bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rapid Room‐Temperature, Chemoselective C−C Coupling of Poly(pseudo)halogenated Arenes Enabled by Palladium(I) Catalysis in Air
Authors: Kalvet Indrek , Magnin Guillaume , Schoenebeck Franziska 
Published: December 2016

AbstractWhile chemoselectivities in Pd0‐catalyzed coupling reactions are frequently non‐intuitive and a result of a complex interplay of ligand/catalyst, substrate, and reaction conditions, we herein report a general method based on PdI that allows for an a priori predictable chemoselective C
−C
coupling at C−Br in preference to C−OTf and C−Cl bonds, regardless of the electronic or steric bias of the substrate. The C−C bond formations are extremely rapid (<5 min at RT) and are catalyzed by an air‐ and moisture‐stable PdI dimer under open‐flask conditions.
Effect of PEG Architecture on the Hybridization Thermodynamics and Protein Accessibility of PEGylated Oligonucleotides
Authors: Jia Fei , Lu Xueguang , Tan Xuyu , Wang Dali , Cao Xueyan , Zhang Ke 
Published: December 2016

AbstractPEGylation is an attractive approach to modifying oligonucleotides intended for therapeutic purposes. PEG conjugation reduces protein interactions with the oligonucleotide, and helps to overcome their intrinsic biopharmaceutical shortcomings, such as poor enzymatic stability, rapid body clearance, and unwanted immunostimulation. However, the effect of PEG architecture and the manner in which the PEG component interferes with the hybridization of the oligonucleotide remain poorly understood. In this study, we systematically compare the hybridization thermodynamics and protein accessibility of several DNA conjugates involving linear, Y‐shaped, and brush‐type PEG. It is found that PEGylated DNA experiences two opposing effects: local excluded volume effect and chemical interactions, the strengths of which are architecture‐dependent. Notably, the brush architecture is able to offer significantly greater protein shielding capacity than its linear or Y‐shaped counterparts, while maintaining nearly identical free energy for DNA hybridization compared with free DNA.
Transient Helicity: Fuel‐Driven Temporal Control over Conformational Switching in a Supramolecular Polymer
Authors: Dhiman Shikha , Jain Ankit , George Subi J. 
Published: December 2016

AbstractSynthetic manifestations of supramolecular chirality have extensively drawn inspiration from naturally occurring systems. Even though in biological systems conformational changes are dissipative, synthetic systems that change conformation under non‐equilibrium conditions have still not been established. Herein, we attempt to alleviate this scenario by reporting a synthetic supramolecular system that undergoes temporal changes in its helical conformation as an active system at the expense of a biologically relevant chemical fuel, ATP. Use of enzymes working in tandem provides transient and switchable helices with modular lifetime and stereomutation rates.
Irresponsible vendors: Non‐native, invasive and threatened animals offered for garden pond stocking
Authors: Patoka Jiří , Bláha Martin , Kalous Lukáš , Kouba Antonín 
Published: December 2016

Abstract

The pet trade has been responsible for many introductions of non‐native species. Freshwater ornamental plants and animals originating from the pet trade are stocked to garden ponds. The present survey focused on awareness and responsible behaviour related to biological invasion risks of companies that designed, built, and stocked garden ponds.
A representative number (n = 124) of companies (commercial garden pond architects and builders) in the Czech Republic were surveyed regarding the offer of non‐native, invasive and threatened native species. The survey was conducted over the entire warm period (from 1 May 2015 to 31 September 2015) while using personal visits, correspondence and interviews to list the species on offer.
‘Traditional’ ornamental species were offered by 39.1% of surveyed vendors, non‐traditional ‘marginal’ species by 5.6%, common native species by 6.5% and threatened native species by 2.4%.
The findings of this study support the hypothesis that ‘garden pond’ vendors offer non‐native species with a risk of biological invasion; moreover, threatened native animals were also on sale. It is probable that a similar situation exists in other countries. It is important for the conservation of native aquatic biota to raise awareness of the need to reduce risk through responsible behaviour of those involved in the pet trade. It is also essential to prohibit stocking of potential invaders and to enforce the illegal capture and sale of native species.
Silyl‐ and Disilanyl‐BODIPYs: Synthesis via Catalytic Dehalosilylation and Spectroscopic Properties
Authors: Wang Sisi , Lu Hua , Wu Yanping , Xiao Xuqiong , Li Zhifang , Kira Mitsuo , Shen Zhen 
Published: December 2016

