a Co (II) boron imidazolate framework CoB(im)4(ndc)0.5 (BIF‐91, im = imidazolate, ndc = 2,6‐naphthalenedicarboxylate) that is rationally designed and successfully tested for electrocatalytic application in strong alkaline (pH ≈ 14) solution is reported. In such a BIF system, the inherent carboxylate species segment large channel spaces into multiple domains in which each single channel is filled with ndc ligands through the effect of zeolite channel confinement. These ligands, with strong CH···π interaction, act as a rigid auxiliary linker to significantly enhance the structural stability of the BIF‐91 framework. Additionally, the π‐conjugated effect in BIF‐91 stabilizes dopant Fe (III) at the atomic scale to construct Fe‐immobilized BIF‐91 (Fe@BIF‐91). Due to the synergistic effect between Fe (III) guest and Co (II) in the framework, the Fe@BIF‐91 acts as an active and stable electrocatalyst for the oxygen evolution reaction in alkaline solution.
Synchrony in fall leaf drop: chlorophyll degradation, color change, and abscission layer formation in three temperate deciduous tree species
Authors: Primka Edward J. , Smith William K. 
Published: March 2019

Premise of the StudyDeciduous tree species remove some nutrients from their leaves during fall leaf senescence through retranslocation. Retranslocation impacts the timeline of leaf fall, amount of active chlorophyll, and overall leaf nitrogen content as fall color change occurs. Our objective was to identify interspecific differences in the timing of abscission layer formation, leaf color change, and the level of chlorophyll degradation of young trees during fall senescence.MethodsLeaf relative chlorophyll content for three tree species was measured during fall 2015 by a greenness meter. These measurements were calibrated for each species through spectrophotometric determination of leaf chlorophyll concentration. Abscission layer formation was tracked using light microscopy of sampled leaves. Excised leaves were photographed on a flat white surface to track species leaf color through time.Key ResultsAll three species had different chlorophyll declination rates throughout the fall season. The maple species started with less chlorophyll and began abscission layer formation earlier. The other two species had a similar starting chlorophyll level and onset timing of abscission layer formation. Visible leaf color change was not associated with a threshold in either chlorophyll degradation or abscission layer formation across species.ConclusionsMaple species degraded less chlorophyll on average, in the fall, than did the oak and beech species. The rate of chlorophyll degradation in coordination with abscission layer formation varied by species. Color change was not a good predictor of level of chlorophyll degradation in leaves across species.
Three‐Component Reaction of Potassium Alkyltrifluoroborates, Sulfur Dioxide and Allylic Bromides under Visible‐Light Irradiation
Authors: Ye Shengqing , Li Xiaofang , Xie Wenlin , Wu Jie 
Published: March 2019

AbstractDiverse allylic sulfones are generated through a three‐component reaction of potassium alkyltrifluoroborates, sulfur dioxide and allylic bromides in the presence of 9‐mesityl‐10‐methyl acridinium perchlorate under visible light irradiation at room temperature. This transformation proceeds efficiently, and a broad reaction scope is demonstrated with good functional groups tolerance. This reaction is initiated by the treatment of potassium alkyltrifluoroborate under visible‐light irradiation in the presence of a photocatalyst, leading to alkyl radical. This alkyl radical intermediate is trapped by sulfur dioxide to provide alkylsulfonyl radical, which then undergoes further transformation to afford the corresponding allylic sulfone.
Costs and training results of an objectively validated cadaveric perfusion‐based internal carotid artery injury simulation during endoscopic skull base surgery
Authors: Donoho Daniel A. , Johnson Cali E. , Hur Kevin T. , Buchanan Ian A. , Fredrickson Vance L. , Minneti Michael , Zada Gabriel , Wrobel Bozena B. 
Published: March 2019

BackgroundInternal carotid artery injury (ICAI) is a rare, life‐threatening complication of endoscopic endonasal approaches (EEAs). High‐fidelity simulation methods exist, but optimization of the training cohort, training paradigm, and costs of simulation training remain unknown.MethodsUsing our previously validated, high‐fidelity, perfused‐cadaver model, participants attempted to manage a simulated ICAI. After a brief instructional video and coaching, the simulation was repeated. Training success was defined as successful ICAI control on the second attempt after failure on the initial attempt. Marginal costs were measured.ResultsSeventy‐two surgeons participated in the standardized simulation, which lasted ≤15 minutes. The marginal cost of simulation was $275.00 per surgeon. A total of 44.4% (n = 32) succeeded on the first attempt before training (previously proficient); 44.4% (n = 32) failed the first attempt, but succeeded after training (training successes); and 11.1% (n = 8) failed both attempts. The cost per training success was $618.75. Forty‐two surgeons had never treated an ICAI, with 24 becoming training successes (57.1% overall, 82.8% when excluding previously proficient surgeons). Twenty‐nine had experienced a real or simulated ICAI, with 8 (27.6% overall, 72.7% excluding previously proficient surgeons) becoming training successes. The cost per training success was lowest in the ICAI‐naive group ($481.25) and highest among surgeons with simulated and real ICAI experience ($1650).ConclusionsSurgeons can be trained to manage ICAI in a single, brief, low‐cost session. Although all groups improved, training an ICAI‐naive or resident cohort may maximize training results. A perfused‐cadaver model is a reproducible, realistic, and low‐cost method for training surgeons to manage life‐threatening ICAI during an EEA.
Disulfide‐Unit Conjugation Enables Ultrafast Cytosolic Internalization of Antisense DNA and siRNA
Authors: Shu Zhaoma , Tanaka Iku , Ota Azumi , Fushihara Daichi , Abe Naoko , Kawaguchi Saki , Nakamoto Kosuke , Tomoike Fumiaki , Tada Seiichi , Ito Yoshihiro , Kimura Yasuaki , Abe Hiroshi 
Published: March 2019

