bluuebunny/crossref_metadata_2025_split huggingface dataset:
Validation of a patient‐reported outcomes symptom measure for patients with nontransfusion‐dependent thalassemia (NTDT‐PRO©)
Authors: Taher Ali , Cappellini Maria Domenica , Viprakasit Vip , Sutcharitchan Pranee , Mahmoud Dalia , Laadem Abderrahmane , Khan Anzalee , Gwaltney Chad , Harding Gale , Attie Kenneth , Zhang Xiaosha , Zou Jun , Pariseau Joseph , Henry Hu X. , Kattamis Antonis 
Published: November 2018

AbstractThis study demonstrates the quantitative characteristics of the first patient‐reported outcome (PRO) tool developed for patients with nontransfusion‐dependent β‐thalassemia (NTDT), the NTDT‐PRO©. A multicenter validation study was performed over 24 weeks, involving 48 patients from Italy, Lebanon, Greece, and Thailand. Most patients were female (68.8%), with a median age of 34.5 years (range, 18‐52); 66.7% were diagnosed with β‐thalassemia intermedia, and median time since diagnosis was 22 years (range, 0‐43). The NTDT‐PRO comprises 6 items across 2 domains (Tiredness/Weakness and Shortness of Breath [SoB]), and was valid and reliable, with good consistency. At baseline, most patients reported symptoms as present via the NTDT‐PRO, and were highly compliant, ≥90% completing the NTDT‐PRO tool. In a pairwise correlation analysis, all items were positively correlated. Correlations between NTDT‐PRO and existing tools—36‐Item Short Form Health Survey version 2 (SF‐36v2) and Functional Assessment of Cancer Therapy‐Anemia (FACT‐An)—were assessed at weeks 1, 3, and 12; robust correlations were seen between SoB and SF‐36v2‐Vitality (rs = −0.53), and between SoB and Fact‐An‐Fatigue Experience (rs = −0.66) at week 1. Internal consistency was high for both Tiredness/Weakness (Cronbach alpha, 0.91) and SoB (Spearman‐Brown coefficient, 0.78); intraclass correlation coefficients were high (Tiredness/Weakness, 0.88 and 0.97; SoB, 0.92 and 0.98), demonstrating stability. Further studies are required to fully support the validity of this tool, this study demonstrated the usefulness of the NTDT‐PRO in the clinical setting and for longitudinal clinical research, particularly in trials where patient health‐related quality of life is expected to change.
Synthetic Approaches toward Vitamin B12 Conjugates
Authors: Wierzba Aleksandra J. , Hassan Sidra , Gryko Dorota 
Published: November 2018

AbstractThe ability to conjugate functional molecules to vitamin B12 (cobalamin) is an important strategy for the construction of hybrid molecules with various applications in medicinal chemistry, diagnostics, and biological sciences. Cobalamin, as an exogenous compound, reaches mammalian cells via a system of transport proteins and therefore the position of conjugation must be selected in such a way that the recognition process is not disturbed. The complex structure of vitamin B12 provides many routes for the synthesis of conjugates containing cargos appended at different sites, however, only the e‐propionamide chain, β‐axial position and R5′‐OH are found to meet the aforementioned criteria. Over the years, a number of synthetic approaches leading to cobalamin conjugates have been developed and, herein, we summarize those leading to conjugates with a cargo tethered at the central cobalt ion, macrocyclic core, ribonucleotide moiety, or a combination thereof.
Rapid Mapping of Protein Interactions Using Tag‐Transfer Photocrosslinkers
Authors: Horne Jim E. , Walko Martin , Calabrese Antonio N. , Levenstein Mark A. , Brockwell David J. , Kapur Nikil , Wilson Andrew J. , Radford Sheena E. 
Published: November 2018

