bluuebunny/crossref_metadata_2025_split huggingface dataset:
Derivatisable Cyanobactin Analogues: A Semisynthetic Approach
Authors: Oueis Emilia , Adamson Catherine , Mann Greg , Ludewig Hannes , Redpath Philip , Migaud Marie , Westwood Nicholas J. , Naismith James H. 
Published: October 2015

AbstractMany natural cyclic peptides have potent and potentially useful biological activities. Their use as therapeutic starting points is often limited by the quantities available, the lack of known biological targets and the practical limits on diversification to fine‐tune their properties. We report the use of enzymes from the cyanobactin family to heterocyclise and macrocyclise chemically synthesised substrates so as to allow larger‐scale syntheses and better control over derivatisation. We have made cyclic peptides containing orthogonal reactive groups, azide or dehydroalanine, that allow chemical diversification, including the use of fluorescent labels that can help in target identification. We show that the enzymes are compatible and efficient with such unnatural substrates. The combination of chemical synthesis and enzymatic transformation could help renew interest in investigating natural cyclic peptides with biological activity, as well as their unnatural analogues, as therapeutics.
Resource utilization for transfemoral transcatheter aortic valve replacement: An international comparison
Authors: Krishnaswamy Amar , Latib Azeem , Malik Ali , Bertoldi Letizia , Poddar Kanhaiya L. , Chieffo Alaide , Montorfano Matteo , Svensson Lars G. , Alfieri Ottavio , Colombo Antonio , Tuzcu E. Murat , Kapadia Samir R. 
Published: October 2015

BackgroundTransfemoral transcatheter aortic valve replacement (TF‐TAVR) has enjoyed a rapid diffusion in the US and Europe, but the procedure is resource intensive.ObjectivesWe sought to identify differences in resource utilization between a US and European center to ascertain opportunities for improvement in the performance of TF‐TAVR.MethodsAll patients undergoing TF‐TAVR using the Edwards SAPIEN valve series at the San Raffaele Hospital (Milan, Italy) and the Cleveland Clinic Foundation (Cleveland, OH) between January 2011 and December 2012 were included. Resource utilization was defined as preprocedural imaging, intraprocedural imaging, and personnel present during the procedure.ResultsA total of 158 patients from Cleveland and 113 from Milan were analyzed. Median logistic EuroScore (22.1 vs. 15.5, P = 0.013) and STS‐PROM (8.9 vs. 5.0%, P < 0.001) were higher in Cleveland. Thirty‐day outcomes were similar. Majority of procedures in Milan were conducted without a cardiac surgeon (79%) or an imaging specialist (99%) present during the case. There was greater reliance on endotracheal intubation (94.3 vs. 3.5%), general anesthesia (GA: 94.3 vs. 4.4%), and intraprocedural TEE (93 vs. 12.4%) in Cleveland, but shorter length of stay (mean: 6.42 vs. 11.16 days).ConclusionsWe characterized resources used for patients undergoing TF‐TAVR in Cleveland and Milan. Important differences included less reliance on GA and TEE and streamlining of procedural personnel in Milan, and reduced length‐of‐stay in Cleveland. Evolution of TF‐TAVR to involve fewer operators must be balanced with the need for ready access to a comprehensive group of specialists in case of emergencies. © 2015 Wiley Periodicals, Inc.
The MitraClip Asia‐Pacific registry: Differences in outcomes between functional and degenerative mitral regurgitation
Authors: Tay Edgar , Muda Nasir , Yap Jonathan , Muller David W.M. , Santoso Teguh , Walters Darren L. , Liu Xianbao , Yamen Eric , Jansz Paul , Yip James , Zambahari Robaayah , Passage Jurgen , Ding Zee Pin , Wang Jian'an , Scalia Gregory , Soesanto Amiliana M. , Yeo Khung Keong 
Published: October 2015

