bluuebunny/crossref_metadata_2025_split huggingface dataset:
Promoted Glycerol Oxidation Reaction in an Interface‐Confined Hierarchically Structured Catalyst
Authors: Chen Zhongxin , Liu Cuibo , Zhao Xiaoxu , Yan Huan , Li Jing , Lyu Pin , Du Yonghua , Xi Shibo , Chi Kai , Chi Xiao , Xu Haisen , Li Xing , Fu Wei , Leng Kai , Pennycook Stephen J. , Wang Shuai , Loh Kian Ping 
Published: November 2018

AbstractConfined catalysis in a 2D system is of particular interest owing to the facet control of the catalysts and the anisotropic kinetics of reactants, which suppress side reactions and improve selectivity. Here, a 2D‐confined system consisting of intercalated Pt nanosheets within few‐layered graphene is demonstrated. The strong metal–substrate interaction between the Pt nanosheets and the graphene leads to the quasi‐2D growth of Pt with a unique (100)/(111)/(100) faceted structure, thus providing excellent catalytic activity and selectivity toward one‐carbon (C1) products for the glycerol oxidation reaction. A hierarchically porous graphene architecture, grown on carbon cloth, is used to fabricate the confined catalyst bed in order to enhance the mass‐diffusion limitation in interface‐confined reactions. Owing to its unique 3D porous structure, this graphene‐confined Pt catalyst exhibits an extraordinary mass activity of 2910 mA mgPt
−1 together with a formate selectivity of 79% at 60 °C. This paves the way toward rational designs of heterogeneous catalysts for energy‐related applications.
Robust Tin‐Based Perovskite Solar Cells with Hybrid Organic Cations to Attain Efficiency Approaching 10%
Authors: Jokar Efat , Chien Cheng‐Hsun , Tsai Cheng‐Min , Fathi Amir , Diau Eric Wei‐Guang 
Published: November 2018

AbstractThe stability of a tin‐based perovskite solar cell is a major challenge. Here, hybrid tin‐based perovskite solar cells in a new series that incorporate a nonpolar organic cation, guanidinium (GA+), in varied proportions into the formamidinium (FA+) tin triiodide perovskite (FASnI3) crystal structure in the presence of 1% ethylenediammonium diiodide (EDAI2) as an additive, are reported. The device performance is optimized at a precursor ratio (GAI:FAI) of 20:80 to attain a power conversion efficiency (PCE) of 8.5% when prepared freshly; the efficiencies continuously increase to attain a record PCE of 9.6% after storage in a glove‐box environment for 2000 h. The hybrid perovskite works stably under continuous 1 sun illumination for 1 h and storage in air for 6 days without encapsulation. Such a tin‐based perovskite passes all harsh standard tests, and the efficiency of a fresh device, 8.3%, is certified. The great performance and stability of the device reported herein attains a new milestone for lead‐free perovskite solar cells on a path toward commercial development.
Improved Outcoupling Efficiency and Stability of Perovskite Light‐Emitting Diodes using Thin Emitting Layers
Authors: Zhao Lianfeng , Lee Kyung Min , Roh Kwangdong , Khan Saeed Uz Zaman , Rand Barry P. 
Published: November 2018

AbstractHybrid organic–inorganic perovskite semiconductors have shown potential to develop into a new generation of light‐emitting diode (LED) technology. Herein, an important design principle for perovskite LEDs is elucidated regarding optimal perovskite thickness. Adopting a thin perovskite layer in the range of 35–40 nm is shown to be critical for both device efficiency and stability improvements. Maximum external quantum efficiencies (EQEs) of 17.6% for Cs0.2FA0.8PbI2.8Br0.2, 14.3% for CH3NH3PbI3 (MAPbI3), 10.1% for formamidinium lead iodide (FAPbI3), and 11.3% for formamidinium lead bromide (FAPbBr3)‐based LEDs are demonstrated with optimized perovskite layer thickness. Optical simulations show that the improved EQEs source from improved light outcoupling. Furthermore, elevated device temperature caused by Joule heating is shown as an important factor contributing to device degradation, and that thin perovskite emitting layers maintain lower junction temperature during operation and thus demonstrate increased stability.
Oxazolinyl‐Assisted Ru(II)‐Catalyzed C−H Functionalization Based on Carbene Migratory Insertion: A One‐Pot Three‐Component Cascade Cyclization
Authors: Kumar Gangam Srikanth , Khot Nandkishor Prakash , Kapur Manmohan 
Published: November 2018

