bluuebunny/crossref_metadata_2025_split huggingface dataset:
Robust set‐membership parameter estimation of the glucose minimal model
Authors: Herrero Pau , Delaunay Benoît , Jaulin Luc , Georgiou Pantelis , Oliver Nick , Toumazou Christofer 
Published: January 2015

SummaryThe minimal model of glucose‐insulin dynamics is currently being used in several diabetes‐related applications, such as investigating the glucose metabolism, and in the developments of model predictive controllers and fault detection techniques for automatic blood glucose control (i.e., artificial pancreas). Different approaches have been proposed to identify this model, but none of them is capable of providing guaranteed robust enclosures for its parameters, something very desired in applications such as the artificial pancreas, where robustness is paramount. This paper presents a novel approach for guaranteed set‐membership parameter estimation of the minimal model based on the well‐renowned Set Inversion via Interval Analysis (SIVIA) algorithm. Because the computational complexity of this algorithm is the main barrier for its applicability, an efficient vectorial implementation of SIVIA was employed. Clinical data from a standard intravenous glucose tolerance test were used to prove the validity of the presented approach. Finally, Modal Interval Analysis was used to reduce the numerical overestimation due to the dependency problem of interval arithmetic and significantly speeding up the computations. Copyright © 2015 John Wiley & Sons, Ltd.
Molecular Recognition in Chemical and Biological Systems
Authors: Persch Elke , Dumele Oliver , Diederich François 
Published: January 2015

AbstractStructure‐based ligand design in medicinal chemistry and crop protection relies on the identification and quantification of weak noncovalent interactions and understanding the role of water. Small‐molecule and protein structural database searches are important tools to retrieve existing knowledge. Thermodynamic profiling, combined with X‐ray structural and computational studies, is the key to elucidate the energetics of the replacement of water by ligands. Biological receptor sites vary greatly in shape, conformational dynamics, and polarity, and require different ligand‐design strategies, as shown for various case studies. Interactions between dipoles have become a central theme of molecular recognition. Orthogonal interactions, halogen bonding, and amide⋅⋅⋅π stacking provide new tools for innovative lead optimization. The combination of synthetic models and biological complexation studies is required to gather reliable information on weak noncovalent interactions and the role of water.
Structure and Mechanism of the Caseinolytic Protease ClpP1/2 Heterocomplex from Listeria monocytogenes
Authors: Dahmen Maria , Vielberg Marie‐Theres , Groll Michael , Sieber Stephan A. 
Published: January 2015

AbstractListeria monocytogenes is a devastating bacterial pathogen. Its virulence and intracellular stress tolerance are supported by caseinolytic protease P (ClpP), an enzyme that is conserved among bacteria. L. monocytogenes expresses two ClpP isoforms that are only distantly related by sequence and differ in catalysis, oligomerization, active‐site composition, and N‐terminal interaction sites for associated AAA+ chaperones. The crystal structure of the ClpP1/2 heterocomplex from L. monocytogenes was solved, and in combination with biochemical studies, it provides insights into the mode of action. The results demonstrate that structural interlocking of LmClpP1 with LmClpP2 leads to the formation of a tetradecamer, aligns all 14 active sites, and enhances proteolytic activity. Furthermore, the catalytic center was identified as being responsible for the transient stability of ClpPs.
Design of Aromatic Helical Polymers for STM Visualization: Imaging of Single and Double Helices with a Pattern of π–π Stacking
Authors: Zhu Junyan , Dong Zeyuan , Lei Shengbin , Cao Lili , Yang Bing , Li Wenfang , Zhang Yuanchao , Liu Junqiu , Shen Jiacong 
Published: January 2015

AbstractFrom scanning tunneling microscopy (STM) images of rationally designed helical polymers with a pattern of π–π stacking, we successfully identified the single‐ and double‐helical superstructures. The STM images of the helical structures revealed the smallest helical architecture (diameter ca. 1.3 nm) that has been seen so far. Furthermore, the interconversion of single and double helices was further underpinned by experimental analyses. Significantly, the formation of double helices induced different supramolecular chirality to that observed for the single helices.
Tracing Binding Modes in Hit‐to‐Lead Optimization: Chameleon‐Like Poses of Aspartic Protease Inhibitors
Authors: Kuhnert Maren , Köster Helene , Bartholomäus Ruben , Park Ah Young , Shahim Amir , Heine Andreas , Steuber Holger , Klebe Gerhard , Diederich Wibke E. 
Published: January 2015