AbstractAnalysing protein complexes by chemical crosslinking‐mass spectrometry (XL‐MS) is limited by the side‐chain reactivities and sizes of available crosslinkers, their slow reaction rates, and difficulties in crosslink enrichment, especially for rare, transient or dynamic complexes. Here we describe two new XL reagents that incorporate a methanethiosulfonate (MTS) group to label a reactive cysteine introduced into the bait protein, and a residue‐unbiased diazirine‐based photoactivatable XL group to trap its interacting partner(s). Reductive removal of the bait transfers a thiol‐containing fragment of the crosslinking reagent onto the target that can be alkylated and located by MS sequencing and exploited for enrichment, enabling the detection of low abundance crosslinks. Using these reagents and a bespoke UV LED irradiation platform, we show that maximum crosslinking yield is achieved within 10 seconds. The utility of this “tag and transfer” approach is demonstrated using a well‐defined peptide/protein regulatory interaction (BID80‐102/MCL‐1), and the dynamic interaction interface of a chaperone/substrate complex (Skp/OmpA).
Intramolecular Consecutive Dehydro‐Diels–Alder Reaction for the Catalytic and Enantioselective Construction of Axial Chirality
Authors: Shibata Takanori , Sekine Ayato , Mitake Akihito , Kanyiva Kyalo Stephen 
Published: November 2018

AbstractConsecutive thermal and metal‐catalyzed dehydro‐Diels–Alder (DDA) reactions of sulfur‐tethered tetraynes, possessing a 1,3‐diyne moiety, proceeded efficiently, and axial chirality was achieved for the resulting dibenzothiophenyl moieties. Chiral‐rhodium catalysis realized a highly enantioselective synthesis, and transformations into bis(benzocarbazole) derivatives were also achieved.
N‐Heterocyclic Carbene Catalyzed Quadruple Domino Reactions: Asymmetric Synthesis of Cyclopenta[c]chromenones
Authors: Liu Qiang , Chen Xiang‐Yu , Puttreddy Rakesh , Rissanen Kari , Enders Dieter 
Published: November 2018

AbstractAn N‐heterocyclic carbene catalyzed domino sequence via α,β‐unsaturated acyl azolium intermediates has been developed. This strategy provides a convenient enantioselective route to functionalized tricyclic coumarin derivatives and cyclopentanes. DFT studies and control experiments were performed to gain better insight into the reaction mechanism.
Templating and Catalyzing [2+2] Photocycloaddition in Solution Using a Dynamic G‐Quadruplex
Authors: Sutyak Keith B. , Lee Wes , Zavalij Peter V. , Gutierrez Osvaldo , Davis Jeffery T. 
Published: November 2018

AbstractWe describe a templating/covalent capture strategy that enables photochemical formation of 8 cyclobutanes in one noncovalent assembly. This process was characterized by experiment and quantum mechanical/molecular mechanics (ONIOM) calculations. Thus, KI and 16 units of 5′‐cinnamate guanosine form a G‐quadruplex where C=C π bonds in neighboring G4‐quartets are separated by 3.3 Å, enabling [2+2] photocycloaddition in solution. This reaction is high‐yielding (>90 %), regio‐ and diastereoselective. Since all components are in dynamic equilibrium this photocycloaddition is catalytic in K+.
A Local‐Desymmetrization‐Based Divergent Synthesis of Quinine and Quinidine
Authors: Lee Jaehoo , Chen David Y.‐K. 
Published: November 2018

AbstractHerein we report a novel synthetic entry to the legendary quinuclidine natural products quinine and quinidine. The developed strategy is based on the use of a symmetrical and nonstereogenic precursor to access quinine and quinidine through a “local‐desymmetrization” approach, in stark contrast conceptually to the preparation of stereodefined disubstituted piperidines (or their acyclic precursors) as featured in all past syntheses. The developed strategy also provided quinine and quinidine derivatives that could not be readily obtained through previous total syntheses or by modification of the naturally occurring substances.
A Noble‐Metal‐Free Heterogeneous Photosensitizer‐Relay Catalyst Triad That Catalyzes Water Oxidation under Visible Light
Authors: Ulusoy Ghobadi T. Gamze , Akhuseyin Yildiz Elif , Buyuktemiz Muhammed , Sadigh Akbari Sina , Topkaya Derya , İsci Ümit , Dede Yavuz , Yaglioglu H. Gul , Karadas Ferdi 
Published: November 2018

