bluuebunny/crossref_metadata_2025_split huggingface dataset:
The massive formation of hybrid shish‐kebab structures in HDPE/PA6 microfibril blend subjected to melt second flow
Authors: Xie Dan‐Dan , Xia Xiao‐Chao , Huang Yan‐Hao , Chen Rui , Xie Bang‐Hu , Yang Ming‐Bo 
Published: May 2017

ABSTRACTDuring the melt second flow process, the synergetic effect of intense shear and polyamide 6 (PA6) microfibrils finally results in the massive formation of highly oriented crystalline structures in the entire thickness of high‐density polyethylene (HDPE)/PA6 microfibril blend. Interestingly, not only does the small microfibril induce HDPE crystallization to form typical hybrid shish–kebab structure, but the large microfibril (about 2 μm in diameter) also induces the formation of local hybrid shish–kebab structure. For the small PA6 microfibril, the oriented HDPE chains caused by the intense shear are absorbed on the whole surface of the microfibril and then a complete polymer underlayer is formed. Subsequently, the crystal nuclei appear on the underlayer, and then the other oriented HDPE chains overgrow from the nuclei in the form of folded chains and grow perpendicular to the microfibril. Finally, the typical hybrid shish–kebab structure is formed. While for the large PA6 microfibril, a few HDPE chains can be still absorbed on the microfibril surface due to the high surface energy of PA6. However, the driving force is insufficient to absorb largely oriented HDPE chains to form complete hybrid shish but only local adsorption layer, so the local hybrid structure is formed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45274.
Photoluminescent properties of novel design heteroleptic Zn(II) complexes
Authors: Vamja Atul C. , Surati Kiran R. 
Published: May 2017

AbstractThree novel heteroleptic Zn(II) complexes containing 8‐hydroxy quinoline and various pyrazolone‐based derivatives were synthesized and their structures confirmed by 1H–nuclear magnetic resonance, mass spectrometry, Fourier transform infra‐red spectroscopy, UV–vis analysis and element analysis. All three complexes showed good photoluminescence properties in the solid state and in solution in the maximum emission range from 475 to 490 nm with a quantum yield of 0.45 to 0.51. Absorption spectra revealed that the complexes possessed a maximum absorption range of 272–281 nm with a band gap of 2.59–2.68 eV. The highest occupied molecular orbital and lowest unoccupied molecular orbital of all the complexes were determine by cyclic voltammetry. All complexes displayed high thermal stability. These characteristics were assessed to find suitability for an alternative cheap light emitter for organic light‐emitting diodes.
Tuneable luminescence properties of EDTA‐assisted ZnS:Mn nanocrystals from a yellow‐orange to a red emission band
Authors: Viswanath R. , Bhojya Naik H. S. , Arun Kumar G. , Suresh Gowda I. K. , Yallappa S. 
Published: May 2017

AbstractLuminescence technology has been improved with the help of semiconductor nanoparticles that possess novel optical and electrical properties compared with their bulk counterpart. The aim of this study was to design semiconductor nanocrystals in their pure (ZnS) or doped form (ZnS:Mn) with different concentrations of Mn2+ ions by a wet chemical route stabilized by ethylenediamine tetra‐acetic acid (EDTA) and to evaluate their luminescence properties. The nanocrystals were characterized by physicochemical techniques such as X‐ray diffraction (XRD), High‐resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SEAD), EDS, and ultraviolet (UV)–visible light and photoluminescence (PL) studies. These results showed the presence of cubic phase and spherically shaped nanocrystals. A blue shift with respect to their bulk counterpart was observed. PL emission spectra were observed with a fixed blue peak and the yellow‐orange bands were red shifted towards the red region under the same excitation wavelength. The orange‐red bands were attributed to the radiation transition of electrons in 3d5 unfilled shells of Mn2+ ions [4T1(4G)‐6A1(6S)]; the ZnS matrix varied with Mn2+ concentration. Shift and increase in the intensity of the PL and absorption bands were observed with increase in Mn content. The study showed that Mn2+‐doped ZnS nanocrystal emission bands can be tuned from the yellow‐orange to the red regions under a controlled synthesis process and could be used as promising luminescent emitters in the biology field upon functionalization with suitable materials. Further studies on construction with various other materials will be useful for practical applications.
Novel enantioselective fluorescent sensors for tartrate anion based on acridinezswsxa
Authors: Wang Chaoyu , Wang Peng , Liu Xiaoyan , Fu Jiaxin , Xue Kun , Xu Kuoxi 
Published: May 2017