AbstractSuccessful lead optimization in structure‐based drug discovery depends on the correct deduction and interpretation of the underlying structure–activity relationships (SAR) to facilitate efficient decision‐making on the next candidates to be synthesized. Consequently, the question arises, how frequently a binding mode (re)‐validation is required, to ensure not to be misled by invalid assumptions on the binding geometry. We present an example in which minor chemical modifications within one inhibitor series lead to surprisingly different binding modes. X‐ray structure determination of eight inhibitors derived from one core scaffold resulted in four different binding modes in the aspartic protease endothiapepsin, a well‐established surrogate for e.g. renin and β‐secretase. In addition, we suggest an empirical metrics that might serve as an indicator during lead optimization to qualify compounds as candidates for structural revalidation.
Efficient Synthesis of Sterically Hindered Arenes Bearing Acyclic Secondary Alkyl Groups by Suzuki–Miyaura Cross‐Couplings
Authors: Li Chengxi , Chen Tianyu , Li Bowen , Xiao Guolan , Tang Wenjun 
Published: January 2015

AbstractBulky P,PO ligands were designed to inhibit isomerization and reduction side reactions during the cross coupling between sterically hindered aryl halides and alkylboronic acids. Suzuki–Miyaura cross‐couplings between di‐ortho‐substituted aryl bromides and acyclic secondary alkylboronic acids have been achieved with high yields. The method has also enabled the preparation of ortho‐alkoxy di‐ortho‐substituted arenes bearing isopropyl groups in excellent yields. The utility of the synthetic method has been demonstrated in a late‐stage modification of estrone and in the application to a new synthetic route toward gossypol.
Enhanced Luminescent Properties of an Open‐Shell (3,5‐Dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl Radical by Coordination to Gold
Authors: Hattori Yohei , Kusamoto Tetsuro , Nishihara Hiroshi 
Published: January 2015

AbstractA gold(I) complex containing an open‐shell luminescent (3,5‐dichloro‐4‐pyridyl)bis(2,4,6‐trichlorophenyl)methyl (PyBTM) radical was prepared. The complex showed fluorescence centered mainly on the coordinated PyBTM ligand. The photophysical and photochemical properties were positively modulated upon coordination to AuI; the photoluminescence quantum yield, fluorescence wavelength, and the stability in the photoexcited state all increased.
Enantioselective Palladium‐Catalyzed Dearomative Cyclization for the Efficient Synthesis of Terpenes and Steroids
Authors: Du Kang , Guo Pan , Chen Yuan , Cao Zhen , Wang Zheng , Tang Wenjun 
Published: January 2015

AbstractA novel enantioselective palladium‐catalyzed dearomative cyclization has been developed for the efficient construction of a series of chiral phenanthrenone derivatives bearing an all‐carbon quaternary center. The effectiveness of this method in the synthesis of terpenes and steroids was demonstrated by a highly efficient synthesis of a kaurene intermediate, the facile construction of the skeleton of the anabolic steroid boldenone, and the enantioselective total synthesis of the antimicrobial diterpene natural product (−)‐totaradiol.
Design and preparation of cross‐linked α‐methylstyrene acrylonitrile copolymer nanoparticles and their interfacial investigation with rubber
Authors: Zhang Huimei , Lu Ming , Lu Qiuyu , He Bo , Zhang Liqun , Liu Yakang 
Published: January 2015

ABSTRACTCross‐linked α‐methylstyrene and acrylonitrile (MStAN) copolymer particles in a latex form were synthesized by free radical emulsion polymerization. The particles showed a narrow size distribution and an average diameter of 65 nm. The amount of the vinyl groups at the surface of the (MStAN) copolymer particles resulted from varied amount of the initiator (APS) and the cross‐linking agent (DVB) was detected by iodine titration method. When filled into ethylene propylene rubber (EPR), the MStAN nano‐particles exhibited excellent reinforcing capabilities, and with the increase of the vinyl groups at the surface of MStAN particles, the tensile stress of MStAN/EPR increased. Results demonstrated that the vinyl groups at the surface of the (MStAN) copolymer particles provided certain chemical interactions between the filler particles and the macromolecular chains of rubber matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41914.
Influence of hydrogen bonding interaction on the damping properties of poly(n‐butyl methacrylate)/small molecule hybrids
Authors: Yin Xiaotong , Liu Chongyang , Lin Yu , Guan Aiguo , Wu Guozhang 
Published: January 2015