AbstractAn entirely earth‐abundant chromophore‐relay water oxidation catalyst triad system, which is robust and efficient at neutral pH, is presented. The synthesis involves the coordination of a porphyrin derivative to a bridging Fe(CN)5 group, which is then reacted with Co ions to prepare a covalently linked chromophore–Prussian blue analogue assembly. Light‐driven water oxidation studies in the presence of an electron scavenger indicate that the triad is active and it maintains a steady activity for at least three hours. Transient absorption experiments and computational studies reveal that the Fe(CN)5 group is more than a linker as it takes part in electron‐transfer and co‐operates with porphyrin in the charge separation process.
Fein‐Tuning der Porengröße in versteiften ZIF‐8_Cm‐Gerüsten durch eine Mixed‐Linker‐Strategie für verbesserte permeative CO2/CH4‐Trennung
Authors: Hou Qianqian , Wu Ying , Zhou Sheng , Wei Yanying , Caro Jürgen , Wang Haihui 
Published: November 2018

AbstractZIF‐8‐Membranen könnten nach dem Prinzip des Größenausschlusses zur CO2/CH4‐Trennung eingesetzt werden. Wenn die ZIF‐8‐Schicht jedoch – wie üblich – solvothermal abgeschieden wird, zeigt sie aufgrund der Linker‐Mobilität nur eine geringe Trennselektivität. Wir können ≈500 nm dünne Hybrid‐ZIF‐7x‐8‐Membranen mit unterdrückter Linker‐Mobilität und verengter Apertur durch eine schnelle gesteuerte Elektro‐Synthese (fast current‐driven synthesis=FCDS) innerhalb von 20 Minuten herstellen. Das in situ anliegende elektrische Feld während der FCDS führt zur Bildung von versteiftem ZIF‐8_Cm als Grundgerüst. Gleichzeitig wird die Mixed‐Linker‐Strategie angewendet, um die Porengröße weiter zu verengen. Die ZIF‐722‐8‐Membran zeigt ein deutlich geschärftes Molekularsieben für CO2/CH4 mit einem Trennfaktor von über 25, der um eine Größenordnung über dem der unmodifizierten ZIF‐8‐Membran liegt. Darüber hinaus zeigt die Membran auch eine verbesserte Trennleistung für H2/CH4 und CO2/N2 mit Trennfaktoren von 71 bzw. 20. Nach 180 h mit zyklischem Temperaturwechsel bleibt die ausgezeichnete Trennleistung erhalten.
Intermolecular C(sp3)−H Amination Promoted by Internal Oxidants: Synthesis of Trifluoroacetylated Hydrazones
Authors: Zhu Chuanle , Zeng Hao , Chen Fulin , Yang Zhiyi , Cai Yingying , Jiang Huanfeng 
Published: November 2018

AbstractAn intermolecular C(sp3)−H amination reaction is reported that is promoted by internal oxidants and occurs via a C=N bond formation step. This intermolecular C(sp3)−H amination reaction of trifluoromethyl ketones and aryldiazonium tetrafluoroborates affords various valuable trifluoroacetylated hydrazones in high yields with excellent E/Z selectivities. The salient features of this reaction type is that it is free of metal, catalyst, directing groups, and azides, and that it can be carried out under mild conditions, is operationally simple and efficient, gram‐scalable, and it tolerates various functional groups. Remarkably, an ectoparasites‐controlling agent was smoothly synthesized on a gram scale using our method. Aryldiazonium tetrafluoroborates served as the aminating reagents as well as an internal oxidant.
Population‐based surveillance of congenital heart defects among adolescents and adults: surveillance methodology
Authors: Glidewell Jill , Book Wendy , Raskind‐Hood Cheryl , Hogue Carol , Dunn Julie E. , Gurvitz Michelle , Ozonoff Al , McGarry Claire , Van Zutphen Alissa , Lui George , Downing Karrie , Riehle‐Colarusso Tiffany 
Published: November 2018

