bluuebunny/crossref_metadata_2025_split huggingface dataset:
“Enzymatic” Photoreduction of Carbon Dioxide using Polymeric Metallofoldamers Containing Nickel–Thiolate Cofactors
Authors: Thanneeru Srinivas , Nganga John K. , Amin Alireza Shirazi , Liu Ben , Jin Lei , Angeles‐Boza Alfredo M. , He Jie 
Published: January 2017

AbstractThe photoreduction of CO2 by using enzyme‐mimicking polymeric metallofoldamers containing Ni–thiolate cofactors was explored. Metallofoldamers consisting of folded polymers incorporated with Ni–thiolate complexes were prepared by intramolecular Ni–thiolate coordination with thiol‐functionalized linear copolymers. The folded polymer backbone may resemble the protein framework to provide a second coordination environment to the active sites. We showed that Ni–metallofoldamers were superiorly active and selective for CO2 photoreduction. At 80 °C, the turnover frequency of the Ni–metallofoldamers could reach 0.69 s−1, which corresponds to 2500 turnovers per hour per Ni site. Our findings are expected to provide useful guidelines to investigate artificial enzymes and to understand the role of protein frameworks in photosynthesis.
Ultrafast Electrodeposition of Ni−Fe Hydroxide Nanosheets on Nickel Foam as Oxygen Evolution Anode for Energy‐Saving Electrolysis of Na2CO3/NaHCO3
Authors: Sun Yanzhi , Liu Chunxiang , Zhang Linying , Wan Pingyu , Zhuang Shuxian , Tang Yang , Chen Yongmei , Pan Junqing 
Published: January 2017

AbstractNickel/iron (Ni−Fe)‐based compounds are known as active electrocatalysts for the oxygen evolution reaction (OER), which plays an important role in metal−air batteries and water splitting. Herein, a three‐dimensional (3D) porous nickel foam electrode (NiFe(OH)x NSs/Nif) modified with Ni−Fe hydroxide nanosheets (NSs) is prepared by using a fast and facile electrodeposition method. The electrode is subsequently applied in the electrolysis of Na2CO3/NaHCO3 to produce hydrogen, oxygen, NaOH, and NaHCO3/CO2. By carefully controlling the electrodeposition time, ultrathin NiFe(OH)x NSs with a thickness of approximately 2–6 nm are interlaced with one another and grown vertically on nickel foam to form a hierarchical composite electrode. The prepared NiFe(OH)x NSs/Nif electrode exhibits superb OER performance with an overpotential of 260 mV at 10 mA cm−2 and a low Tafel slope of 29 mV dec−1 in 1 mol L−1 NaOH solution. In 0.5 mol L−1 Na2CO3/NaHCO3 solution, the NiFe(OH)x NSs/Nif electrode exhibits a low OER potential of 290 mV, which is lower than the commercial RuO2/Ti electrode at a current density of 100 mA cm−2, and shows good long‐term stability. During electrolysis of Na2CO3/NaHCO3, the cell voltage with the NiFe(OH)x NSs/Nif anode is 2.52 V, which is 280 mV lower than that with a commercial RuO2/Ti anode.
Theory and Simulation for Optimising Electrogenerated Chemiluminescence from Tris(2,2′‐bipyridine)‐ruthenium(II)‐Doped Silica Nanoparticles and Tripropylamine
Authors: Daviddi Enrico , Oleinick Alexander , Svir Irina , Valenti Giovanni , Paolucci Francesco , Amatore Christian 
Published: January 2017

AbstractElectrochemiluminescence (ECL), that is, light emission from an electronically excited species generated by electrochemical means, sustains powerful (bio)analytical methods for the ultrasensitive detection of biological targets. Co‐reactant systems involving an inexpensive organic molecule, most generally a tertiary amine, and a metal complex luminophore are commonly used for such purposes. Owing to the high cost of the luminophore moiety, several groups have considered minimising its quantity by sequestrating it at high concentration inside nanoparticles. However, to be efficient and to optimise ECL responses, this strategy requires that the nanoparticle carrier is suitably placed inside the diffusion layer of the oxidised organic co‐reactant. In this work, we firstly investigated this optimisation problem by introducing a rather simple analytical model to delineate qualitatively the main mechanistic features controlling the ECL intensity. This was then analysed in more detail by using 2D simulations. Analysis of these 2D‐heavy simulations in terms of memory occupation and CPU time, evidenced that similar results (i. e. with a relative precision best than a few percent) could be achieved with much faster 1D simulations. These 1D simulations allowed specifying quantitatively the main features of the analytical model qualitative predictions and to propose simple rules for the optimisation of the luminophore‐doped nanoparticles placement inside the diffusion layer of the organic co‐reactant.
Conformational Analysis of an Antibacterial Cyclodepsipeptide Active against Mycobacterium tuberculosis by a Combined ROE and RDC Analysis
Authors: Fredersdorf Maic , Kurz Michael , Bauer Armin , Ebert Marc‐Olivier , Rigling Carla , Lannes Laurie , Thiele Christina Marie 
Published: January 2017