ABSTRACTThe hydrogen bonding interactions between poly(n‐butyl methacrylate) and a series of low molecular weight phenols containing two to four hydroxyl groups with different steric effects were investigated by differential scanning calorimetry and Fourier‐transform infrared spectroscopy. Results showed that the hydrogen bonding strength between the two components varies greatly according to the steric effects of the phenolic hydroxyl group. As the size of the group beside the hydroxyl increases, the hydrogen bond strength weakens. The glass transition temperature of binary hybrid systems was put into relation with the corresponding hydrogen bonding interaction strength. Strong hydrogen bonding strength increased Tg to higher values than that predicted by the linear additivity rule; by contrast, Tg of hybrid systems with weak hydrogen bonds showed linear changes. All of the samples showed linear variations at low concentrations of small molecules. The damping properties of five systems were analyzed by dynamic mechanical analysis. Either the loss factor or area of tan δ peak of the five systems increased compared with that of the pure polymer, thereby showing great improvements in the damping properties of the poly(n‐butyl methacrylate)/small molecule hybrid material. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41954.
Randomized clinical trial of sacral versus percutaneous tibial nerve stimulation in patients with faecal incontinence
Authors: Thin N N , Taylor S J C , Bremner S A , Emmanuel A V , Hounsome N , Williams N S , Knowles C H , Alam A , Bannister S , Scott S M , Allison M E , Vaizey C J , Thomas G P 
Published: January 2015

Abstract

Background
Sacral nerve stimulation (SNS) is a well established therapy for faecal incontinence (FI). Percutaneous tibial nerve stimulation (PTNS) is a newer, less invasive, treatment. The effectiveness and acceptability of these treatments have not been compared systematically.

Methods
An investigator-blinded randomized pilot trial of PTNSversus SNS with a parallel qualitative study was performed. Quantitative clinical outcomes and qualitative data from patient interviews were collected for both interventions.

Results
Forty patients (39 women; mean age 59 years) met the eligibility criteria; 23 were randomized to receive SNS and 17 to PTNS. Fifteen patients progressed to permanent SNS implantation and 16 received a full course of PTNS. Within-group effect sizes were marginally greater for SNS than for PTNS on available-case analysis. Mean(s.d.) FI episodes per week at baseline, and 3 and 6 months of follow-up were: 11·4(12·0), 4·0(4·0) and 4·9(6·9) respectively for SNS compared with 10·6(11·2), 5·8(6·9) and 6·3(6·9) for PTNS. Mean(s.d.) Cleveland Clinic Incontinence Score values at baseline, and 3 and 6 months were: 16·2(3·0), 11·1(5·2) and 10·4(5·6) for SNSversus 15·1(2·7), 11·7(4·4) and 12·1(5·2) for PTNS. Improvement of at least 50 per cent in FI episodes per week at 6 months was seen in 11 of 18 patients in the SNS group compared with seven of 15 in the PTNS group. Effect estimates for SNS with chronic implanted stimulation were larger (10 of 15 patients at 6 months). Disease-specific and generic quality-of-life improvements complemented clinical outcome data. Qualitative analysis of interview data suggested that both treatments had high acceptability amongst patients.

Conclusion
In the short term, both SNS and PTNS provide some clinical benefit to patients with FI. Registration numbers: 2010-018728-15 and 10479 (http://public.ukcrn.org.uk/search/StudyDetail.aspx?StudyID=10479).
Variability in the reported management of pulmonary metastases in osteosarcoma
Authors: Bhattasali Onita , Vo Andrea T. , Roth Michael , Geller David , Randall R. Lor , Gorlick Richard , Gill Jonathan 
Published: January 2015

AbstractNearly 20% of patients with newly diagnosed osteosarcoma have detectable metastases at diagnosis; the majority of which occur in the lungs. There are no established recommendations for the timing and modality of metastasectomy. Members of the Connective Tissue Oncology Society (CTOS) were emailed an anonymous 10‐min survey assessing their management practices for pulmonary findings at the time of an osteosarcoma diagnosis. The questionnaire presented three scenarios and discussed the choice to perform surgery, the timing of resection, and the choice of surgical procedure. Analyses were stratified by medical profession. One hundred and eighty‐three physicians responded to our questionnaire. Respondents were comprised of orthopedic surgeons (37%), medical oncologists (31%), pediatric oncologists (22%), and other medical subspecialties (10%). There was variability among the respondents in the management of the pulmonary nodules. The majority of physicians chose to resect the pulmonary nodules following neoadjuvant chemotherapy (46–63%). Thoracotomy was the preferred technique for surgical resection. When only unilateral findings were present, the majority of physicians did not explore the contralateral lung. The majority of respondents did not recommend resection if the pulmonary nodule disappeared following chemotherapy. The survey demonstrated heterogeneity in the management of pulmonary metastases in osteosarcoma. Prospective trials need to evaluate whether these differences in management have implications for outcomes for patients with metastatic osteosarcoma.
Functional Characterization of MpaG′, the O‐Methyltransferase Involved in the Biosynthesis of Mycophenolic Acid
Authors: Zhang Wei , Cao Shaona , Qiu Li , Qi Fengxia , Li Zhong , Yang Ying , Huang Shaohua , Bai Fali , Liu Changning , Wan Xiaobo , Li Shengying 
Published: January 2015