ObjectivesThe objective of this study is to describe and compare the use of the MitraClip therapy in mitral regurgitation (MR) patients with degenerative MR (DMR) and functional MR (FMR).IntroductionPercutaneous edge‐to‐edge repair of severe MR using the MitraClip device is approved for use in the USA for high risk DMR while European guidelines include its use in FMR patients as well.MethodsThe MitraClip in the Asia‐Pacific Registry (MARS) is a multicenter retrospective registry, involving eight sites in five Asia‐Pacific countries. Clinical and echocardiographic characteristics, procedural outcomes and 1‐month outcomes [death and major adverse events (MAE)] were compared between FMR and DMR patients treated with the MitraClip.ResultsA total of 163 patients were included from 2011 to 2014. The acute procedural success rates for FMR (95.5%, n = 84) and DMR (92%, n = 69) were similar (P = 0.515). 45% of FMR had ≥2 clips inserted compared to 60% of those with DMR (P = 0.064).The 30‐day mortality rate for FMR and DMR was similar at 4.5% and 6.7% respectively (P = 0.555). The 30‐day MAE rate was 9.2% for FMR and 14.7% for DMR (P = 0.281). Both FMR and DMR patients had significant improvements in the severity of MR and NYHA class after 30 days. There was a significantly greater reduction in left ventricular end‐diastolic diameter (P = 0.002) and end systolic diameter (P = 0.017) in DMR than in FMR.ConclusionsThe MitraClip therapy is a safe and efficacious treatment option for both FMR and DMR. Although, there is a significantly greater reduction in LV volumes in DMR, patients in both groups report clinical benefit with improvement in functional class. © 2015 Wiley Periodicals, Inc.
Endobronchial mass formation after endobronchial ultrasound–transbronchial needle aspiration mimicking implantation metastasis
Authors: Kim Soo Han , Lee Yunkyoung , Park Shinhee , Choi Chang Min , Jo Jungmin , Lee Jae Cheol 
Published: October 2015

Key Clinical MessageEndobronchial ultrasound‐guided transbronchial needle aspiration (EBUS‐TBNA) has been widely used for diagnosing intrathoracic lymphadenopathy. Here, we present two cases of endobronchial polyp formation after an EBUS‐TBNA for suspicious malignant lymph nodes. An inflammatory polyp should be considered as a possible differential diagnosis for a newly developed mass after an EBUS‐TBNA.
Preparation of Highly Active Triflic Acid Functionalized SBA‐15 Catalysts for the Synthesis of Coumarin under Solvent‐Free Conditions
Authors: Kalita Pranjal , Baskar Arun V. , Choy Jin‐Ho , Lakhi Kripal S. , El‐Newehy Mohamed , Lawrence Geoffrey , Al‐deyab Salem S. , Balasubramanian Veerappan V. , Vinu Ajayan 
Published: October 2015

AbstractHighly acidic SBA‐15 with different pore diameters has been prepared by functionalizing the mesoporous walls with different amounts of triflic acid (TFA). The structure of the SBA‐15 before and after the functionalization with TFA was investigated by powder X‐ray diffraction and nitrogen adsorption isotherms. The interaction of TFA with the surface silanol groups of SBA‐15 and the acidity of the materials have been investigated by FTIR spectroscopy and temperature‐programmed desorption of ammonia, respectively. The characterization results reveal that the mesoporous structure of the SBA‐15 is retained even after the loading of TFA in the mesochannels and that the TFA molecules are bonded with the surface silanol groups of the SBA‐15 supports. The acidity of the materials increases with increasing amount of TFA from 5 to 20 wt %. These functionalized, highly acidic materials are found to be highly active in the synthesis of coumarin and the catalytic efficiency was found to correlate with the total acidity or the amount of TFA in the porous channels of the SBA‐15 catalysts. It has also been found that the activity of the TFA‐functionalized SBA‐15 in the synthesis of coumarin is much higher than that of different zeolites, pure mesoporous silica SBA‐15, and other mesoporous catalysts used in this study.
Synthesis of Planar Chiral Ferrocenes by Transition‐Metal‐Catalyzed Enantioselective C−H Activation
Authors: Zhu Dao‐Yong , Chen Ping , Xia Ji‐Bao 
Published: October 2015