AbstractGriselimycin (GM) and methylgriselimycin (MGM), naturally produced by microorganisms of the genus Streptomyces, are cyclic depsipeptides composed of ten amino acids. They exhibit antibacterial activity against Mycobacterium species by inhibiting the sliding clamp of prokaryotic DNA polymerase III and are therefore considered as potential anti‐tuberculosis drugs. The difference between the peptides is the presence of l‐(R)‐4‐methyl‐proline in MGM instead of l‐proline in GM at position 8 of the amino acid sequence. Methylation increases both metabolic stability and activity of MGM compared to GM. To get deeper insight into the structure–activity relationship, the solution structure of the cyclic part of MGM was determined using rotating‐frame nuclear Overhauser effect (ROE) distance restraints and residual dipolar couplings (RDC). The structure of MGM in solution is compared to the structure of GM in a co‐crystal with DNA polymerase III subunit beta. As a result, a highly defined structural model of MGM is obtained, which shows related characteristics to the bound GM.
Carbatriphyrin(3.1.1)–A Distinct Coordination Approach of BIII to Generate Organoborane and Weak C−H⋅⋅⋅B Interactions
Authors: Adinarayana B. , Thomas Ajesh P. , Yadav Prerna , Mukundam Vanga , Srinivasan A. 
Published: January 2017

AbstractCarbatriphyrin(3.1.1) is the structural isomer of biphenylcorrole and achieved by switching the bonding mode of biphenyl unit from 3,3′ to 2,3′ which turns the corrole into a triphyrin analogue. The presence of a m‐arene unit in the framework restricts the overall conjugation and thus leads to a nonaromatic macrocycle. The protonation experiments afford a trifluoroacetate ion complex. The coordination chemistry reveals that the bottom approach of boron(III) ion forms weak C−H⋅⋅⋅B interactions, however a top approach stabilizes the organoborane complex and the product distribution relies on the basicity of the proton scavengers. These results are unambiguously confirmed by single‐crystal X‐ray analyses.
A Cryptand Metal–Organic Framework as a Platform for the Selective Uptake and Detection of Group I Metal Cations
Authors: Sapchenko Sergey A. , Demakov Pavel A. , Samsonenko Denis G. , Dybtsev Danil N. , Schröder Martin , Fedin Vladimir P. 
Published: January 2017

AbstractThe metal–organic framework (MOF) complex (H3O)2[Zn4(ur)(Hfdc)2(fdc)4] (1, ur=urotropine, H2fdc=furan‐2,5‐dicarboxylic acid) incorporates cryptand‐like cavities, which can be used to separate and detect Rb+ and Cs+ optically. This is the first example of the effective employment of a MOF material for optical detection of these cations.
Nano “Koosh Balls” of Mesoporous MnO2: Improved Supercapacitor Performance through Superior Ion Transport
Authors: Maqbool Qysar , Singh Chanderpratap , Jash Priyajit , Paul Amit , Srivastava Aasheesh 
Published: January 2017

AbstractManganese dioxide nanomaterials with “Koosh‐ball”‐like morphology (MnO2‐KBs) as well as worm‐like nanotubes (MnO2‐NWs) are obtained by employing Tween 20 as the reducing and structure‐directing agent, and KMnO4 as a MnO2 precursor. Whereas the MnO2‐KBs are interconnected through tubular extensions, the MnO2‐NWs are largely disconnected. Both MnO2‐KBs and MnO2‐NWs have large BET surface areas (>200 m2 g−1), and are thermally robust up to 300 °C. Electrochemical studies reveal that the highest specific capacitance (Csp) obtained for MnO2‐KBs (272 F g−1) is significantly higher than that of MnO2‐NWs (129 F g−1). The Csp values correlate well with the electroactive surface areas of the materials: MnO2‐KBs have a significantly higher electrolyte‐accessible surface area. Electrochemical impedance spectroscopy (EIS) reveals a higher electron‐transfer rate at the electrode/electrolyte interface for MnO2‐KBs than for MnO2‐NWs. The multiple tubular interconnections between individual MnO2‐KBs allow improved ion penetration and act as conduits for their propagation, shortening the diffusion distances of the ions from external electrolytes to the interior of the MnO2 framework. Thus, this work exemplifies the importance of interconnections for enhancing the electrochemical performance of nanomaterials employed for energy storage.
Competition between Cation–Solvent and Cation–Anion Interactions in Imidazolium Ionic Liquids with Polar Aprotic Solvents
Authors: Marekha Bogdan A. , Kalugin Oleg N. , Bria Marc , Takamuku Toshiyuki , Gadžurić Slobodan , Idrissi Abdenacer 
Published: January 2017