AbstractWe describe herein the first synthesis of silyl‐ and disilanyl‐BODIPYs through transition‐metal‐catalyzed dehalosilylation of iodo‐BODIPYs using a Pd(P(tBu)3)2/Et3N/toluene system. Various mono‐ and bis‐silyl‐BODIPYs, mono‐ and bis‐disilanyl‐BODIPYs and bis‐BODIPYs linked by silylene and SiOSi groups were synthesized by using this straightforward method. Silyl‐ and disilanyl‐substitution significantly modifies the spectroscopic properties of the BODIPY, in which the fluorescence quantum yields of the silyl‐BODIPYs are remarkably increased, whereas the emission spectra of disilanyl‐BODIPYs are red‐shifted due to effective σ(SiSi)–π(BODIPY) conjugation.
Modal Kalman Filter
Authors: Mohammaddadi Gh. , Pariz N. , Karimpour A. 
Published: December 2016

AbstractIn the Extended Kalman Filter (EKF), only the first‐order term of the Taylor series is employed. Hence, the nonlinearities in the system dynamics are not fully considered. In the proposed method, to overcome this drawback, the higher‐order terms of the Taylor series are considered and a new filter, based on the Modal series, is designed. In this paper, based on the Modal series and careful approximations, a nonlinear filter is converted to a series of linear filters, and the extracted filter is named the Modal Kalman Filter (MKF). The efficiency and advantage of MKF are analytically proven and its applicability examined with some simulations.
Prioritizing pharmacokinetic drug interaction precipitants in natural products: application to OATP inhibitors in grapefruit juice
Authors: Johnson Emily J. , Won Christina S. , Köck Kathleen , Paine Mary F. 
Published: December 2016

AbstractNatural products, including botanical dietary supplements and exotic drinks, represent an ever‐increasing share of the health‐care market. The parallel ever‐increasing popularity of self‐medicating with natural products increases the likelihood of co‐consumption with conventional drugs, raising concerns for unwanted natural product–drug interactions. Assessing the drug interaction liability of natural products is challenging due to the complex and variable chemical composition inherent to these products, necessitating a streamlined preclinical testing approach to prioritize precipitant individual constituents for further investigation. Such an approach was evaluated in the current work to prioritize constituents in the model natural product, grapefruit juice, as inhibitors of intestinal organic anion‐transporting peptide (OATP)‐mediated uptake. Using OATP2B1‐expressing MDCKII cells (Madin‐Darby canine kidney type II) and the probe substrate estrone 3‐sulfate, IC50s were determined for constituents representative of the flavanone (naringin, naringenin, hesperidin), furanocoumarin (bergamottin, 6′,7′‐dihydroxybergamottin) and polymethoxyflavone (nobiletin and tangeretin) classes contained in grapefruit juice. Nobiletin was the most potent (IC50, 3.7 μm); 6′,7′‐dihydroxybergamottin, naringin, naringenin and tangeretin were moderately potent (IC50, 20–50 μm); and bergamottin and hesperidin were the least potent (IC50, >300 μm) OATP2B1 inhibitors. Intestinal absorption simulations based on physiochemical properties were used to determine the ratios of unbound concentration to IC50 for each constituent within enterocytes and to prioritize in order of pre‐defined cut‐off values. This streamlined approach could be applied to other natural products that contain multiple precipitants of natural product–drug interactions. Copyright © 2016 John Wiley & Sons, Ltd.
Design, synthesis, and biological evaluation of cyclic peptidotriazoles derived from BPC194 as novel agents for plant protection
Authors: Güell Imma , Vilà Sílvia , Badosa Esther , Montesinos Emilio , Feliu Lidia , Planas Marta 
Published: December 2016

AbstractThe search for novel antimicrobial agents to be used for plant protection has prompted us to design analogues incorporating non‐natural amino acids. Herein, we designed and synthesized cyclic peptidotriazoles derived from the lead antimicrobial cyclic peptide c(Lys‐Lys‐Leu3‐Lys‐Lys5‐Phe‐Lys‐Lys‐Leu‐Gln) (BPC194). In particular, Leu3 and Lys5 were replaced by a triazolyl alanine, a triazolyl norleucine or a triazolyl lysine. These peptides were screened for their antibacterial activity against Xanthomonas axonopodis pv. vesicatoria, Erwinia amylovora, and Pseudomonas syringae pv. syringae, for their hemolysis and for their phytotoxicity. Results showed that the type of triazolyl amino acid and the substituent present at the triazole influenced the antibacterial and hemolytic activities. Moreover, the position of this residue was also crucial for the hemolysis. The lead compounds BPC548 and BPC550 exhibited high antibacterial activity (MIC of 3.1 to 25 μM), low hemolysis (19 and 26% at 375 μM, respectively) and low phytotoxicity. Therefore, these analogues could be used as new leads for the development of effective agents to control pathogenic bacteria responsible for plant diseases of economic importance.
MicroRNA‐210 is increased and it is required for dedifferentiation of osteosarcoma cell line
Authors: Zhang Haixia , Mai Qing , Chen Juntao 
Published: December 2016

