bluuebunny/crossref_metadata_2025_split huggingface dataset:
Heterostructured Bismuth Vanadate/Cobalt Phosphate Photoelectrodes Promote TEMPO‐Mediated Oxidation of 5‐Hydroxymethylfurfural
Authors: Chadderdon David J. , Wu Li‐Pin , McGraw Zachary A. , Panthani Matthew , Li Wenzhen 
Published: May 2019

AbstractMotivated by replacing the kinetically unfavorable oxygen evolution reaction (OER) and producing value‐added products in photoelectrochemical cells (PECs), we report that bismuth vanadate (BiVO4) photoelectrodes modified with a cobalt phosphate (CoPi) overlayer facilitate 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO)‐mediated selective oxidation of 5‐hydroxymethylfurfural (HMF). CoPi layers with sufficient thickness were found to reduce the potential required for TEMPO oxidation by 0.5 V, as well as increase charge injection efficiency sevenfold compared to BiVO4 without CoPi. Furthermore, the undesired OER was completely suppressed when using the heterostructured photoanodes. Transient photocurrent measurements suggested that CoPi alleviates recombination losses resulting from the back reduction of oxidized TEMPO. The PECs with BiVO4/CoPi bilayer achieved 88 % yield to 2,5‐furandicarboxylic acid (FDCA) from HMF oxidation under mild conditions, whereas <1 % FDCA was generated with BiVO4. These findings suggest that suppression of the back reduction process substantially improves the efficiency of the oxidation, giving a potential route to more efficient solar fuel/chemical production.
Humidity‐Induced Switching between Two Magnetic and Structural Phases in a CoII‐[WV(CN)8] Molecular Magnet
Authors: Komori‐Orisaku Keiko , Stefańczyk Olaf , Ohishi Saori , Ozaki Noriaki , Miyamoto Yasuto , Imoto Kenta , Ohkoshi Shin‐ichi 
Published: May 2019

AbstractThe self‐assembly of cobalt(II) with purine and octacyanidotungstate(V) results in the formation of the three‐dimensional Co3[W(CN)8]2(purine)2⋅8.5H2O (1) coordination polymer. This compound exhibits humidity‐induced variation of the number of water molecules of crystallisation leading to a reversible structural phase transition and the alternation of the long‐range ferromagnetic ordering temperature from TC=29 K for the pristine assembly (1) to TC=49 K for the sample stored in a low‐humidity atmosphere (1‐deh). This phenomenon can be attributed to a reversible change in the hydrogen‐bonding network resulting in the modification of the local geometries of cobalt(II) as well as the cyanido bridges.
Reactivity of C1‐Symmetric Heteroarylamido Hafnium Complexes towards Unsaturated Electrophilic Molecules: Development of New Families of Olefin Polymerization Catalysts
Authors: Kulyabin Pavel S. , Goryunov Georgy P. , Mladentsev Dmitry Y. , Uborsky Dmitry V. , Voskoboynikov Alexander Z. , Canich Jo Ann M. , Hagadorn John R. 
Published: May 2019

AbstractHeteroarylamido hafnium post‐metallocenes with [C,N,N] ligands were functionalized by the insertion of small electrophilic unsaturated molecules into the CAr−Hf bond of the ligand, which gave rise to various 1,1‐ and 1,2‐insertion complexes with the modified ligands of previously unknown [O,N,N], [N,N,N], [O,N,N,N], and [N,N,N,N] types. It was found that C1 symmetry of the starting complexes, in some cases, results in the formation of two diastereoisomers after 1,1‐ or 1,2‐insertion. Most of the obtained novel complexes were shown to form active catalysts for olefin polymerization in the presence of MAO (methylaluminoxane). Thus, a new approach to the feasible and easy “late stage” modification of the precatalyst structure has been suggested; it can be performed immediately prior to the polymerization tests without isolation and even in a high‐throughput manner.
Impact of C=C/B−N Replacement on the Diels–Alder Reactivity of Curved Polycyclic Aromatic Hydrocarbons
Authors: García‐Rodeja Yago , Fernández Israel 
Published: May 2019