AbstractThe subtle interplay between ion solvation and association was analyzed in mixtures of imidazolium‐based ionic liquids (ILs) with polar aprotic solvents. A site‐specific pattern of cation–solvent and cation–anion interactions was disclosed by a careful analysis of the 1H and 13C NMR chemical shift dependence of the mixture composition. It was established that the less polar but more donating γ‐butyrolactone is more prone to establish H‐bonds with the imidazolium‐ring hydrogen atoms of the IL cations than propylene carbonate, particularly at the H2 site and at high dilutions xIL<0.1. The H2 site was found to be more sensitive to intermolecular interactions compared to H4, 5 in the case of ILs with asymmetric anions like trifluoromethanesulfonate (TfO−) or bis(trifluoromethylsulfonyl)amide (TFSA−).
Prognostic Impact of Lymphocyte Subpopulations in Peripheral Blood after Hematopoietic Stem Cell Transplantation for Hematologic Malignancies
Authors: Park Sang Hyuk , Park Chan‐Jeoung , Park Borae G. , Bae Mi‐Hyun , Kim Bo‐Hyun , Cho Young‐Uk , Jang Seongsoo , Park Ae‐Ja , Kim Dae‐Young , Lee Jung‐Hee , Lee Je‐Hwan , Lee Kyoo‐Hyung 
Published: January 2017

BackgroundWe prospectively evaluated prognostic value of lymphocyte subpopulations in peripheral blood of allogeneic hematopoietic stem cell transplant (HSCT) recipients.Methods113 allogeneic HSCT (47 sibling matched, 37 unrelated matched, 29 haploidentical)‐performed patients diagnosed as AML (n = 66), ALL (n = 28), and MDS (n = 19) were prospectively enrolled. 14 lymphocyte subpopulations were quantified by flow cytometry of PB at specific time‐points after HSCT, and their prognostic impacts were analyzed.ResultsAt 1, 2, and 3 months post‐HSCT, significant adverse impact on overall survival (OS) and/or event free survival (EFS) was exhibited by low levels of natural killer (NK) cells (≤32 and ≤90/µL at 1 and 2 months on OS and EFS); regulatory T cells (≤1/µL) on EFS at 2 months; and B cells (≤19 and ≤92/µL for OS and EFS at 3 months). At 12 months, low levels of T cells (≤1180/µL), helper/inducer (H/I) T cells (≤250/µL), cytotoxic/suppressor (C/S) T cells (≤541/µL), and NK cells (≤138/µL) were associated with significantly higher risk of relapse. Low levels of T cells (≤879/µL) and C/S T cells (≤541/µL), and high level of naïve thymic T cells (>115/µL) showed a significant association with poor OS; low levels of C/S T cells (≤541/µL) and NK cells (≤138/µL) showed a significant adverse impact on EFS.ConclusionsLow levels of NK cells, regulatory T cells, and B cells at early stage post‐HSCT are adverse prognostic indicators. At late stage, low levels of T cells and their subpopulations, NK cells, and high level of naïve thymic T cells are adverse prognostic indicators. © 2017 International Clinical Cytometry Society
Flow cytometric osmotic fragility test: Increased assay sensitivity for clinical application in pediatric hematology
Authors: Ciepiela Olga , Adamowicz‐Salach Anna , Zgodzińska Agata , Łazowska Magdalena , Kotuła Iwona 
Published: January 2017