BackgroundImproved treatment of congenital heart defects (CHDs) has increased survival of persons with CHDs; however, no U.S. population‐based systems exist to assess prevalence, healthcare utilization, or longer‐term outcomes among adolescents and adults with CHDs.MethodsNovel approaches identified individuals aged 11–64 years who received healthcare with ICD‐9‐CM codes for CHDs at three sites: Emory University in Atlanta, Georgia (EU), Massachusetts Department of Public Health (MA), New York State Department of Health (NY) between January 1, 2008 (2009 for MA) and December 31, 2010. Case‐finding sources included outpatient clinics; Medicaid and other claims data; and hospital inpatient, outpatient, and emergency visit data. Supplemental information came from state vital records (EU, MA), and birth defects registries (EU, NY). Demographics and diagnostic and procedural codes were linked, de‐duplicated, and shared in a de‐identified dataset. Cases were categorized into one of five mutually exclusive CHD severity groups; non‐cardiac comorbidity codes were grouped into broad categories.Results73,112 individuals with CHD codes in healthcare encounters were identified. Primary data source type varied: clinics (EU, NY for adolescents), claims (MA), hospital (NY for adults). There was a high rate of missing data for some variables and data varied in format and quality. Some diagnostic codes had poor specificity for CHD ascertainment.ConclusionsTo our knowledge, this is the first population‐based, multi‐site CHD surveillance among adolescents and adults in the U.S. Identification of people living with CHDs through healthcare encounters using multiple data sources was feasible, though data quality varied and linkage/de‐duplication was labor‐intensive.
Sex differences in national rates of repair of emergency abdominal aortic aneurysm
Authors: Aber A , Tong T S , Chilcott J , Thokala P , Maheswaran R , Thomas S M , Nawaz S , Walters S , Michaels J 
Published: November 2018

Abstract

Background
The aim of this study was to assess the sex differences in both the rate and type of repair for emergency abdominal aortic aneurysm (AAA) in England.

Methods
Hospital Episode Statistics (HES) data sets from April 2002 to February 2015 were obtained. Clinical and administrative codes were used to identify patients who underwent primary emergency definitive repair of ruptured or intact AAA, and patients with a diagnosis of AAA who died in hospital without repair. These three groups included all patients with a primary AAA who presented as an emergency. Sex differences between repair rates and type of surgery (endovascular aneurysm repair (EVAR) versus open repair) over time were examined.

Results
In total, 15 717 patients (83·3 per cent men) received emergency surgical intervention for ruptured AAA and 10 276 (81·2 per cent men) for intact AAA; 12 767 (62·0 per cent men) died in hospital without attempted repair. The unadjusted odds ratio for no repair in women versus men was 2·88 (95 per cent c.i. 2·75 to 3·02). Women undergoing repair of ruptured AAA were older and had a higher in-hospital mortality rate (50·0 versus 41·0 per cent for open repair; 30·9 versus 23·5 per cent for EVAR). After adjustment for age, deprivation and co-morbidities, the odds ratio for no repair in women versus men was 1·34 (1·28 to 1·40). The in-hospital mortality rate after emergency repair of an intact AAA was also higher among women.

Conclusion
Women who present as an emergency with an AAA are less likely to undergo repair than men. Although some of this can be explained by differences in age and co-morbidities, the differences persist after case-mix adjustment.
A low‐cost, free‐software platform with hard real‐time performance for control engineering education
Authors: González‐Vargas Andrés M. , Serna‐Ramirez Juan M. , Fory‐Aguirre Carlos , Ojeda‐Misses Alejandro , Cardona‐Ordoñez John M. , Tombé‐Andrade Jimmy , Soria‐López Alberto 
Published: November 2018

AbstractIn this paper, we present a novel portable servomechanism control platform for educational purposes. The platform main features are: low cost, reliable and robust hardware, high‐speed USB interface, free open source software (FOSS), graphical interface modeling (via Scilab/XCos) and hard real‐time performance based on the Real‐Time Application Interface for Linux (RTAI). The platform is easy to interface with any computer and can be carried home by students, opening many new possibilities for practical assignments in control courses. We include application examples and student feedback regarding their experience during various workshops in which the system was demonstrated.
Recent Advances in Artificially Sulfated Polysaccharides for Applications in Cell Growth and Differentiation, Drug Delivery, and Tissue Engineering
Authors: Zeng Kui , Groth Thomas , Zhang Kai 
Published: November 2018