AbstractThe influence of the replacement of C=C bonds by isoelectronic B−N moieties on the reactivity of π‐curved polycyclic aromatic hydrocarbons has been computationally explored by means of density functional theory calculations. To this end, we selected the Diels–Alder cycloaddition reactions of the parent corannulene and its BN‐doped counterparts with either cyclopentadiene or maleic anhydride. In addition, the analogous reactions involving larger buckybowls, such as BN‐hemifullerene, BN‐circumtrindene, and BN‐fullerene, have been also considered. It has been found that whereas corannulene behaves as a dienophile, its BN counterpart better acts as a diene. In contrast, the larger BN‐curved systems cannot be used as dienes in Diels–Alder reactions, but undergo facile (i.e., low barrier) cycloaddition reactions with cyclopentadiene. The observed trends in reactivity, which cannot be directly explained by using typical frontier molecular orbital arguments, are quantitatively described in detail by means of state‐of‐the‐art computational methods, namely the activation strain model of reactivity combined with the energy decomposition analysis method. The results of our calculations highlight the crucial role of the curvature of the system on the reactivity and its influence on the strength of the orbital interactions between the deformed reactants during their transformations.
Tumor downstaging as an intermediate endpoint to assess the activity of neoadjuvant systemic therapy in patients with muscle‐invasive bladder cancer
Authors: Martini Alberto , Jia Rachel , Ferket Bart S. , Waingankar Nikhil , Plimack Elizabeth R. , Crabb Simon J. , Harshman Lauren C. , Yu Evan Y. , Powles Thomas , Rosenberg Jonathan E. , Pal Sumanta K. , Vaishampayan Ulka N. , Necchi Andrea , Wiklund N. Peter , Mehrazin Reza , Mazumdar Madhu , Sfakianos John P. , Galsky Matthew D. 
Published: May 2019

BackgroundAchieving a pathologic complete response (pCR) with neoadjuvant chemotherapy (NAC) in patients with muscle‐invasive bladder cancer (MIBC) has been associated with improved overall survival (OS). This study was aimed at evaluating the impact of pathologic downstaging (pDS; ie, a pT stage at least 1 stage lower than the pre‐NAC cT stage) on the OS of patients with MIBC treated with NAC.MethodsThe Retrospective International Study of Cancers of the Urothelial Tract (RISC) and the National Cancer Database (NCDB) were queried for cT2‐4N0M0 patients treated with NAC. A multivariable Cox model including either pDS or pCR was generated. A nested model was built to evaluate the added value of pDS (excluding patients achieving a pCR) to a model including pCR alone. C indices were computed to assess discrimination. NCDB was used for validation. The treatment effect of NAC versus cystectomy alone in achieving pDS was estimated through an inverse probability–weighted regression adjustment.ResultsOverall, 189 and 2010 patients from the RISC and NCDB cohorts, respectively, were included; pDS and pCR were achieved by 33% and 35% and by 20% and 15% in RISC and NCDB, respectively. In both data sets, pDS and pCR were associated with better OS and C indices. Adding pDS excluding pCR to the model with pCR fit the data better (likelihood ratio, P = .019 for RISC and P < .001 for NCDB), and it yielded better discrimination (incremental C index, 4.2 for RISC and 1.6 for NCDB). The treatment effect of NAC in achieving pDS was 2.07‐fold (P < .001) in comparison with cystectomy alone.ConclusionsA decrease of at least 1 stage from the cT stage to the pT stage is associated with improved OS in patients with MIBC treated with NAC.
Use and early mortality outcomes of active surveillance in patients with intermediate‐risk prostate cancer
Authors: Butler Santino S. , Mahal Brandon A. , Lamba Nayan , Mossanen Matthew , Martin Neil E. , Mouw Kent W. , Nguyen Paul L. , Muralidhar Vinayak 
Published: May 2019

BackgroundCertain patients with intermediate‐risk prostate cancer (PCa) may be appropriate candidates for active surveillance (AS). In the current study, the authors sought to characterize AS use and early mortality outcomes for patients with intermediate‐risk PCa in the United States.MethodsThe novel Surveillance, Epidemiology, and End Results Active Surveillance/Watchful Waiting database identified 52,940 men diagnosed with National Comprehensive Cancer Network intermediate‐risk PCa (cT2b‐c, Gleason score of 7, or a prostate‐specific antigen level of 10‐20 ng/mL) and actively managed (AS, radiotherapy, or radical prostatectomy) from 2010 through 2015. The Cuzick test assessed AS time trends, and logistic multivariable regression characterized features associated with AS. Fine‐Gray and Cox modeling determined PCa‐specific mortality (PCSM) and overall survival, respectively.ResultsThe rate of AS increased from 3.7% in 2010 to 7.3% in 2015, and from 7.2% to 11.7% among men aged ≥70 years. Among men with favorable and unfavorable intermediate‐risk disease, the use of AS increased from 7.2% to 14.9% and from 2.2% to 3.8%, respectively (all P value for trend, <.001). The mean age of those patients managed with AS decreased from 69.9 years to 67.9 years (P = .0004). Factors found to be associated with AS included favorable risk disease; black race; higher socioeconomic status; older age; and diagnosis in the West, Northwest, or Midwest regions of the United States. The 5‐year PCSM rate was comparable to AS versus treatment among patients with low‐risk and favorable intermediate‐risk disease, but was worse with AS among those with unfavorable intermediate‐risk disease (PCSM, 1.3% vs 0.5%; adjusted hazard ratio, 2.48 [95% CI, 1.11‐5.50; P = .026]) and intermediate‐risk disease overall (PCSM, 1.1% vs 0.4%; adjusted hazard ratio, 2.34 [95% CI, 1.25‐4.37; P = .008]).ConclusionsThe use of AS for patients with intermediate‐risk PCa is increasing across the United States, particularly for older men and those with favorable intermediate‐risk disease. Early estimates of cancer‐specific and overall mortality rates are low with AS, although significantly higher compared with treatment.
Effects of Food and Gender on Pharmacokinetics of Rosuvastatin in a Chinese Population Based on 4 Bioequivalence Studies
Authors: Chen Jinliang , Lou Honggang , Jiang Bo , Shao Rong , Yang Dandan , Hu Yin , Xu Yichao , Ruan Zourong 
Published: May 2019