AbstractOsteosarcoma (OS) is the most common malignant bone tumor and is prevalent in adolescents. In clinical studies, miR‐210 has been reported to be tightly correlated to the poor prognosis of OS. Nevertheless, its roles in OS have not been fully elucidated. In view of the central role played by OS stem cells (OSCs) in the malignant progression of OS, this study investigated the influence of miR‐210 on the formation of OSCs. Our previous findings suggested that the microenvironment of bone, abundant TGF‐β1 and hypoxia, could induce OS cells to dedifferentiate into OSCs. In this study, we found that miR‐210 participated in the dedifferentiation of OS cells into OSCs, and inhibiting it significantly suppressed the formation of OSCs. Further results suggested that miR‐210 promoted the expression of TGF‐β1 and its downstream effectors Snail1 and Slug which were highly elevated in the process of OS dedifferentiation. Additionally, the target gene of miR‐210 was also investigated. It was found that NFIC was significantly reduced by miR‐210 treatment and also during OS dedifferentiation. Therefore, this study suggested that miR‐210 promoted OS cells dedifferentiation and uncovered its role in the malignant progress of OS.
Function Calculation: A Simple Way to Predict the Geometry Parameters of Self‐Organized Titania Nanotube Arrays
Authors: Chen Yan‐Xin , Jacob Timo 
Published: December 2016

AbstractTNTAs were grown by anodization of titanium in mixed electrolytes consisting of water, ethylene‐glycol and NH4F. With this electrolyte composition, the obtained nanotube layers show a high level of flexibility towards controllable tube geometries. We carefully investigated the internal relationship between the synthesis parameters and the resulting TNTA morphology, deriving a set of relations to link the preparation parameters with the geometric dimensions of the obtained TNTAs. We show that the nanotube outer diameter not only increases linearly with the applied anodization voltage, but also relates to the water content in the electrolyte, and that both the water content and fluoride content determines the kinetics of the tube growth. Thus, by adjusting the electrolyte composition and optimizing the anodization procedure, a wide range of pre‐defined morphologies can be realized.
Effects of Chlorination on the Tautomeric Equilibrium of 2‐Hydroxypyridine: Experiment and Theory
Authors: Calabrese Camilla , Maris Assimo , Uriarte Iciar , Cocinero Emilio J. , Melandri Sonia 
Published: December 2016

AbstractThe effects of halogenation on the tautomeric and conformational equilibria of the model system 2‐hydroxypyridine/2‐pyridone have been investigated through chlorine substitution at positions 3, 4, 5, and 6. In the gas phase, the lactim syn‐periplanar tautomer (OHs) was the predominant species for all compounds over the lactam form (C=O) and the less abundant anti‐periplanar lactim (OHa). However, the population of the three species was shown to be dependent on the position of the chlorine substitution. Chlorination in position 5 or 6 strongly stabilizes the OHs tautomer, whereas the C=O form has a significant population when the ring is chlorinated in positions 3 or 4. Overall, the OHa form is the least favourable form, although the 3‐substitution favours the population of this tautomer. In addition, the C=O tautomer is strongly stabilized in the solvent, which makes it the dominant form in some substituted species. This study has been performed by means of rotational spectroscopy in the gas phase and/or theoretical calculations in the isolated phase and in solution. Both the OHs and C=O forms of 5‐chloro‐2‐hydroxypyridine and the OHs form of 6‐chloro‐2‐hydroxypyridine were experimentally observed. All transitions displayed a complex nuclear hyperfine structure owing to the presence of the chlorine and nitrogen nuclei. For all species, a full quadrupolar hyperfine analysis has been performed. This has provided crucial information for the unambiguous identification of tautomers.
Nacnac‐Cobalt‐Mediated P4 Transformations
Authors: Spitzer Fabian , Graßl Christian , Balázs Gábor , Mädl Eric , Keilwerth Martin , Zolnhofer Eva M. , Meyer Karsten , Scheer Manfred 
Published: December 2016