AbstractMycophenolic acid (MPA, 1) is a clinically important immunosuppressant. In this report, a gene cluster mpa′ responsible for the biosynthesis of 1 was identified from Penicillium brevicompactum NRRL 864. The S‐adenosyl‐L‐methionine‐dependent (SAM‐dependent) O‐methyltransferase encoded by the mpaG′ gene was functionally and kinetically characterized in vitro. MpaG′ catalyzes the methylation of demethylmycophenolic acid (DMMPA, 6) to form 1. It also showed significant substrate flexibility by methylating two structural derivatives of 6 prepared by organic synthesis.
A Cascade Synthesis of Aminohydantoins Using In Situ‐Generated N‐Substituted Isocyanates
Authors: Vincent‐Rocan Jean‐François , Clavette Christian , Leckett Kyle , Beauchemin André M. 
Published: January 2015

AbstractNitrogen‐substituted isocyanates are rarely utilized but powerful building blocks for the development of cascade reactions in heterocyclic synthesis. These reactive amphoteric intermediates can be accessed in situ via an equilibrium that allows controlled reactivity in the presence of bifunctional partners such as α‐amino esters. A cascade reaction has been carried out that forms 3‐aminohydantoin derivatives using simple phenoxycarbonyl derivatives of hydrazides and hydrazones as precursors of N‐substituted‐isocyanates. This method allows rapid assembly of complex aminohydantoin derivatives, including analogues of medicinally‐relevant compounds, using simple reactants.
Sensing of 2,4,6‐Trinitrotoluene (TNT) and 2,4‐Dinitrotoluene (2,4‐DNT) in the Solid State with Photoluminescent RuII and IrIII Complexes
Authors: Mosca Lorenzo , Khnayzer Rony S. , Lazorski Megan S. , Danilov Evgeny O. , Castellano Felix N. , Anzenbacher Pavel 
Published: January 2015

AbstractA series of metal–organic chromophores containing RuII or IrIII were studied for the luminometric detection of nitroaromatic compounds, including trinitrotoluene (TNT). These complexes display long‐lived, intense photoluminescence in the visible region and are demonstrated to serve as luminescent sensors for nitroaromatics. The solution‐based behavior of these photoluminescent molecules has been studied in detail in order to identify the mechanism responsible for metal‐to‐ligand charge‐transfer (MLCT) excited state quenching upon addition of TNT and 2,4‐dinitrotoluene (2,4‐DNT). A combination of static and dynamic spectroscopic measurements unequivocally confirmed that the quenching was due to a photoinduced electron transfer (PET) process. Ultrafast transient absorption experiments confirmed the formation of the TNT radical anion product following excited state electron transfer from these metal complexes. Reported for the first time, photoluminescence quenching realized through ink‐jet printing and solid‐state titrations was used for the solid‐state detection of TNT; achieving a limit‐of‐quantitation (LOQ) as low as 5.6 ng cm−2. The combined effect of a long‐lived excited state and an energetically favorable driving force for the PET process makes the RuII and IrIII MLCT complexes discussed here particularly appealing for the detection of nitroaromatic volatiles and related high‐energy compounds.
Synthesis of Bicyclic Proline Derivatives by the Aza‐Cope–Mannich Reaction: Formal Synthesis of (±)‐Acetylaranotin
Authors: Belov Dmitry S. , Ratmanova Nina K. , Andreev Ivan A. , Kurkin Alexander V. 
Published: January 2015