AbstractA rare, ruthenium‐catalyzed, oxazolinlyl assisted C−H functionalization and three‐component cascade cyclization for the synthesis of isoquinolinones via a metal‐carbene migratory insertion is reported. The transformation is unique since it involves the formation of multiple bonds in one pot via C−H functionalization and ring opening of oxazolines. Detailed mechanistic investigations reveal interesting insights on the mode of transformation, involving reversible C−H activation, migratory insertion of the diazo compound and cascade cyclization as the key step of the transformation.magnified image
Comparative Analysis of Protein Hydration from MD simulations with Additive and Polarizable Force Fields
Authors: Ngo Van A. , Fanning John Keenan , Noskov Sergei Yu 
Published: November 2018

AbstractRecent development of the Drude polarizable (Drude) force field (FF), based on the extension of an induced dipole model, has reached a milestone in the past few years providing a complete set of polarizable parameters for proteins, water, ions, and many lipid types. This FF enables stable simulations up to microseconds, surpassing the capability of other polarizable FFs. The quality of the Drude FF, however, has remained largely untested for modeling the secondary structures of small peptides in explicit solvents compared with classical non‐polarizable FFs. It is critical to benchmark the complex and mutually dependent dynamics of hydrogen‐bond (H‐bond) networks formed by water–water, protein–water, and protein–protein interactions that are expected to have a major impact on the stability of protein structures and their conformational space. Here, a direct comparison is presented between the current Drude FF and the CHARMM‐36 non‐polarizable classical FF for 1) the solvation free energy of mimetics for all amino acid side‐chain equivalents, 2) limited conformational space, 3) protein–water and protein–protein interactions, and 4) the comparative lifetimes of H‐bonds. The impact of counterions on the stabilization of secondary structure in model peptides is additionally discussed and compared between these FFs.
Role of induction chemotherapy in sinonasal malignancies: a systematic review
Authors: Khoury Tawfiq , Jang David , Carrau Ricardo , Ready Neal , Barak Ian , Hachem Ralph Abi 
Published: November 2018

BackgroundCancers of the paranasal sinuses are rare tumors that tend to be aggressive and usually are diagnosed at an advanced stage. Despite being rare, these tumors include a wide spectrum of histological subtypes with different biological behaviors. Choosing the optimal treatment modalities and analyzing the different oncological outcomes is therefore challenging. This study aims to evaluate the role of induction chemotherapy prior to definitive local therapy for sinonasal malignancies.MethodsA systematic review of the literature in accordance with Preferred Reporting Items for Systematic Reviews and Meta‐Analyses (PRISMA) guidelines was conducted. With the assistance of a medical librarian, data sources including MEDLINE, PubMed, Cochrane library, EMBASE, NCBI Bookshelf, National Guideline Clearinghouse, and Clinicaltrials.gov were searched using a customized search strategy that yielded 1758 articles. Inclusion criteria used were as follows: (1) the study has a patient population with 3 or more patients with previously untreated sinonasal malignancies; (2) patients underwent induction chemotherapy prior to definitive local therapy; (3) pretreatment staging information was documented; (4) overall survival was reported by histology type either in table or Kaplan‐Meier format. Nine studies with 220 patients ultimately met inclusion criteria and were analyzed in groups based on tumor histology.ResultsFor squamous cell carcinoma (SCC), the 5‐year overall survival was 51%. For neuroendocrine tumors, the 5‐year overall survival was 78%. Eighteen percent (18%) of patients with pretreatment orbital involvement ultimately underwent orbital exenteration.ConclusionInduction chemotherapy in the management of sinonasal malignancies has similar overall survival outcomes as other standard treatment modalities and can be offered as an option to patients as part of multimodality therapy.
Pd‐Catalyzed Atroposelective C−H Allylation through β‐O Elimination: Diverse Synthesis of Axially Chiral Biaryls
Authors: Liao Gang , Li Bing , Chen Hao‐Ming , Yao Qi‐Jun , Xia Yu‐Nong , Luo Jun , Shi Bing‐Feng 
Published: November 2018