AbstractA comparison of P4 activations mediated by low‐valent β‐diketiminato (L) cobalt complexes is presented. The formal Co0 source [K2(L3Co)2(μ2:η1,η1‐N2)] (1) reacts with P4 to form a mixture of the monoanionic complexes [K(thf)6][(L3Co)2(μ2:η4,η4‐P4)] (2) and [K(thf)6][(L3Co)2(μ2:η3,η3‐P3)] (3). The analogue CoI precursor [L3Co(tol)] (4 a), however, selectively yields the corresponding neutral derivative [(L3Co)2(μ2:η4,η4‐P4)] (5 a). Compound 5 a undergoes thermal P atom loss to form the unprecedented complex [(L3Co)2(μ2:η3,η3‐P3)] (6). The products 2 and 3 can be obtained selectively by an one‐electron reduction of their neutral precursors 5 a and 6, respectively. The electrochemical behaviour of 2, 3, 5 a, and 6 is monitored by cyclic voltammetry and their magnetism is examined by SQUID measurements and the Evans method. The initial CoI‐mediated P4 activation is not influenced by applying the structurally different ligands L1 and L2, which is proven by the formation of the isostructural products [(LCo)2(μ2:η4,η4‐P4)] [L=L3 (5 a), L1 (5 b), L2 (5 c)].
Thermodynamically‐based response time as controllability indicator in heat exchanger networks
Authors: de León Carmen , Miranda Camila B. , Andrade Cid M. G. , Ravagnani Mauro A. S. S. 
Published: December 2016

AbstractRecently, research and development has focused on how to integrate process design and process control, considering that the most outstanding process design does not always result in the best dynamic performance, involving plant controllability. A steady‐state controllability and resiliency analysis provides useful information for the assessment of heat exchanger networks (HEN) and requires less work than the dynamic analysis. In the interests of obtaining the best balance between process integration and controllability, a thermodynamic analysis from the dissipative point of view can be a starting point. This paper presents a simultaneous approach for finding controllability and economic goals in early stages of process design. An index based on response time is obtained, which is a controllability measure of the system. It is applied to a HEN and the results obtained are compared with known controllability and resiliency measures tools on steady state, showing consistency. The proposed methodology serves as a starting point for controllability evaluation, making it possible to relate the stages of process control and design.
The Development of Next‐Generation Pyridinium‐Based multiQAC Antiseptics
Authors: Al‐Khalifa Saleh E. , Jennings Megan C. , Wuest William M. , Minbiole Kevin P. C. 
Published: December 2016

AbstractA series of 18 bis‐ and tris‐pyridinium amphiphiles were prepared and tested for both antimicrobial activity and lytic capability, in comparison with the commercially available pyridinium antiseptic cetylpyridinium chloride (CPC). Assessments were made against Gram‐positive and Gram‐negative bacteria, including two methicillin‐resistant Staphylococcus aureus (MRSA) strains. While 2Pyr‐11,11 was identified as one of the most potent antimicrobial quaternary ammonium compounds (QACs) reported to date, boasting nanomolar inhibition against five of six bacteria tested, no significant improvement in bioactivity of tris‐pyridinium amphiphiles over their bis‐pyridinium counterparts was observed. However, the multicationic QACs (multiQACs) presented herein did display significant advantages over the monocationic CPC; while similar red blood cell lysis was observed, superior activity against both Gram‐negative bacteria and resistant S. aureus strains led to the discovery of four pyridinium‐based multiQACs with advantageous therapeutic indices.
Discovery of Macrocyclic Pyrimidines as MerTK‐Specific Inhibitors
Authors: McIver Andrew L. , Zhang Weihe , Liu Qingyang , Jiang Xinpeng , Stashko Michael A. , Nichols James , Miley Michael J. , Norris‐Drouin Jacqueline , Machius Mischa , DeRyckere Deborah , Wood Edgar , Graham Douglas K. , Earp H. Shelton , Kireev Dmitri , Frye Stephen V. , Wang Xiaodong 
Published: December 2016

AbstractMacrocycles have attracted significant attention in drug discovery recently. In fact, a few de novo designed macrocyclic kinase inhibitors are currently in clinical trials with good potency and selectivity for their intended target. In this study, we successfully engaged a structure‐based drug design approach to discover macrocyclic pyrimidines as potent Mer tyrosine kinase (MerTK)‐specific inhibitors. An enzyme‐linked immunosorbent assay (ELISA) in 384‐well format was employed to evaluate the inhibitory activity of macrocycles in a cell‐based assay assessing tyrosine phosphorylation of MerTK. Through structure–activity relationship (SAR) studies, analogue 11 [UNC2541; (S)‐7‐amino‐N‐(4‐fluorobenzyl)‐8‐oxo‐2,9,16‐triaza‐1(2,4)‐pyrimidinacyclohexadecaphane‐1‐carboxamide] was identified as a potent and MerTK‐specific inhibitor that exhibits sub‐micromolar inhibitory activity in the cell‐based ELISA. In addition, an X‐ray structure of MerTK protein in complex with 11 was resolved to show that these macrocycles bind in the MerTK ATP pocket.
Population Pharmacokinetics of Edoxaban in Japanese Atrial Fibrillation Patients With Severe Renal Impairment
Authors: Shimizu Takako , Tachibana Masaya , Kimura Tetsuya , Kumakura Tomohiko , Yoshihara Kazutaka 
Published: December 2016