BackgroundOsmotic fragility test (OFT) is widely considered as a sensitive indicator of red blood cells' sensitivity to the hypotonic solution. It is often used as a screening test for the diagnosis of hereditary spherocytosis (HS). Nowadays, the osmotic fragility test based on flow cytometric analysis (FCM OF) is widely used in laboratory practice. The purpose of this study was to optimize the assay sensitivity and to validate its clinical application in the diagnostic screening of childhood anemias.MethodsThe study was conducted on 175 children suffering from various types of anemia (including 30 children with proven hereditary spherocytosis, HS) and 16 healthy subjects. All children were aged between 3 months and 17 years, including 94 boys and 97 girls. FCM OF was performed on every subject according to two different analysis time patterns (hemolysis was analyzed for 214 or 300 s) using Cytomics FC500 flow cytometer.ResultsSignificant higher sensitivity was demonstrated by the tests carried out according to the longer analysis time pattern (90.0 vs. 83.33%). The level of specificity of both the analysis patterns was similar. When an extended analysis time was used, the percentage of red cell survival levels in HS patients were significantly lowered compared to the same cases analyzed with shorter incubation times and all other non‐HS anemic cases (9.31 ± 4.69 vs. 35.59 ± 15.30%, P < 0.05). During the shorter analysis time, the values obtained were 13.76 ± 7.92% for HS and 48.18 ± 19.04% for non‐HS, P < 0.0001. The 300‐s test is very useful in distinguishing thalassemia patients from patients with other types of anemias (94.74% sensitivity and 90.12% specificity) and provided the values of remaining red blood cells as 70.46 ± 12.29% for thalassemia and 27.16 ± 13.01% for nonthalassemia subjects, P < 0.0001.ConclusionFlow cytometric osmotic fragility test with a longer (300‐s) analysis time demonstrated an increased sensitivity in detecting HS in anemic children. © 2017 International Clinical Cytometry Society
On efficient downlink channel aggregation in adaptive wireless push systems
Authors: Nicopolitidis Petros 
Published: January 2017

SummaryThis short paper proposes a method for performance increase of adaptive wireless push systems in environments where a large number of channels are available for broadcasting. Such environments have appeared with the advent of the latest generation of cellular networks, e.g., with the multitude of downlink subcarriers in Long‐Term Evolution. The proposed method is shown to increase the performance of wireless push systems.
Analytical characterization and pharmacological evaluation of the new psychoactive substance 4‐fluoromethylphenidate (4F‐MPH) and differentiation between the (±)‐threo and (±)‐erythro diastereomers
Authors: McLaughlin Gavin , Morris Noreen , Kavanagh Pierce V. , Power John D. , Dowling Geraldine , Twamley Brendan , O'Brien John , Hessman Gary , Murphy Brian , Walther Donna , Partilla John S. , Baumann Michael H. , Brandt Simon D. 
Published: January 2017

Misuse of (±)‐threo‐methylphenidate (methyl‐2‐phenyl‐2‐(piperidin‐2‐yl)acetate; Ritalin®; MPH) has long been acknowledged, but the appearance of MPH analogs in the form of ‘research chemicals’ has only emerged in more recent years. 4‐Fluoromethylphenidate (4F‐MPH) is one of these recent examples. This study presents the identification and analytical characterization of two powdered 4F‐MPH products that were obtained from an online vendor in 2015. Interestingly, the products appeared to have originated from two distinct batches given that one product consisted of (±)‐threo‐4F‐MPH isomers whereas the second sample consisted of a mixture of (±)‐threo and (±)‐erythro 4F‐MPH. Monoamine transporter studies using rat brain synaptosomes revealed that the biological activity of the 4F‐MPH mixture resided with the (±)‐threo and not the (±)‐erythro isomers based on higher potencies determined for blockage of dopamine uptake (IC50 4F‐MPHmixture = 66 nM vs. IC50 (±)‐threo = 61 nM vs. IC50 (±)‐erythro = 8,528 nM) and norepinephrine uptake (IC50 4F‐MPHmixture = 45 nM vs. (±)‐threo = 31 nM vs. IC50 (±)‐erythro = 3,779 nM). In comparison, MPH was three times less potent than (±)‐threo‐4F‐MPH at the dopamine transporter (IC50 = 131 nM) and around 2.5 times less potent at the norepinephrine transporter (IC50 = 83 nM). Both substances were catecholamine selective with IC50 values of 8,805 nM and >10,000 nM for (±)‐threo‐4F‐MPH and MPH at the serotonin transporter. These findings suggest that the psychostimulant properties of (±)‐threo‐4F‐MPH might be more potent in humans than MPH. Copyright © 2017 John Wiley & Sons, Ltd.
Addressing critical gaps in the treatment of eating disorders
Authors: Kazdin Alan E. , Fitzsimmons‐Craft Ellen E. , Wilfley Denise E. 
Published: January 2017