AbstractDevelopment of intracellular delivery methods for antisense DNA and siRNA is important. Previously reported methods using liposomes or receptor‐ligands take several hours or more to deliver oligonucleotides to the cytoplasm due to their retention in endosomes. Oligonucleotides modified with low molecular weight disulfide units at a terminus reach the cytoplasm 10 minutes after administration to cultured cells. This rapid cytoplasmic internalization of disulfide‐modified oligonucleotides suggests the existence of an uptake pathway other than endocytosis. Mechanistic analysis revealed that the modified oligonucleotides are efficiently internalized into the cytoplasm through disulfide exchange reactions with the thiol groups on the cellular surface. This approach solves several critical problems with the currently available methods for enhancing cellular uptake of oligonucleotides and may be an effective approach in the medicinal application of antisense DNA and siRNA.
Azoniadibenzo[a,j]phenalenide: A Polycyclic Zwitterion with Singlet Biradical Character
Authors: Arikawa Shinobu , Shimizu Akihiro , Shintani Ryo 
Published: March 2019

AbstractA polycyclic zwitterion, azoniadibenzo[a,j]phenalenide, having a singlet biradical character, was synthesized and isolated for the first time. The negative charge was found to be delocalized over the periphery of the main core of the zwitterion and the positive charge was localized near the nitrogen atom. Its singlet biradical character was confirmed by a small HOMO–LUMO energy gap with their spatial overlap, and observation of thermally excited triplet species together with DFT calculations.
Electrochemical [4+2] Annulation‐Rearrangement‐Aromatization of Styrenes: Synthesis of Naphthalene Derivatives
Authors: Ma Yueyue , Lv Jufeng , Liu Chengyu , Yao Xiantong , Yan Guoming , Yu Wei , Ye Jinxing 
Published: March 2019

AbstractWe report the first electrochemical strategy to synthesize functionalized naphthalene derivatives through [4+2] annulation—rearrangement–aromatization from styrenes under mild conditions. The electrolysis does not require metals, oxidants and high valence substrates, indicating the atom and step‐economy ideals. The dehydrodimer produced through [4+2] cycloaddition of 4‐methoxy α‐methyl styrene is isolated and proved to be the key intermediate for the following oxydehydrogenation to form carbon cation, which undergoes rearrangement–aromatization to afford the final products. This reaction represents a powerful access to construct multi‐substituted naphthalene blocks in a single step.
A Rigid Trigonal‐Prismatic Hexagold Metallocage That Behaves as a Coronene Trap
Authors: Ibáñez Susana , Peris Eduardo 
Published: March 2019

AbstractA trigonal‐prismatic hexagold cage was obtained by combining a triphenylene‐tris(N‐heterocyclic carbene) ligand and a carbazolyl‐bis(alkynyl) linker. The metallocage has a slot‐like cavity with a volume of about 300 Å3. The cage was used for the recognition of several polycyclic aromatic hydrocarbons. Due to the perfect dimensional match, the supramolecular complex shows a very high affinity for trapping coronene.
Revisiting the Mechanism of the Anaerobic Coproporphyrinogen III Oxidase HemN
Authors: Ji Xinjian , Mo Tianlu , Liu Wan‐Qiu , Ding Wei , Deng Zixin , Zhang Qi 
Published: March 2019

AbstractHemN is a radical S‐adenosyl‐l‐methionine (SAM) enzyme that catalyzes the oxidative decarboxylation of coproporphyrinogen III to produce protoporphyrinogen IX, an intermediate in heme biosynthesis. HemN binds two SAM molecules in the active site, but how these two SAMs are utilized for the sequential decarboxylation of the two propionate groups of coproporphyrinogen III remains largely elusive. Provided here is evidence showing that in HemN catalysis a SAM serves as a hydrogen relay which mediates a radical‐based hydrogen transfer from the propionate to the 5′‐deoxyadenosyl (dAdo) radical generated from another SAM in the active site. Also observed was an unexpected shunt product resulting from trapping of the SAM‐based methylene radical by the vinyl moiety of the mono‐decarboxylated intermediate, harderoporphyrinogen. These results suggest a major revision of the HemN mechanism and reveal a new paradigm of the radical‐mediated hydrogen transfer in radical SAM enzymology.