AbstractThis minireview focuses on recent advancements in the synthesis of planar chiral ferrocenes by means of transition‐metal‐catalyzed enantioselective C−H activation. Enantioenriched planar chiral ferrocenes are synthesized through simple straightforward asymmetric carbon−carbon or carbon−heteroatom bond‐formation reactions. In these reports, site selectivity of ferrocene C−H activation is controlled by two strategies, coordination direction and intramolecular cyclization. Herein the significance of these results is summarized.
Chemical Vapor Deposition of FeOCl Nanosheet Arrays and Their Conversion to Porous α‐Fe2O3 Photoanodes for Photoelectrochemical Water Splitting
Authors: Wang Chong Wu , Yang Shuang , Jiang Hai Bo , Yang Huagui 
Published: October 2015

AbstractFeOCl nanosheet arrays were deposited on fluorine‐doped tin oxide glass substrates through a chemical vapor deposition method and further converted to hematite porous nanosheet arrays. A much enhanced photocurrent was obtained for such hematite films, which was three times higher than that of a planar hematite film at 1.23 V versus a reversible hydrogen reference electrode.
A Combined Crystallographic and Theoretical Study Explains the Capability of Carboxylic Acids to Adopt Multiple Binding Modes in the Active Site of Carbonic Anhydrases
Authors: Langella Emma , D'Ambrosio Katia , D'Ascenzio Melissa , Carradori Simone , Monti Simona M. , Supuran Claudiu T. , De Simone Giuseppina 
Published: October 2015

AbstractCarboxylates are the least investigated class of inhibitors of carbonic anhydrases (CAs). Here we explain the versatility of binding of these molecules to CAs by examining a new adduct of hCA II with N‐carboxymethyl‐saccharin.
A Robust, Eco‐Friendly Access to Secondary Thioamides through the Addition of Organolithium Reagents to Isothiocyanates in Cyclopentyl Methyl Ether (CPME)
Authors: Pace Vittorio , Castoldi Laura , Monticelli Serena , Safranek Sandra , Roller Alexander , Langer Thierry , Holzer Wolfgang 
Published: October 2015

AbstractThe nucleophilic addition of widely available and variously functionalized organolithium reagents to isothiocyanates represents a straightforward, high‐yielding, one‐pot method to access secondary thioamides. The simple reaction conditions required and the broad scope (>50 cases examples) makes it a robust and reliable method to access both simple and complex thioamides, including enantiopure ones. Noxious and unpleasant‐smelling sulfurating agents, usually employed in the literature established methods, are avoided during the whole synthetic procedure thus, rendering the protocol highly attractive, also for sustainability aspects.
Intramolecular Charge Transfer‐Enhanced BODIPY Photosensitizer in Photoinduced Electron Transfer and Its Application to Photoxidation under Mild Condition
Authors: Wang Ruiqin , Geng Ying , Zhang Lili , Wu Wenting , Fan Weiyu , Li Zhongtao , Wang Lizhuo , Zhan Liying , Wu Xueyan , Wu Mingbo 
Published: October 2015

AbstractPhotoinduced electron transfer process is a crucial step in photooxidation to obtain synthetic chemicals. However, the driving forces of electron transfer as priority in all have been rarely studied in stepwise detail. Herein, we report a series of BODIPY derivatives with an emphasis on the intramolecular charge transfer, enhancing the key step of photoinduced electron transfer process and photooxidation performances. A series of novel BODIPY photosensitizers (B‐1–B‐5) were prepared, wherein diethylamine amino of B‐3 as charge injection group was conjugated to the 2,6‐diiodo‐styryl‐BODIPY, and the electron transfer impetus was enhanced 1.6 times due to its more negative redox potentials. These results were also confirmed by the DFT/TDDFT calculation. Without pure oxygen, B‐3 still can exhibit an exceptional performance in photoxidative aromatization of 1,4‐DHP under mild condition. After irradiation for 28 min, the conversion rate came to 98.2%.
Capacitive Performances of Reduced Graphene Oxide Hydrogel Prepared by Using Sodium Hypophosphite as Reducer
Authors: Liu Cuixian , Han Gaoyi , Chang Yunzhen , Xiao Yaoming , Li Yanping , Li Miaoyu , Zhou Haihan 
Published: October 2015