AbstractThis is a population pharmacokinetic (PopPK) analysis to predict PK of edoxaban, a direct‐acting oral anticoagulant, in nonvalvular atrial fibrillation (NVAF) patients with severe renal impairment (SRI; creatinine clearance [CLcr] <30 mL/min). Data from a phase 3 study recently conducted in Japanese NVAF patients (n = 90), including patients with SRI, were used to update the ENGAGE PopPK model that had been developed based on pooled data from the phase 3 ENGAGE AF‐TIMI 48 study and 13 phase 1 PK studies, which included few patients with SRI. The final model indicated that the ENGAGE PopPK model was applicable to Japanese patients in that the model‐simulated and study‐observed concentration‐time profiles were in agreement. Estimated model parameters after the addition of Japanese SRI data were consistent with those derived from the original ENGAGE PopPK data set. The model‐predicted exposure in NVAF patients with SRI who received edoxaban at a 15‐mg, once‐daily dose was similar to that in patients with normal renal function or with mild renal impairment receiving a 30‐mg dose. This suggests that efficacy and safety data from the ENGAGE AF study can be used to support dose setting for NVAF patients with SRI.
A cloud‐assisted publish/subscribe service for time‐critical dissemination of bulk content
Authors: Ma Xingkong , Wang Yijie , Pei Xiaoqiang , Xu Fangliang 
Published: December 2016

SummaryCharacterized by the increasing arrival rate of live content, emergency applications pose a great challenge: how to disseminate data with diverse sizes to interested users in a real‐time manner. Most file sharing applications focus on the dissemination of bulk content with less consideration of users' interests. On the other hand, existing publish/subscribes are designed for notifying interested users with small‐sized content. To bridge this gap, we propose CAPS, a cloud‐assisted publish/subscribe service for time‐critical bulk content dissemination. In CAPS, a hybrid 2‐layer architecture is proposed to knit servers in the cloud and clients in the internet. Through dividing each event into attribute‐value pairs and the data content, CAPS provides both event matching service and data distribution in a parallel manner. To improve the upload bandwidth of data distribution, we propose a helper‐based content distribution protocol, where the servers not only guide the clients with similar interests to exchange their received data blocks but also contribute their own upload capacities to clients. Moreover, a volume‐aware helper renting scheme is proposed to adaptively adjust the scale of servers according to the churn of data volume, leading to a high‐performance price ratio. So as to evaluate the performance of CAPS, about 1000 virtual machines are deployed in our Cloud‐Stack testbed. Extensive experiments confirm that CAPS can linearly reduce the download completion time with the growing number of servers, adaptively adjust the upload capacity in tens of seconds according to the change of the workloads, and ensure reliable data dissemination even if a large number of nodes frequently churn or instantaneously fail. Compared with the state‐of‐the‐art approaches, CAPS demonstrates better performance under various parameter settings.
Direct Synthesis of Renewable Dodecanol and Dodecane with Methyl Isobutyl Ketone over Dual‐Bed Catalyst Systems
Authors: Sheng Xueru , Li Ning , Li Guangyi , Wang Wentao , Wang Aiqin , Cong Yu , Wang Xiaodong , Zhang Tao 
Published: December 2016

AbstractFor the first time, we demonstrated two integrated processes for the direct synthesis of dodecanol or 2,4,8‐trimethylnonane (a jet fuel range C12‐branched alkane) using methyl isobutyl ketone (MIBK) that can be derived from lignocellulose. The reactions were carried out in dual‐bed continuous flow reactors. In the first bed, MIBK was selectively converted to a mixture of C12 alcohol and ketone. Over the Pd‐modified magnesium– aluminium hydrotalcite (Pd‐MgAl‐HT) catalyst, a high total carbon yield (73.0 %) of C12 oxygenates can be achieved under mild conditions. In the second bed, the C12 oxygenates generated in the first bed were hydrogenated to dodecanol over a Ru/C catalyst or hydrodeoxygenated to 2,4,8‐trimethylnonane over a Cu/SiO2 catalyst. The as‐obtained dodecanol can be used as feedstock in the production of sodium dodecylsulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS), which are widely used as surfactants or detergents. The asobtained 2,4,8‐trimethylnonane can be blended into conventional jet fuel without hydroisomerization.