AbstractRemarkable progress has been made in developing psychosocial interventions for eating disorders and other mental disorders. Two priorities in providing treatment consist of addressing the research‐practice gap and the treatment gap. The research‐practice gap pertains to the dissemination of evidence‐based treatments from controlled settings to routine clinical care. Closing the gap between what is known about effective treatment and what is actually provided to patients who receive care is crucial in improving mental health care, particularly for conditions such as eating disorders. The treatment gap pertains to extending treatments in ways that will reach the large number of people in need of clinical care who currently receive nothing. Currently, in the United States (and worldwide), the vast majority of individuals in need of mental health services for eating disorders and other mental health problems do not receive treatment. This article discusses the approaches required to better ensure: (1) that more people who are receiving treatment obtain high‐quality, evidence‐based care, using such strategies as train‐the‐trainer, web‐centered training, best‐buy interventions, electronic support tools, higher‐level support and policy; and (2) that a higher proportion of those who are currently underserved receive treatment, using such strategies as task shifting and disruptive innovations, including treatment delivery via telemedicine, the Internet, and mobile apps.
Renal tubular resistance is the primary driver for loop diuretic resistance in acute heart failure
Authors: ter Maaten Jozine M. , Rao Veena S. , Hanberg Jennifer S. , Perry Wilson F. , Bellumkonda Lavanya , Assefa Mahlet , Sam Broughton J. , D'Ambrosi Julie , Wilson Tang W.H. , Damman Kevin , Voors Adriaan A. , Ellison David H. , Testani Jeffrey M. 
Published: January 2017

AbstractBackgroundLoop diuretic resistance is a common barrier to effective decongestion in acute heart failure (AHF), and is associated with poor outcome. Specific mechanisms underlying diuretic resistance are currently unknown in contemporary AHF patients. We therefore aimed to determine the relative importance of defects in diuretic delivery vs. renal tubular response in determining diuretic response (DR) in AHF.Methods and resultsFifty AHF patients treated with intravenous bumetanide underwent a 6‐h timed urine collection for sodium and bumetanide clearance. Whole‐kidney DR was defined as sodium excreted per doubling of administered loop diuretic and represents the sum of defects in drug delivery and renal tubular response. Tubular DR, defined as sodium excreted per doubling of renally cleared (urinary) loop diuretic, captures resistance specifically in the renal tubule. Median administered bumetanide dose was 3.0 (2.0–4.0) mg with 52 (33–77)% of the drug excreted into the urine. Significant between‐patient variability was present as the administered dose only explained 39% of variability in the quantity of bumetanide in urine. Cumulatively, factors related to drug delivery such as renal bumetanide clearance, administered dose, and urea clearance explained 28% of the variance in whole‐kidney DR. However, resistance at the level of the renal tubule (tubular DR) explained 71% of the variability in whole‐kidney DR.ConclusionDefects at the level of the renal tubule are substantially more important than reduced diuretic delivery in determining diuretic resistance in patients with AHF.
Technical Potential of Buildings in Germany as Flexible Power‐to‐Heat Storage for Smart‐Grid Operation
Authors: Kohlhepp Peter , Hagenmeyer Veit 
Published: January 2017

AbstractStorage is a key concept to cope with a growing supply of volatile renewable energy. Compared with genuine grid storage (power↔X), domestic heating and cooling, operated as flexible loads (power to heat), promises to lower infrastructure costs and offers potential for a short‐term demand response. Before designing new service markets, the true technical potential must be assessed. Herein, storage capacity is estimated by exploiting the entire thermally usable building mass as back‐end storage. Balancing power is determined from the steady‐state coincidence factor of buildings seen as thermostatically controlled load (TCL) populations. Results are reported for the residential and tertiary sectors in Germany by considering six classes of heating and cooling equipment. One advantage of the method is simplicity, which results in closed‐form estimates derived top‐down from nationwide and publicly available data on the building stock.
CO2 Hydrate Formation Promoted by a Natural Amino Acid l‐Methionine for Possible Application to CO2 Capture and Storage
Authors: Cai Yuanhao , Chen Yulong , Li Qijie , Li Liang , Huang Haoxin , Wang Suying , Wang Weixing 
Published: January 2017

AbstractWe demonstrate that l‐methionine, a natural amino acid, can be used to dramatically enhance CO2 uptake kinetics in the formation of CO2 hydrate without the use of energy‐intensive mixing technologies or environmentally harmful chemicals. To the best of our knowledge, l‐methionine is the most effective promoter to enhance CO2 hydrate formation (at a concentration of 0.2 wt %, the gravimetric capacity reached up to 356 mg g−1 in 1000 min, and t90 (the time to achieve 90 % of this capacity) was only 15 min). We also present a tentative explanation for the promotion mechanism of l‐methionine in the formation of CO2 hydrate from the point of view of structure–property relationship that will help search for more effective promoters. Our results may offer the possibility of practical application of hydrate‐based CO2 capture and storage technology.