AbstractNovel chiral fluorescence sensors L‐1 and D‐1 incorporating N‐Boc‐protected alanine and acridine moieties were synthesized. The recognition ability of the sensors was studied by fluorescence titration, 1H NMR spectroscopy and density functional theory (DFT) calculations. The sensors exhibited good enantioselective fluorescent sensing ability toward enantiomers of tartrate anion for the selected carboxylate anions and formed 1: 1 complexes by multiple hydrogen bonding interactions.
Universal label‐free in‐process quantification of influenza virus‐like particles
Authors: Carvalho Sofia B. , Moleirinho Mafalda G. , Wheatley David , Welsh John , Gantier René , Alves Paula M. , Peixoto Cristina , Carrondo Manuel J. T. 
Published: May 2017

AbstractVirus‐like particles (VLPs) are becoming established as vaccines, in particular for influenza pandemics, increasing the interest in the development of VLPs manufacturing bioprocess. However, for complex VLPs, the analytical tools used for quantification are not yet able to keep up with the bioprocess progress. Currently, quantification for Influenza relies on traditional methods: hemagglutination assay or Single Radial Immunodiffusion. These analytical technologies are time‐consuming, cumbersome, and not supportive of efficient downstream process development and monitoring. Hereby we report a label‐free tool that uses Biolayer interferometry (BLI) technology applied on an Octet platform to quantify Influenza VLPs at all stages of bioprocess. Human (α2,6‐linked sialic acid) and avian (α2,3‐linked sialic acid) biotinylated receptors associated with streptavidin biosensors were used, to quantify hemagglutinin content in several mono‐ and multivalent Influenza VLPs. The applied method was able to quantify hemagglutinin from crude samples up to final bioprocessing VLP product. BLI technology confirmed its value as a high throughput analytical tool with high sensitivity and improved detection limits compared to traditional methods. This simple and fast method allowed for real‐time results, which are crucial for in‐line monitoring of downstream processing, improving process development, control and optimization.
Electrogenerated Chemiluminescence of Semiconductor Nanoparticles and Their Applications in Biosensors
Authors: Benoit Lora , Choi Jai‐Pil 
Published: May 2017

AbstractCompared to fluorescence, electrogenerated chemiluminescence (ECL) can be a superior analytical tool in terms of sensitivity and signal‐to‐noise ratios, owing to the absence of background emissions from unwanted photoexcitation. Semiconductor nanoparticles (NPs) are highly promising in many analytical applications, because they can produce stable ECL and possess surface‐dependent, tunable ECL properties. This Minireview gives a brief overview of ECL energetics and processes, the current progress of ECL of semiconductor NPs, and recent advances in biological sensing based on ECL of semiconductor NPs. The current challenges and perspectives on ECL of semiconductor NPs and their biological sensing applications are also discussed.
Role of Halide Ions in the Nature of the Magnetic Anisotropy in Tetrahedral CoII Complexes
Authors: Vaidya Shefali , Singh Saurabh Kumar , Shukla Pragya , Ansari Kamaluddin , Rajaraman Gopalan , Shanmugam Maheswaran 
Published: May 2017

AbstractA series of mononuclear tetrahedral CoII complexes with a general molecular formula [CoL2X2] [L=thiourea and X=Cl (1), Br (2) and I (3)] were synthesized and their structures were characterized by single‐crystal X‐ray diffraction. Direct‐current (dc) magnetic susceptibility [χMT(T) and M(H)] and its slow relaxation of magnetization were measured for all three complexes. The experimental dc magnetic data are excellently reproduced by fitting both χMT(T) and M(H) simultaneously with the parameters D=+10.8 cm−1, g1=2.2, g2=2.2, and g3=2.4 for 1; D=−18.7 cm−1, giso=2.21 for 2; and D=−19.3 cm−1, giso=2.3 for 3. The replacement of chloride in 1 by bromide or iodide (in 2 and 3, respectively) was accompanied by a change in both sign and magnitude of the magnetic anisotropy D. Field‐induced out‐of‐phase susceptibility signals observed in 10 % diluted samples of 1–3 imply slow relaxation of magnetization of molecular origin. To better understand the magnetization relaxation dynamics of complexes 1–3, detailed ab initio CASSCF/NEVPT2 calculations were performed. The computed spin Hamiltonian parameters are in good agreement with experimental data. In particular, the calculations unveil the role of halide ions in switching the sign of D on moving from Cl− to I−. The large spin–orbit coupling constant associated with the heavier halide ion and weaker π donation reduces the ground state–excited state gap, which leads to a larger contribution to negative D for complex 3 compared to complex 1. Further magnetostructural D correlations were developed to understand the role of structural distortion in the sign and magnitude of D values in this family of complexes.
Fluorinated Porous Conjugated Polyporphyrins through Direct C−H Arylation Polycondensation: Preparation, Porosity, and Use as Heterogeneous Catalysts for Baeyer–Villiger Oxidation
Authors: Cao Qiang , Yin Qing , Chen Qi , Dong Zhi‐Bing , Han Bao‐Hang 
Published: May 2017