AbstractArtificially sulfated polysaccharides, as the mimetics of native heparin and heparan sulfate, are important bioactive compounds, since they show great potential for tuning crucial biological activities within living organisms. Herein, we summarize progress in the development of artificially sulfated polysaccharides, such as cellulose sulfate, chitosan sulfate, and other sulfated polysaccharides, with a particular focus on the fields of biomedical and bioengineering applications in the past ten years. Their effects on cell growth and differentiation, but also as building blocks for drug carriers and medical implants, are emphasized.
Diterpene Synthase‐Catalyzed Biosynthesis of Distinct Clerodane Stereoisomers
Authors: Pelot Kyle A. , Hagelthorn David M. , Hong Young J. , Tantillo Dean J. , Zerbe Philipp 
Published: November 2018

AbstractThe diterpene synthase clerodienyl diphosphate synthase 1 (PvCPS1) from the crop plant switchgrass (Panicum virgatum) stereoselectively converts (E,E,E)‐geranylgeranyl diphosphate (GGPP) into the clerodane natural product, cis‐trans‐clerodienyl diphosphate (CLPP, 1). Structure‐guided point mutations of PvCPS1 redirected product stereoselectivity toward the formation of a rare cis‐clerodane diastereomer, cis‐cis‐CLPP (2). Additionally, an alternative cis‐clerodane diastereomer, (5S,8S,9R,10R)‐13Z‐CLPP (3), was produced when treating PvCPS1 and select variants thereof with the cis‐prenyl substrate (Z,Z,Z)‐nerylneryl diphosphate (NNPP). These results support the hypothesis that substrate configuration and minor active‐site alterations impact precatalysis substrate folding in the stereoselective biosynthesis of clerodane diterpenoid scaffolds, and can be employed to provide enzymatic access to a broader range of bioactive clerodane natural products.
Minimizing radiographic contrast administration during coronary angiography using a novel contrast reduction system: A multicenter observational study of the DyeVert™ plus contrast reduction system
Authors: Gurm Hitinder S. , Mavromatis Kreton , Bertolet Barry , Kereiakes Dean J. , Amin Amit P. , Shah Atman P. , Hanzel George S. , Rao Siddhartha , Thomas Joseph L. , Kumar Gautam 
Published: November 2018

AbstractObjectiveTo evaluate contrast media (CM) volume (CMV) saved using the DyeVert™ Plus Contrast Reduction System (DyeVert Plus System, Osprey Medical) in patients undergoing diagnostic coronary angiogram (CAG) and/or percutaneous coronary interventional (PCI) procedures performed with manual injections.BackgroundCurrent guidelines advocate for monitoring and minimization of the total volume of CM in chronic kidney disease (CKD) patients undergoing invasive cardiac procedures. The DyeVert Plus System is an FDA cleared device designed to reduce CMV delivered during angiography and permit real‐time CMV monitoring.MethodsWe performed a multicenter, single‐arm, observational study. Eligible subjects were ≥ 18 years old with baseline estimated glomerular filtration rate (eGFR) 20–60 mL/min/1.73 m2. The primary endpoint was % CMV saved over the total procedure. A secondary objective was to evaluate adverse events (AEs) related to DyeVert Plus System or to CM use.ResultsA total of 114 subjects were enrolled at eight centers. Mean age was 72 ± 9 years, 72% were male, and mean body mass index was 29 ± 5. Baseline eGFR was 43 ± 11 mL/min/1.73 m2. CAG‐only was performed in 65% of cases. One hundred and five subjects were evaluable for the primary endpoint. Mean CMV attempted was 112 ± 85 mL (range 22–681) and mean CMV delivered was 67 ± 51 mL (range 12–403), resulting in an overall CMV savings of 40.1 ± 8.8% (95% CI 38.4, 41.8; P < 0.0001) per procedure. Image quality was maintained in all but one case where the system was turned off for one injection. No DyeVert Plus System‐related AEs were reported. Acute kidney injury (AKI; defined as serum creatinine rise of >0.3 mg/dL from baseline) was reported in 11 cases with seven occurring in subjects with baseline eGFR < 30 and three AKI events were attributed to CM. AKI rates increased as CMV/eGFR ratios increased.ConclusionsThese data suggest DyeVert Plus System use in CKD patients undergoing CAG and/or PCI results in clinically meaningful CMV savings while maintaining image quality.
Molecular QTAIM Topology Is Sensitive to Relativistic Corrections
Authors: Anderson James S. M. , Rodríguez Juan I. , Ayers Paul W. , Trujillo‐González Daniel E. , Götz Andreas W. , Autschbach Jochen , Castillo‐Alvarado Fray L. , Yamashita Koichi 
Published: November 2018