AbstractThe hydrogels of reduced graphene oxide (rGOHGs) have been synthesized through treating GO with various concentrations of sodium hypophosphite (NaH2PO2) under hydrothermal condition. The results reveal that the structure of rGOHGs changes along with the increase of the concentration of NaH2PO2. The rGO sheets prepared with low concentration of NaH2PO2 exhibit more crimples and larger specific surface area than those prepared with high concentration of NaH2PO2. The measurements of the capacitive performances of rGOHGs reveal that the rGOHGs prepared with low concentration of NaH2PO2 possess larger specific capacitance (Cs) than that prepared with high concentration of NaH2PO2 at low cyclic voltammetry scan rates. However, the rGOHGs prepared with high concentration of NaH2PO2 possess larger Cs at high scan rates, more stability and better high‐rate capability than those prepared at low concentration. It is believed that the structures and properties of rGOHGs can be adjusted by controlling the concentration of NaH2PO2 according to the requirement.
Efficient One‐Pot Access to 2,9‐Dihydrothiopyrano[2,3‐b]indole Scaffolds Showing Large Stokes Shifts
Authors: Singh Shivendra , Samanta Sampak 
Published: October 2015

AbstractA simple, mild and efficient one‐pot approach for the construction of 2‐aryl‐3‐nitro‐2,9‐dihydrothiopyrano[2,3‐b]indole derivatives has been realized in CH2Cl2 medium at ambient temperature via three‐component tandem reaction of N‐protected‐2‐chloro‐3‐formylindoles, sodium hydrosulfide and β‐substituted nitroolefins/δ‐substituted nitrodienes using DABCO (10 mol%) as an organocatalyst, followed by dehydration in the presence of activated molecular sieves (4 Å). The significant advantages of this protocol are simple operation, shorter reaction time, high atom economy, good to high yields (73% –89%) and wider substrate scope. In addition, all the synthesized compounds have shown the large positive Stokes shift values (5632–6081 cm−1).
Organocatalytic Oxidative Amidation of Aldehydes with Tetrazoles to Construct 2,5‐Diaryl 1,3,4‐Oxadiazoles
Authors: Cao Jing , Wang Liang 
Published: October 2015

AbstractA practical and metal‐free oxidative amidation of aldehydes with tetrazoles into 1,3,4‐oxadiazoles has been developed by employing tetrabutylammonium iodide (TBAI) as catalyst and tert‐butyl hydroperoxide (TBHP) as oxidant. A wide range of 2,5‐disubstituted 1,3,4‐oxadiazoles can be conveniently generated in moderate to good yields. Gram‐scale reaction was also realized in this catalytic system.
Multitarget Strategy to Address Alzheimer's Disease: Design, Synthesis, Biological Evaluation, and Computational Studies of Coumarin‐Based Derivatives
Authors: Montanari Serena , Bartolini Manuela , Neviani Paolo , Belluti Federica , Gobbi Silvia , Pruccoli Letizia , Tarozzi Andrea , Falchi Federico , Andrisano Vincenza , Miszta Przemysław , Cavalli Andrea , Filipek Sławomir , Bisi Alessandra , Rampa Angela 
Published: October 2015