AbstractHerein we suggest an approach to oxygenated bicyclic amino acids based on an aza‐Cope–Mannich rearrangement. Seven distinct amino acid scaffolds analogous to the natural products were prepared on a gram scale with precise control of stereochemistry. Successful implementation of our strategy resulted in the formal synthesis of acetylaranotin.
Triflic Acid Mediated Cascade Cyclization of Aryldiynes for the Synthesis of Indeno[1,2‐c]chromenes: Application to Dye‐Sensitized Solar Cells
Authors: Jiang Hua , Ferrara Giovanni , Zhang Xuan , Oniwa Kazuaki , Islam Ashraful , Han Liyuan , Sun Ying‐Ji , Bao Ming , Asao Naoki , Yamamoto Yoshinori , Jin Tienan 
Published: January 2015

AbstractA new triflic acid (TfOH)‐mediated cascade cyclization of ortho‐anisole‐substituted aryldiynes is described for the construction of indeno[1,2‐c]chromenes. The cascade cyclization proceeds through an unusual TfOH‐induced alkyne‐alkyne cyclization followed by nucleophilic attack of the methoxy group on the benzylidene cation, which is completely different to the cyclization of ortho‐aniline‐ or ortho‐thioanisole‐substituted aryldiynes. A new class of organic dyes with the indeno[1,2‐c]chromene framework as both donor and π‐linker were synthesized. These compounds exhibit high photovoltaic performances in dye‐ sensitized solar cells (DSCs).
Dialkylzinc‐Mediated Cross‐Coupling Reactions of Perfluoroalkyl and Perfluoroaryl Halides with Aryl Halides
Authors: Kato Hisano , Hirano Keiichi , Kurauchi Daisuke , Toriumi Naoyuki , Uchiyama Masanobu 
Published: January 2015

AbstractA highly chemoselective perfluoroalkylation reaction of aromatic halides is reported. Thermally stable perfluoroalkylzinc reagents, generated by a rapid halogen–zinc exchange reaction between diorganozinc and perfluoroalkyl halide species, couple with a wide range of aryl halides in the presence of a copper catalyst, in moderate to high yields. Good stability of the perfluoroalkylzinc species was indicated by DFT calculation and the reagents were storable for at least three months under argon without loss of activity. This method is applicable to gram‐scale synthesis, and its functional group tolerance compares favorably with reported protocols.
Initial Radical Cation Pathway in the Mo2Cl10‐Mediated Dehydrogenative Arene Coupling
Authors: Leppin Jana , Schubert Moritz , Waldvogel Siegfried R. , Heinze Katja 
Published: January 2015

AbstractExperimental (EPR) and theoretical (DFT) evidence is provided for radical cation formation as initial step in the Mo2Cl10‐mediated dehydrogenative arene coupling. The initial electron transfer from methoxyarenes to molybdenum proceeds via an inner sphere mechanism.
Preclinical Characterization of Acyl Sulfonimidamides: Potential Carboxylic Acid Bioisosteres with Tunable Properties
Authors: Borhade Sanjay R. , Svensson Richard , Brandt Peter , Artursson Per , Arvidsson Per I. , Sandström Anja 
Published: January 2015

AbstractHerein we present the preclinical characterization of novel compounds containing the linear acyl sulfonimidamide functionality. Specifically, we studied the pKa, lipophilicity, in vitro metabolic stability, plasma protein binding, Caco‐2 permeability, and aqueous solubility for nine aryl acyl sulfonimidamides. In comparison with widely used carboxylic acid bioisosteres, the acyl sulfonimidamides were found to be less acidic and more lipophilic depending on the substitution pattern in the studied compounds. Importantly, the pKa values (5.9–7.6) were significantly influenced by substituents on the nitrogen atom and the aryl substituents. Moreover, the acyl sulfonimidamides displayed membrane permeabilities ranging from moderate to very high, which correlated with decreased pKa and low to negligible efflux ratios. We foresee that the chiral sulfur center and the two handles for structural diversity of linear acyl sulfonimidamides will offer new opportunities for drug design and for improving the oral bioavailability of acidic drug candidates.
Augmenting basic colour terms in english
Authors: Mylonas Dimitris , MacDonald Lindsay 
Published: January 2015

AbstractIn an unconstrained colour naming experiment conducted over the web, 330 participants named 600 colour samples in English. The 30 most frequent monolexemic colour terms were analyzed with regards to frequency, consensus among genders, response times, consistency of use, denotative volume in the Munsell and OSA colour spaces and inter‐experimental agreement. Each of these measures served for ranking colour term salience; rankings were then combined to give a composite index of basicness. The results support the extension of English inventory from the 11 basic colour terms of Berlin and Kay to 13 terms by the addition of lilac and turquoise. © 2015 Wiley Periodicals, Inc. Col Res Appl, 41, 32–42, 2016