AbstractBy considering the high reactivity of fluorinated iron–porphyrin and good stability of porphyrin‐based porous polymers, fluorinated iron–porphyrin conjugated porous polymers (FPOP‐3–6) were synthesized through direct C−H arylation polymerization. The obtained materials are chemically and thermally stable, of which FPOP‐3 exhibits the highest Brunauer–Emmett–Teller specific surface area (about 840 m2 g−1). For functional studies of the obtained polymers as heterogeneous catalysts, catalytic transformation of cycloketones into lactones by oxygen through Baeyer–Villiger oxidation was used as a model reaction. Fluorinated phenyl substituents of the iron–porphyrin not only are beneficial to the conversion, but also can stabilize the porphyrin to resist catalyst breakdown. The polymer FPOP‐3, with high porosity, exhibits the best catalytic efficiency and recycling effect. The recovered catalyst also shows good catalytic activities after recycling three times with a small loss in yield.
Nitramino‐ and Dinitromethyl‐Substituted 1,2,4‐Triazole Derivatives as High‐Performance Energetic Materials
Authors: Tang Yongxing , Dharavath Srinivas , Imler Gregory H. , Parrish Damon A. , Shreeve Jean'ne M. 
Published: May 2017

AbstractSince highly nitrated nitrogen‐rich heterocycles are important motifs in high energy density materials, extensive studies for the development of such novel molecules have been underway. A highly energetic moiety, 3‐dinitromethyl‐5‐nitramino‐1,2,4‐triazole, which consists of a triazole ring, and nitramino and dinitromethyl groups, has been designed and synthesized. By pairing with nitrogen‐rich cations, several ionic derivatives were obtained. Theoretical and experimental studies show that the hydroxylammonium salt (7) is highly dense, and has excellent detonation performance with acceptable thermal stablity and sensitivities, which are superior to those of RDX.
Competition versus Cooperation in Catalytic Hydrogelators for anti‐Selective Mannich Reaction
Authors: Singh Nishant , Escuder Beatriu 
Published: May 2017

AbstractChemical systems find similarities in different sociological and biological processes, in which the entities compete or cooperate for a favorable outcome. The structural and functional adaptations leading to emergent properties, especially in catalysis, are based on factors such as abundance of substrates, stability of the transition state, and structural/functional attributes of catalysts. Proline and acid groups appended to catalytic fibers of two self‐sorting hydrogelators compete for the Mannich reaction between aniline, benzaldehyde, and cyclohexanone to give low overall selectivity (anti/syn 77:23). In a sol–gel system of the same molecules, on the other hand, the soluble acid appended molecules tend to cooperate with the fibers of proline‐appended catalyst to give improved selectivity (anti/syn 95:5). The available options for the catalytic molecules are to carry out the reaction independently or in cooperation. However, these options are chosen based on the efficiency, selectivity, and mobility of catalysts as a result of their abilities to self‐assemble.
Unraveling the Coulombic Forces in Electronically Decoupled Bichromophoric Systems during Two Successive Electron Transfers
Authors: Ivanov Maxim V. , Wadumethrige Shriya H. , Wang Denan , Rathore Rajendra 
Published: May 2017

AbstractCoulombic forces are vital in modulating the electron transfer dynamics in both synthetic and biological polychromophoric assemblies, yet quantitative studies of the impact of such forces are rare, as it is difficult to disentangle electrostatic forces from simple electronic coupling. To address this problem, the impact of Coulombic interactions in the successive removal of two electrons from a model set of spirobifluorenes, where the interchromophoric electronic coupling is nonexistent, is quantitatively assessed. By systematically varying the separation of the bifluorene moieties using model compounds, ion pairing, and solvation, these interactions, with energies up to about 0.4 V, are absent at distances greater than about 9 Å. These findings can be (quantitatively) applied for the design of polychromophoric assemblies, whereby the redox properties of donors and/or acceptors can be tuned by judicious positioning of the charged groups to control the electron‐transfer dynamics.
Development of helical coil based fluidic diode pump for liquid pumping
Authors: Manavalan Balamurugan , Pandey Niranjan K. , Kumar Shekhar , Mudali Kamachi U. , Joshi Jyeshtharaj B. 
Published: May 2017