AbstractThe effects of food and gender on the pharmacokinetics of rosuvastatin in healthy Chinese subjects were investigated from 4 bioequivalence studies. These studies were designed as randomized, open‐label, and 2‐period crossover in both fasting and fed states. A total of 204 subjects were enrolled, 134 men and 70 women. These subjects received a single oral 10‐mg dose of rosuvastatin with a 7‐day washout between 2 periods. The plasma concentrations were determined using a validated liquid chromatography tandem mass spectrometry method, and pharmacokinetic parameters were calculated by noncompartmental methods. Compared with the fasting condition, administration after a high‐fat and high‐calorie meal resulted in an approximately 40% reduction of rosuvastatin exposure and a near 50% decrease in absorption rate. Moreover, the apparent clearance was significantly greater in the fed state than that in the fasting state. It was noted that the adverse events incidence is increased by approximately 30% in the fasting state; however, no serious adverse events were observed. Additionally, small differences in pharmacokinetic characteristics were found between male and female subjects. Food effect might be considered for optimal effectiveness and safety of rosuvastatin therapy.
Development of a lateral flow dipstick for simultaneous and semi‐quantitative analysis of dihydroartemisinin and piperaquine in an artemisinin combination therapy
Authors: Ning Xiangxue , Tan Guiyu , Chen Xiaojiao , Wang Mian , Wang Baomin , Cui Liwang 
Published: May 2019

AbstractDihydroartemisinin (DHA) and piperaquine (PPQ) are two drugs used in an artemisinin‐based combination therapy (ACT). The circulation of counterfeit antimalarial drugs demands the development of simple, point‐of‐care (POC) tests for monitoring drug quality. Here we aimed to design an antibody‐based lateral flow dipstick assay for simultaneous quality control of DHA and PPQ. To obtain a monoclonal antibody (mAb) for PPQ, one structural unit of the symmetric PPQ molecule was used to derive a carboxylic acid for linkage to a carrier protein as immunogen. Screening of hybridoma cells identified an mAb 4D112B2 that reacted with the PPQ‐based immunogen. A highly‐sensitive icELISA was designed based on this mAb, which showed 50% inhibition concentration of PPQ at 1.66 ng/mL and a working range of 0.35 – 7.40 ng/mL. The mAb showed 10.2, 15.9 and 30.4% cross reactivity to hydroxychloroquine sulfate, chloroquine and amodiaquine, respectively. No cross reactivity was observed to lumefantrine, mefloquine artemisinin and its derivatives. Using our previous DHA dipstick design, a lateral flow dipstick for simultaneous analysis of PPQ and DHA was developed. The indicator ranges for PPQ and DHA were 2 – 5 μg/mL and 250 – 500 ng/mL, respectively. The dipstick was used to semi‐quantitatively analyze PPQ and DHA content in commercial ACT drugs, which produced agreeable results to those determined by high‐performance liquid chromatography. This combination dipstick makes it a potential POC device for quality control of the two active ingredients in a commonly used ACT.
Detection of cocaine and its metabolites in whole blood and plasma following a single dose, controlled administration of intranasal cocaine
Authors: Menzies Eleanor L. , Archer John R.H. , Dargan Paul I. , Parkin Mark C. , Yamamoto Takahiro , Wood David M. , Braithwaite Robin A. , Elliott Simon P. , Kicman Andrew T. 
Published: May 2019