AbstractBiaryl atropisomers are of great importance in natural products, pharmaceuticals, and asymmteric synthesis. The efficient synthesis of these chiral scaffolds with full enantiocontrol and high diversity remains challenging. Reported herein is a Pd‐catalyzed atroposelective C−H allylation with tert‐leucine as an efficient catalytic chiral transient auxiliary. A wide range of enantioenriched biaryl aldehydes were prepared in synthetically useful yields with excellent enantioselectivity (up to >99 % ee) through β‐O elimination. The reaction could be carried out on a gram scale without erosion of the ee value. A variety of axially chiral carboxylic acids could be obtained with high enantiopurity. The resulting axially chiral biaryl aldehydes and carboxylic acids might be used in asymmetric synthesis as chiral ligands and/or organocatalysts.
Mechanistic investigation of Sono–Phosphotungstic acid/phase transfer agent assisted oxidative desulfurization of liquid fuel
Authors: Bal Dharmendra Kumar , Bhasarkar Jaykumar B. 
Published: November 2018

AbstractThe aim of this paper is to identify the physical and chemical mechanism of ultrasound in presence of phase transfer agent (PTA) and phosphotungstic acid on desulfurization process. With different experimental procedures, we made an effort to identify the individual effect of phase transfer agent and ultrasound on oxidative desulfurization. Ultrasound‐assisted process is the modern technique to enhance the kinetic of the liquid–liquid heterogeneous system. Physical and intrinsic properties of liquid fuels such as diffusivity of PTA‐cation complex and also through effect on cavitation have a strong influence on Desulfurization of liquid fuels. Due to low vapor pressure of solvents, the beneficial effect of higher static pressure (that eliminates cavitation effect) is not seen in present reaction system. Phase transfer agent or phosphotungustic acid‐assisted ultrasound desulfurization has radical and ionic reaction mechanism, which is revealed in terms of lower activation energy (energetic nature of radicals) as well as collision factor (due to instability of radicals) than magnetically stirred system. This study has revealed crucial mechanistic aspects of ultrasound assisted oxidative desulfurization in presence of phase transfer agent and phosphotungustic acid, which will give more insight for further research.
Overview of the History of the Cranial Nerves: From Galen to the 21st Century
Authors: Porras‐Gallo María Isabel , Peña‐Meliáan Áangel , Viejo Fermín , Hernáandez Tomáas , Puelles Eduardo , Echevarria Diego , Ramón Sañudo José 
Published: November 2018

ABSTRACTThroughout history the description and classification of the cranial nerves has been linked to the development and characteristics of anatomy and the role that it played as a tool in providing rationality to medicine, together with social, cultural, religious, and philosophical factors. Anatomists were interested in the cranial nerves, but they disagreed on their number and their paths. We can divide the history of the cranial nerves into three different periods: the first, early or macroscopic period; the second or microscopic period; and the third period or ontogenesis and genoarchitecture. The main aim of this article is to show how the description and knowledge of the cranial nerves were developed in the course of these three periods, and to highlight the main changes produced and the factors related to these changes. We describe how the first period was mainly focused on establishing the definition, number and paths of the cranial nerves, through contributions ranging from Galen's studies in the second century to Sömmerring's Doctoral Dissertation in 1778 that described 12 cranial nerves for the first time. Then, the microscopic period was concentrated on the identification of the real nuclei of origin of the different cranial nerves located in the brain stem. Finally came the third period, or ontogenesis and genoarchitecture of the rhombecephalic and mesencephalic cranial nerve nuclei. Anat Rec, 302:381–393, 2019. © 2018 Wiley Periodicals, Inc.
Maternal hypertension and hypospadias in offspring: A systematic review and meta‐analysis
Authors: Sheriff Fatima R. , Lopez Adriana , Lupo Philip J. , Seth Abhishek , Jorgez Carolina , Agopian A.J. 
Published: November 2018

BackgroundSeveral studies have reported an association between maternal hypertensive disorders and hypospadias in offspring; however there is still debate on the role of maternal hypertension and preeclampsia on this relatively common congenital malformation. Therefore, we conducted a systematic review and meta‐analysis to comprehensively evaluate the relationship between these frequent maternal conditions and hypospadias in offspring.MethodsFifteen articles meeting the eligibility criteria were identified in our search and included in the analysis. A meta‐analysis was conducted and pooled odds ratio (OR) estimates were calculated separately for hypertension and preeclampsia using meta‐analysis. We also conducted several secondary analyses, including (a) studies conducted before versus after January 1, 1998; (b) studies in United States versus other countries; and (c) studies that accounted for ≥3 versus fewer or no potential confounders, among others.ResultsSignificant positive associations were observed between hypertension and hypospadias (OR 1.68; 95% CI 1.46–1.93), as well as preeclampsia and hypospadias (OR 2.18; 95% CI 1.63–2.91). The direction and magnitude of effect was comparable for the majority of secondary analyses conducted.ConclusionsOur results indicate that maternal hypertensive disorders are positively associated with hypospadias in offspring. Further research is needed to better understand the mechanisms involved, and to ultimately develop public health strategies geared toward prevention of hypospadias.
Metabolic flux balance analysis during lactate and glucose concomitant consumption in HEK293 cell cultures
Authors: Martínez‐Monge Iván , Albiol Joan , Lecina Martí , Liste‐Calleja Leticia , Miret Joan , Solà Carles , Cairó Jordi J. 
Published: November 2018