The main selection criterion for pumps in reprocessing applications is the absence of any moving parts or the moving parts not having any direct contact with the process fluid. There are different types of fluidic pumps such as vortex diode, reverse flow diode, etc. In this work, a new design of helical coil fluidic pump has been developed and demonstrated. Helical coils are widely used in process industries as heat exchangers, reactors, motionless mixers, etc. It is for the first time that the authors are proposing the use of helical coil as a fluidic pump based on its inherent property of high pressure drop as compared to a straight tube.The main objective of this work is to develop an alternate pumping system for reprocessing applications to replace the conventional air lift pump. The helical coil based fluidic diode pump was made up of SS 304 seamless pipe (pipe inner diameter is 9.5 mm) with a 36 mm diameter of helical coil and pitch of 14 mm. In this work, friction factor for the given helical coil was measured from pressure drop experiments. This information was also useful for understanding the transition of the laminar to turbulent region. In order to propose the operating region, the pumping capacity was measured for the helical coil based fluidic pump at different operating conditions. Experimental results show that the proposed hardware is able to pump up to 54 dm3/h. Recommendations have been made for proposing an optimum design.
Heart rate and outcome in heart failure with reduced ejection fraction: Differences between atrial fibrillation and sinus rhythm—A CIBIS II analysis
Authors: Mulder Bart A. , Damman Kevin , Van Veldhuisen Dirk J. , Van Gelder Isabelle C. , Rienstra Michiel 
Published: May 2017

BackgroundHeart rate has been associated with prognosis in patients with heart failure with reduced ejection fraction (HFREF) and sinus rhythm; whether this also holds true in patients with atrial fibrillation (AF) is unknown.HypothesisTo evaluate cardiac rhythm and baseline heart rate and the influence of outcome in patients with HFREF enrolled in the Cardiac Insufficiency Bisoprolol Study II.MethodsIn total, 2539 patients were stratified according to their baseline heart rhythm (AF or sinus rhythm) and into quartiles of heart rate (≤70 bpm, 71–78 bpm, 79–90 bpm, and >90 bpm). The primary outcome was all‐cause mortality. Mean follow‐up was 1.3 years.ResultsMean age was 61 years, mean left ventricular ejection fraction was 28%, and 80% were male. A total of 521 (21%) patients had AF at baseline. The risk associated with all‐cause mortality for each 5 bpm increase in heart rate in patients with sinus rhythm (hazard ratio [HR]: 1.06, 95% confidence interval [CI]: 1.01‐1.11, P = 0.012) was significantly different from those with AF (HR: 1.00, 95% CI: 0.94‐1.07, P = 0.90, P for interaction = 0.041). The risk associated with higher heart rate in sinus rhythm was primarily attributable to excess risk in the highest quartile (HR: 1.64, 95% CI: 1.18–2.30, P = 0.003). Allocation to bisoprolol did not modify the interaction between heart rate, rhythm and outcome.ConclusionsIn HFREF patients with AF, a higher heart rate is not associated with increased event rates in contrast to HFREF patients with sinus rhythm.
Adjuvant radiotherapy improves overall survival in patients with resected gastric adenocarcinoma: A National Cancer Data Base analysis
Authors: Stumpf Priscilla K. , Amini Arya , Jones Bernard L. , Koshy Matthew , Sher David J. , Lieu Christopher H. , Schefter Tracey E. , Goodman Karyn A. , Rusthoven Chad G. 
Published: May 2017

BACKGROUNDFor patients with resectable gastric adenocarcinoma, perioperative chemotherapy and adjuvant chemoradiotherapy (CRT) are considered standard options. In the current study, the authors used the National Cancer Data Base to compare overall survival (OS) between these regimens.METHODSPatients who underwent gastrectomy for nonmetastatic gastric adenocarcinoma from 2004 through 2012 were divided into those treated with perioperative chemotherapy without RT versus those treated with adjuvant CRT. Survival was estimated and compared using univariate and multivariate models adjusted for patient and tumor characteristics, surgical margin status, and the number of lymph nodes examined. Subset analyses were performed for factors chosen a priori, and potential interactions between treatment and covariates were assessed.RESULTSA total of 3656 eligible patients were identified, 52% of whom underwent perioperative chemotherapy and 48% of whom received postoperative CRT. The median follow‐up was 47 months, and the median age of the patients was 62 years. Analysis of the entire cohort demonstrated improved OS with adjuvant RT on both univariate (median of 51 months vs 42 months; P = .013) and multivariate (hazard ratio, 0.874; 95% confidence interval, 0.790‐0.967 [P = .009]) analyses. Propensity score‐matched analysis also demonstrated improved OS with adjuvant RT (median of 49 months vs 39 months; P = .033). On subset analysis, a significant interaction was observed between the survival impact of adjuvant RT and surgical margins, with a greater benefit of RT noted among patients with surgical margin‐positive disease (hazard ratio with RT: 0.650 vs 0.952; P for interaction <.001).CONCLUSIONSIn this National Cancer Data Base analysis, the use of adjuvant RT in addition to chemotherapy was associated with a significant OS advantage for patients with resected gastric cancer. The survival advantage observed with adjuvant CRT was most pronounced among patients with positive surgical margins. Cancer 2017;123:3402‐9. © 2017 American Cancer Society.
Association between mutations of critical pathway genes and survival outcomes according to the tumor location in colorectal cancer
Authors: Lee Dae‐Won , Han Sae‐Won , Cha Yongjun , Bae Jeong Mo , Kim Hwang‐Phill , Lyu Jaemyun , Han Hyojun , Kim Hyoki , Jang Hoon , Bang Duhee , Huh Iksoo , Park Taesung , Won Jae‐Kyung , Jeong Seung‐Yong , Park Kyu Joo , Kang Gyeong Hoon , Kim Tae‐You 
Published: May 2017