AbstractAlzheimer's disease (AD) is a major public health challenge that faces an aging global population. Current drug treatment has demonstrated only symptomatic efficacy, leaving an unmet medical need for a new generation of disease‐modifying therapies. Following the multitarget‐directed ligand approach, a small library of coumarin‐based derivatives was designed and synthesized as a follow‐up to our studies on AP2238, aimed at expanding its biological profile. The coumarin substitution pattern at the 6‐ or 7‐position was modified by introducing alkyl chains of variable lengths and with different terminal amino functional groups. 3‐(4‐{[Benzyl(ethyl)amino]methyl}phenyl)‐6‐({5‐[(7‐methoxy‐6H‐indeno[2,1‐b]quinolin‐11‐yl)amino]pentyl}oxy)‐2H‐chromen‐2‐one, bearing the bulkiest amine, emerged as a non‐neurotoxic dual acetylcholinesterase (AChE)/butyrylcholinesterase (BuChE) inhibitor, potentially suitable for the treatment of the middle stage of AD. Furthermore, the introduction of a diethylamino spacer, as in 3‐(4‐{[benzyl(ethyl)amino]methyl}phenyl)‐6‐{[5‐(diethylamino)pentyl]oxy}‐2H‐chromen‐2‐one and 3‐(4‐{[benzyl(ethyl)amino]methyl}phenyl)‐7‐[4‐(diethylamino)butoxy]‐2H‐chromen‐2‐one, led to nanomolar human AChE inhibitors endowed with significant inhibitory activity toward Aβ42 self‐aggregation, whereas the reference compound was completely ineffective. Furthermore, 3‐(4‐{[benzyl(ethyl)amino]methyl}phenyl)‐7‐[4‐(diethylamino)butoxy]‐2H‐chromen‐2‐one also showed promising neuroprotective behavior, which makes it a potential candidate for development into a disease‐modifying agent.
We Need 2C but Not 2B: Developing Serotonin 2C (5‐HT2C) Receptor Agonists for the Treatment of CNS Disorders
Authors: Cheng Jianjun , Kozikowski Alan P. 
Published: October 2015

AbstractThe serotonin 2C (5‐HT2C) receptor has been identified as a potential drug target for the treatment of a variety of central nervous system (CNS) disorders, such as obesity, substance abuse, and schizophrenia. In this Viewpoint article, recent progress in developing selective 5‐HT2C agonists for use in treating these disorders is summarized, including the work of our group. Challenges in this field and the possible future directions are described. Homology modeling as a method to predict the binding modes of 5‐HT2C ligands to the receptor is also discussed. Compared to known ligands, the improved pharmacological profiles of the 2‐phenylcyclopropylmethylamine‐based 5‐HT2C agonists make them preferred candidates for further studies.
Dual‐Responsive Mechanized Mesoporous Silica Nanoparticles Based on Sulfonatocalixarene Supramolecular Switches
Authors: Zhou Ting , Song Nan , Xu Shi‐Han , Dong Biao , Yang Ying‐Wei 
Published: October 2015

AbstractMesoporous silica nanoparticles (MSNs) have been functionalized with supramolecular switches, composed of cleavable disulfide bond‐containing alkylammonium stalks encircled by water‐soluble sulfonatocalix[4,6]arenes, to result in smart mechanized MSNs. Cargo can be encased tightly in the nanopores of these mechanized MSNs in their closed state, but are released efficiently either in response to L‐glutathione (GSH), by cleaving the disulfide bonds in the stalks, or in response to pH variation, by turning on the calixarene‐based supramolecular switches. The higher concentration of GSH in cancer cell cytosol and the relatively lower pH value of cancer cell lysosome can simultaneously activate the mechanized MSNs, enabling them to release the pre‐loaded cargo in place. This sufficient use of the different environment of cancer cells and normal healthy cells can enhance the targeting effect of delivery vehicles and effectively lower the side effects of delivered anti‐cancer drugs. In vitro cytotoxicity tests suggest good biocompatibility and low toxicity of these newly developed drug‐delivery systems.
Electron Density Analysis of Hyperconjugation
Authors: Azami S. M. 
Published: October 2015

AbstractHyperconjugation is analyzed through the electron density of orbitals responsible for hyperconjugative interactions, which cannot be detected by means of conventional electron‐density‐based calculations. This interaction is detected through the π electron density topology, by excluding σ electron density from the total. As the presence of the hyperconjugation phenomenon in carbocation systems is well understood, several carbocations are benchmarked, and the results show that the positive carbon atom establishes a hyperconjugative critical point with the adjacent methyl group(s). Also, π localization and delocalization indices are employed to support the conclusions made by the topological analysis.
Lignin Modification for Biopolymer/Conjugated Polymer Hybrids as Renewable Energy Storage Materials
Authors: Nilsson Ting Yang , Wagner Michal , Inganäs Olle 
Published: October 2015