AbstractThe topology of the molecular electron density of benzene dithiol gold cluster complex Au4−S−C6H4−S′−Au′4changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.
Morphology Driven by Molecular Structure of Thiazole‐Based Polymers for Use in Field‐Effect Transistors and Solar Cells
Authors: Hong Jisu , Wang Canjie , Cha Hyojung , Kim Hyung Nam , Kim Yebyeol , Park Chan Eon , An Tae Kyu , Kwon Soon‐Ki , Kim Yun‐Hi 
Published: November 2018

AbstractThe effects of the molecular structure of thiazole‐based polymers on the active layer morphologies and performances of electronic and photovoltaic devices were studied. Thus, thiazole‐based conjugated polymers with a novel thiazole‐vinylene‐thiazole (TzVTz) structure were designed and synthesized. The TzVTz structure was introduced to extend the π conjugation and coplanarity of the polymer chains. By combining alkylthienyl‐substituted benzo[1,2‐b:4,5‐b′]dithiophene (BDT) or dithieno[2,3‐d:2′,3′‐d′]benzo[1,2‐b:4,5‐b′]dithiophene (DTBDT) electron‐donating units and a TzVTz electron‐accepting unit, enhanced intermolecular interactions and charge transport were obtained in the novel polymers BDT‐TzVTz and DTBDT‐TzVTz. With a view to using the polymers in transistor and photovoltaic applications, the molecular self‐assembly in and their nanoscale morphologies of the active layers were controlled by thermal annealing to enhance the molecular packing and by introducing a diphenyl ether solvent additive to improve the miscibility between polymer donors and [6,6]phenyl‐C71‐butyric acid methyl ester (PC71BM) acceptors, respectively. The morphological characterization of the photoactive layers showed that a higher degree of π‐electron delocalization and more favorable molecular packing in DTBDT‐TzVTz compared with in BDT‐TzVTz leads to distinctly higher performances in transistor and photovoltaic devices. The superior performance of a photovoltaic device incorporating DTBDT‐TzVTz was achieved through the superior miscibility of DTBDT‐TzVTz with PC71BM and the improved crystallinity of DTBDT‐TzVTz in the nanofibrillar structure.
Light‐Controlled Chemoenzymatic Immobilization of Proteins towards Engineering of Bioactive Papers
Authors: Hilberg Valentina , Avrutina Olga , Ebenig Aileen , Yanakieva Desislava , Meckel Tobias , Biesalski Markus , Kolmar Harald 
Published: November 2018

AbstractEfficient and reliable methods for the generation of bioactive papers are of growing interest in relation to point‐of‐care testing devices that do not require extensive analytical equipment. Herein, we report the immobilization of functional proteins on paper fibers using a modular chemoenzymatic approach. The synthetic strategy relies on a combination of highly efficient spatially controllable photo‐triggered cycloaddition followed by site‐specific sortase A‐catalyzed transamidation. This site‐directed and regiospecific method has allowed unidirectional and covalent immobilization of several proteins displaying different functional properties, with ramifications for application in paper‐based diagnostics.