AbstractThe disposition of drugs and their metabolites have been extensively described in the literature, based primarily on the analysis of plasma and urine. However, there are more limited data on their disposition in whole blood, which is often the only specimen available in forensic investigations and cases of driving under the influence of drugs. In this study, we have, for the first time, established pharmacokinetic properties of cocaine (COC) and its metabolites from concurrently collected whole blood and plasma samples, following a single 100 mg dose of cocaine hydrochloride administered via nasal insufflation to seven healthy volunteers. The median Cmax of COC and its major metabolites, benzoylecgonine (BZE) and ecgonine methyl ester (EME), were closely related in whole blood and plasma. The median Cmax for COC in plasma was 379.7 ng/mL (347.5–517.7) and 344.24 ng/mL (271.6–583.2) in whole blood. The median Cmax for BZE in plasma was 441.2 ng/mL (393.6–475. and 371.18 ng/mL (371.1–477.3) in whole blood, EME was 105.5 ng/mL (93.6–151.8) in plasma and 135.5 ng/mL (87.8–183) in whole blood. Calculated medians of the whole blood to plasma ratio of COC (0.76), BZE (0.98) and EME (1.02) of approximately 1, strongly suggesting that the erythrocyte cell wall presents no barrier to COC and its metabolites. Furthermore, whole blood and plasma concentrations of COC were strongly correlated (R2 = 0.0914 R = 0.956, p < 0.0001), as was BZE (R2 = 0.0932 R = 0.965, p < 0.0001) and EME (R2 = 0.0964R = 0.928, p < 0.0001). The minor oxidative metabolite norcocaine (NCOC) was detected in both whole blood and plasma at concentrations between 1 and 5 ng/mL within 60–180 minutes, suggesting that NCOC could be indicator of recent COC administration. Data from this study have shown for the first time that COC and its metabolites BZE and EME are evenly distributed between plasma and whole blood following controlled single‐dose intranasal COC administration.
An alternative approach to reduce algorithm‐derived biases in monitoring soil organic carbon changes
Authors: Zhang Weixin , Chen Yuanqi , Shi Leilei , Wang Xiaoli , Liu Yongwen , Mao Rong , Rao Xingquan , Lin Yongbiao , Shao Yuanhu , Li Xiaobo , Zhao Cancan , Liu Shengjie , Piao Shilong , Zhu Weixing , Zou Xiaoming , Fu Shenglei 
Published: May 2019

AbstractQuantifying soil organic carbon (SOC) changes is a fundamental issue in ecology and sustainable agriculture. However, the algorithm‐derived biases in comparing SOC status have not been fully addressed. Although the methods based on equivalent soil mass (ESM) and mineral‐matter mass (EMMM) reduced biases of the conventional methods based on equivalent soil volume (ESV), they face challenges in ensuring both data comparability and accuracy of SOC estimation due to unequal basis for comparison and using unconserved reference systems. We introduce the basal mineral‐matter reference systems (soils at time zero with natural porosity but no organic matter) and develop an approach based on equivalent mineral‐matter volume (EMMV). To show the temporal bias, SOC change rates were recalculated with the ESV method and modified methods that referenced to soils at time t1 (ESM, EMMM, and EMMV‐t1) or referenced to soils at time zero (EMMV‐t0) using two datasets with contrasting SOC status. To show the spatial bias, the ESV‐ and EMMV‐t0‐derived SOC stocks were compared using datasets from six sites across biomes. We found that, in the relatively C‐rich forests, SOC accumulation rates derived from the modified methods that referenced to t1 soils and from the EMMV‐t0 method were 5.7%–13.6% and 20.6% higher than that calculated by the ESV method, respectively. Nevertheless, in the C‐poor lands, no significant algorithmic biases of SOC estimation were observed. Finally, both the SOC stock discrepancies (ESV vs. EMMV‐t0) and the proportions of this unaccounted SOC were large and site‐dependent. These results suggest that although the modified methods that referenced to t1 soils could reduce the biases derived from soil volume changes, they may not properly quantify SOC changes due to using unconserved reference systems. The EMMV‐t0 method provides an approach to address the two problems and is potentially useful since it enables SOC comparability and integrating SOC datasets.
Development of data‐based controller synthesis by convex optimization
Authors: Yubai Kazuhiro 
Published: May 2019