AbstractAt early stages of the exponential growth phase in HEK293 cell cultures, the tricarboxylic acid cycle is unable to process all the amount of NADH generated in the glycolysis pathway, being lactate the main by‐product. However, HEK293 cells are also able to metabolize lactate depending on the environmental conditions. It has been recently observed that one of the most important modes of lactate metabolization is the cometabolism of lactate and glucose, observed even during the exponential growth phase. Extracellular lactate concentration and pH appear to be the key factors triggering the metabolic shift from glucose consumption and lactate production to lactate and glucose concomitant consumption. The hypothesis proposed for triggering this metabolic shift to lactate and glucose concomitant consumption is that HEK293 cells metabolize extracellular lactate as a response to both extracellular protons and lactate accumulation, by means of cotransporting them (extracellular protons and lactate) into the cytosol. At this point, there exists a considerable controversy about how lactate reaches the mitochondrial matrix: the first hypothesis proposes that lactate is converted into pyruvate in the cytosol, and afterward, pyruvate enters into the mitochondria; the second alternative considers that lactate enters first into the mitochondria, and then, is converted into pyruvate. In this study, lactate transport and metabolization into mitochondria is shown to be feasible, as evidenced by means of respirometry tests with isolated active mitochondria, including the depletion of lactate concentration of the respirometry assay. Although the capability of lactate metabolization by isolated mitochondria is demonstrated, the possibility of lactate being converted into pyruvate in the cytosol cannot be excluded from the discussion. For this reason, the calculation of the metabolic fluxes for an HEK293 cell line was performed for the different metabolic phases observed in batch cultures under pH controlled and noncontrolled conditions, considering both hypotheses. The main objective of this study is to evaluate the redistribution of cellular metabolism and compare the differences or similarities between the phases before and after the metabolic shift of HEK293 cells (shift observed when pH is not controlled). That is from a glucose consumption/lactate production phase to a glucose‐lactate coconsumption phase. Interestingly, switching to a glucose and lactate cometabolization results in a better‐balanced cell metabolism, with decreased glucose and amino acids uptake rates, affecting minimally cell growth. This behavior could be applied to further develop new approaches in terms of cell engineering and to develop improved cell culture strategies in the field of animal cell technology.
Bioanalytical technique for determination of tasimelteon in human plasma by LC–MS/MS and its application to pharmacokinetic study in humans
Authors: Yadlapalli Siva Sankara Rao , Karra Vijaya Kumari , Kommineni Vinutha , Katari Naresh Kumar , Manabolu Surya Surendra Babu 
Published: November 2018

AbstractA highly sensitive, specific and rapid liquid chromatography–tandem mass spectrometry technique for the quantification of tasimelteon in human plasma has been developed and validated using tasimelteon‐d5 as internal standard. Liquid–liquid extraction technique with ethyl acetate was used for extraction of tasimelteon from the plasma. The chromatographic separation was achieved on an Agilent Zorbax, Eclipse, C18 (4.6 × 50 mm, 5 μm) column using a mobile phase of acetonitrile and 0.02% formic acid buffer (85:15, v/v) with a flow rate of 0.5 mL/min. A detailed method validation was performed as per the United States Food and Drug Administration guidelines. The linear calibration curve was obtained over the concentration range 0.30–299 ng/mL. The API‐4000 liquid chromatography–tandem mass spectrometry was operated under multiple reaction monitoring mode during analysis. The validated method was successfully applied to estimate plasma concentration of tasimelteon after oral administration of a single dose of a 20 mg capsule in healthy volunteers under fasting conditions. The maximum concentration of the drug achieved in the plasma was 314 ± 147 ng/mL and the time at which this concentration was attained was 0.54 ± 0.22 h.
Natural Multi‐Target Inhibitors of Cholinesterases and Monoamine Oxidase Enzymes with Antioxidant Potential from Skin Extracts of Hypsiboas cordobae and Pseudis minuta (Anura: Hylidae)
Authors: Spinelli Roque , Sanchis Ivan , Aimaretti Florencia M. , Attademo Andres M. , Portela Madelon , Humpola Maria V. , Tonarelli Georgina G. , Siano Alvaro S. 
Published: November 2018