AbstractLignin derivatives, which arise as waste products from the pulp and paper industry and are mainly used for heating, can be used as charge storage materials. The charge storage function is a result of the quinone groups formed in the lignin derivative. Herein, we modified lignins to enhance the density of such quinone groups by covalently linking monolignols and quinones through phenolation. The extra guaiacyl, syringyl, and hydroquinone groups introduced by phenolation of kraft lignin derivatives were monitored by 31P nuclear magnetic resonance and size exclusion chromatography. Electropolymerization in ethylene glycol/tetraethylammonium tosylate electrolyte was used to synthesize the kraft lignin/polypyrrole hybrid films. These modifications changed the phenolic content of the kraft lignin with attachment of hydroquinone units yielding the highest specific capacity (around 70 mA h g−1). The modification of softwood and hardwood lignin derivatives yielded 50 % and 23 % higher charge capacity than the original lignin, respectively.
Infant and adult pupil dilation in response to unexpected sounds
Authors: Wetzel Nicole , Buttelmann David , Schieler Andy , Widmann Andreas 
Published: October 2015

ABSTRACTSurprisingly occurring sounds outside the focus of attention can involuntarily capture attention. This study focuses on the impact of deviant sounds on the pupil size as a marker of auditory involuntary attention in infants. We presented an oddball paradigm including four types of deviant sounds within a sequence of repeated standard sounds to 14‐month‐old infants and to adults. Environmental and noise deviant sounds elicited a strong pupil dilation response (PDR) in both age groups. In contrast, moderate frequency deviants elicited a significant PDR in adults only. Moreover, a principal component analysis revealed two components underlying the PDR. Component scores differ, depending on deviant types, between age groups. Results indicate age effects of parasympathetic inhibition and sympathetic activation of the pupil size caused by deviant sounds with a high arousing potential. Results demonstrate that the PDR is a sensitive tool for the investigation of involuntary attention to sounds in preverbal children. © 2015 Wiley Periodicals, Inc. Dev Psychobiol 58: 382–392, 2016.
The past, present, and future of basal insulins
Authors: Pettus Jeremy , Santos Cavaiola Tricia , Tamborlane William V. , Edelman Steven 
Published: October 2015

SummaryInsulin production by the pancreas follows a basic pattern where basal levels of insulin are secreted during fasting periods, with prandial increases in insulin associated with food ingestion. The aim of insulin therapy in patients with diabetes is to match the endogenous pattern of insulin secretion as closely as possible without causing hypoglycaemia. There are several optimal pharmacokinetic and pharmacodynamic properties of long‐acting basal insulins that can help to achieve this aim, namely, as follows: activity that is flat and as free of peaks as possible, a duration of action of ≥24‐h, and as little day‐to‐day variation as possible. The long‐acting basal insulins are a fundamental therapy for patients with type 1 and type 2 diabetes, and those that are currently available have many benefits; however, the development of even longer‐acting insulins and improved insulin delivery techniques may lead to better glycemic control for patients in the future. Established long‐acting basal insulins available in the United States and Europe include insulin glargine 100 units/mL and insulin detemir, both of which exhibit similar glycemic control to that of the intermediate‐acting neutral protamine Hagedorn insulin, but with a reduction in hypoglycaemia. Newer insulin products available include new insulin glargine 300 units/mL (United States and Europe) and the ultra‐long‐acting insulin degludec (Europe) with basal insulin peglispro currently in development. These new insulins demonstrate different pharmacokinetic/pharmacodynamic profiles and longer durations of action (>24 h) compared with insulin glargine 100 units/mL, which may lead to potential benefits. The introduction of biosimilar insulins may also broaden access to insulins by reducing treatment costs. Copyright © 2015 John Wiley & Sons, Ltd.