AbstractRecently, many researches extracting an essence from a huge number of data receive much attention in the various field of engineering. In the field of control engineering, the controller syntheses from time‐domain and/or frequency domain data are energetically studied based on numerical optimization techniques. This paper presents a recent development of data‐based controller synthesis by convex optimization, and shows that a special case of nonconvex optimization problems, which is often encountered in the control field, is reformulated as a convex optimization problem by introducing the concave‐convex procedure or the Iterated LMI constraints. As an application, the H∞ loop shaping design procedure reformulated using frequency response data of a controlled plant is presented.
Suppression of Aiolos and Ikaros expression by lenalidomide reduces human ILC3−ILC1/NK cell transdifferentiation
Authors: Mazzurana Luca , Forkel Marianne , Rao Anna , Van Acker Aline , Kokkinou Efthymia , Ichiya Tamaki , Almer Sven , Höög Charlotte , Friberg Danielle , Mjösberg Jenny 
Published: May 2019

AbstractThe Ikaros family of transcription factors (TFs) are important regulators of lymphocyte function. However, their roles in human innate lymphoid cell (ILC) function remain unclear. Here, we found that Ikaros (IKZF1) is expressed by all ILC subsets, including NK cells, in blood, tonsil, and gut, while Helios (IKZF2) is preferentially expressed by ILC3 in tonsil and gut. Aiolos (IKZF3) followed the expression pattern of T‐bet and Eomes, being predominantly expressed by ILC1 and NK cells. Differentiation of IFN‐γ‐producing ILC1 and NK cells from ILC3 by IL‐1β plus IL‐12‐stimulation was associated with upregulation of T‐bet and Aiolos. Selective degradation of Aiolos and Ikaros by lenalidomide suppressed ILC1 and NK cell differentiation and expression of ILC1 and NK cell‐related transcripts (LEF1, PRF1, GRZB, CD244, NCR3, and IRF8). In line with reduced ILC1/NK cell differentiation, we observed an increase in the expression of the ILC3‐related TF Helios, as well as ILC3 transcripts (TNFSF13B, IL22, NRP1, and RORC) and in the frequency of IL‐22 producing ILC3 in cultures with IL‐1β and IL‐23. These data suggest that suppression of Aiolos and Ikaros expression inhibits ILC1 and NK cell differentiation while ILC3 function is maintained. Hence, our results open up for new possibilities in targeting Ikaros family TFs for modulation of type 1/3 immunity in inflammation and cancer.
Preservative Effect of Algae Extracts on Lipid Composition and Rancidity Development in Brine‐Canned Atlantic Chub Mackerel (Scomber colias)
Authors: Barbosa Roberta G. , Trigo Marcos , Campos Carmen A. , Aubourg Santiago P. 
Published: May 2019

This research focuses on the lipid fraction and the rancidity stability of commercial canned Atlantic Chub mackerel (Scomber colias). For it, two different concentrations of aqueous extracts of two abundant algae (Fucus spiralis and Ulva lactuca) are included in the brine‐packing (aq. 2% NaCl) medium during mackerel canning. Quality analyses are carried out after a 3‐month canned storage (20 °C). Phospholipids, sterols, and α‐tocopherol contents show a marked loss as a result of canning, this loss being mostly inhibited when considering the canned fish packed in the presence of the most concentrated algae extracts. Breakdown of free fatty acids and peroxides produced during the thermal treatment is inhibited by the presence of the algae extracts, a higher retention of such molecules being observed by increasing the algae extract concentration. Analysis of fluorescent compounds formation (tertiary lipid oxidation) shows a marked increase after canning, this increase being partly inhibited by the presence of antioxidant compounds present in the algae extracts; interestingly, oxidation inhibition is found more important in canned fish corresponding to F. spiralis batches than U. lactuca. A preservative effect on lipid constituents and rancidity development is concluded by the presence of algae extracts in the packing medium.Practical Applications: The extensive heat treatment involved during fish canning has been reported to produce breakdown of constituents, lipid damage (oxidation and hydrolysis) development showing a marked effect on nutritional and sensory properties; furthermore, this effect has shown to be greater when a brine medium is applied as packing system. Marine algae have been described as being a relevant source of chemical constituents including an antioxidant and antibacterial behavior. In the current work, employment of a commercial brine‐packing including aqueous algae extracts shows a preservative effect on the lipid fraction (composition and rancidity stability) during the canning process of Atlantic Chub mackerel. The proposed strategy may open the way to the development of a natural biopreservation for commercial canned fish due to the simple methodology employed and the abundancy of the two algae chosen for the study. Further research should envisage optimization of the preservative compounds extraction by advanced technologies.Aqueous extracts of algae Fucus spiralis and Ulva lactuca are included in the packing medium during Atlantic Chub mackerel (Scomber colias) canning. As a result, an inhibitory effect on lipid composition changes and rancidity development is obtained. Better results are observed by employing alga F. spiralis.