BACKGROUNDColorectal cancer (CRC) develops through the alteration of several critical pathways. This study was aimed at evaluating the influence of critical pathways on survival outcomes for patients with CRC.METHODSTargeted next‐generation sequencing of 40 genes included in the 5 critical pathways of CRC (WNT, P53, RTK‐RAS, phosphatidylinositol‐4,5‐bisphosphate 3‐kinase [PI3K], and transforming growth factor β [TGF‐β]) was performed for 516 patients with stage III or high‐risk stage II CRC treated with surgery followed by adjuvant fluoropyrimidine and oxaliplatin chemotherapy. The associations between critical pathway mutations and relapse‐free survival (RFS) and overall survival were analyzed. The associations were further analyzed according to the tumor location.RESULTSThe mutation rates for the WNT, P53, RTK‐RAS, PI3K, and TGF‐β pathways were 84.5%, 69.0%, 60.7%, 30.0%, and 28.9%, respectively. A mutation in the PI3K pathway was associated with longer RFS (adjusted hazard ratio [HR], 0.59; 95% confidence interval [CI], 0.36‐0.99), whereas a mutation in the RTK‐RAS pathway was associated with shorter RFS (adjusted HR, 1.60; 95% CI, 1.01‐2.52). Proximal tumors showed a higher mutation rate than distal tumors, and the mutation profile was different according to the tumor location. The mutation rates of Kirsten rat sarcoma viral oncogene homolog (KRAS), phosphatidylinositol‐4,5‐bisphosphate 3‐kinase catalytic subunit α (PIK3CA), and B‐Raf proto‐oncogene serine/threonine kinase (BRAF) were higher in proximal tumors, and the mutation rates of adenomatous polyposis coli (APC), tumor protein 53 (TP53), and neuroblastoma RAS viral oncogene homolog (NRAS) were higher in distal tumors. The better RFS with the PI3K pathway mutation was significant only for proximal tumors, and the worse RFS with the RTK‐RAS pathway mutation was significant only for distal tumors.CONCLUSIONSA PI3K pathway mutation was associated with better RFS for CRC patients treated with adjuvant chemotherapy, and an RTK‐RAS pathway mutation was associated with worse RFS. The significance of the prognostic impact differed according to the tumor location. Cancer 2017;123:3513‐23. © 2017 American Cancer Society.
Self‐Assembly and Local Manipulation of Au‐Pyridyl Coordination Networks on Metal Surfaces
Authors: Song Yang , Wang Yuxu , Jin Qiao , Zhou Kun , Shi Ziliang , Liu Pei‐Nian , Ma Yu‐qiang 
Published: May 2017

AbstractUsing scanning tunnelling microscopy (STM), we demonstrate that Au‐pyridyl coordination can be used to assemble two‐dimensional coordination network structures on metal surfaces. The polymorphism of the coordination network structures can be manipulated at both the micro‐ and nanoscale. Using the same organic ligand, we assembled two distinct polymorphic network structures, which were assisted by threefold Au‐pyridyl coordination on Ag(111) with predeposited Au atoms (α‐network), and by twofold Au‐pyridyl coordination on Au(111) (β‐network), respectively. Specifically on the Au(111) surface, single‐oriented β‐network domains as large as ≈400 nm were selected by thermal annealing. We ascribe this global control strategy to distinct Au bonding modes tuned by molecule–substrate interactions. Using an STM tip, we succeeded in creating α‐network domains (≈10 nm) locally within the homogeneous β‐network domain areas on Au(111) in a controlled manner.