AbstractAlzheimer's disease (AD) is the most common cause of dementia, characterized by loss of selective neuronal and normal brain functions. Every year, ten million new cases are diagnosed worldwide. AD is a complex disease associated with all kind of different pathways, making their simultaneous modulation necessary. Nowadays anti‐AD treatments are focused on enzymatic inhibitors. The study of the amphibians’ skin had acquired great importance in the fields of biology and human health and represents an attractive and novel source for natural compounds with high potential in the development of new drugs. The present work exhibits the power of amphibian skins as a source of bioactive compounds. Herein we report the activity of extracts of two species from Hylidae family (H. cordobae and P. minuta) as reversible inhibitors of acetylcholinesterase and butyrylcholinesterase enzymes. Furthermore, the extracts inhibit MAO−B enzyme and showed antioxidant activities, acting on four important pathways of AD.
Production of (S)‐β‐Nitro Alcohols by Enantioselective C−C Bond Cleavage with an R‐Selective Hydroxynitrile Lyase
Authors: Rao D. H. Sreenivasa , Padhi Santosh Kumar 
Published: November 2018

AbstractHydroxynitrile lyase (HNL)‐catalysed stereoselective synthesis of β‐nitro alcohols from aldehydes and nitroalkanes is considered an efficient biocatalytic approach. However, only one S‐selective HNL—Hevea brasiliensis (HbHNL)—exists that is appropriate for the synthesis of (S)‐β‐nitro alcohols from the corresponding aldehydes. Further, synthesis catalysed by HbHNL is limited by low specific activity and moderate yields. We have prepared a number of (S)‐β‐nitro alcohols, by kinetic resolution with the aid of an R‐selective HNL from Arabidopsis thaliana (AtHNL). Optimization of the reaction conditions for AtHNL‐catalysed stereoselective C−C bond cleavage of racemic 2‐nitro‐1‐phenylethanol (NPE) produced (S)‐NPE (together with benzaldehyde and nitromethane, largely from the R enantiomer) in up to 99 % ee and with 47 % conversion. This is the fastest HNL‐catalysed route known so far for the synthesis of a series of (S)‐β‐nitro alcohols. This approach widens the application of AtHNL for the synthesis not only of (R)‐ but also of (S)‐β‐nitro alcohols from the appropriate substrates. Without the need for the discovery of a new enzyme, but rather by use of a retro‐Henry approach, it was used to generate a number of (S)‐β‐nitro alcohols by taking advantage of the substrate selectivity of AtHNL.
Long‐term results of carotid stenting and risk factors in patients with severe carotid artery stenosis undergoing subsequent cardiac surgery
Authors: Habib Najibullah , Mahmoodi Bakhtawar K. , Suttorp Maarten J. , Kelder Johannes C. , Tromp Selma C. , Sonker Uday , Van der Heyden Jan 
Published: November 2018

AbstractAimsTo identify risk factors for composite outcome of mortality, stroke or myocardial infarction in patients with severe carotid stenosis undergoing staged carotid artery stenting (CAS) with subsequent cardiac surgery.Methods and ResultsIn this prospective observational study, we enrolled 643 consecutive patients with both symptomatic (i.e., with history of stroke) and asymptomatic severe carotid artery disease, who required cardiac surgery. Generally, cardiac surgery was planned 30 days after the CAS procedure. The composite outcome consisted of death, stroke and myocardial infarction.The composite outcome rate was 26.3% at 5 years and 47% at 8 years after CAS. Age ≥ 80 years (hazard ratio [HR] = 1.89; 95%CI, 1.18–3.03; P = 0.008), history of stroke (HR = 1.66, 1.16–2.37; P = 0.006), chronic obstructive pulmonary disease (HR = 1.86; 1.07–3.24; P = 0.03) and kidney disease (HR = 1.83, 1.11–3.04; P = 0.02) were independent risk factors for the composite outcome during long‐term follow‐up.ConclusionsIn this study with staged CAS followed by cardiac surgery, we confirm previously reported event‐free survival rates and identify several risk factors for the composite outcome. Future studies are needed to confirm the importance of the identified risk factors and to assess their predictive ability.