bluuebunny/crossref_metadata_2025_split huggingface dataset:
Breaking Bonds and Forming Nanographene Diradicals with Pressure
Authors: Desroches Maude , Mayorga Burrezo Paula , Boismenu‐Lavoie Joël , Peña Álvarez Miriam , Gómez‐García Carlos J. , Matxain Jon M. , Casanova David , Morin Jean‐François , Casado Juan 
Published: October 2017

AbstractNew anthanthrone‐based polycyclic scaffolds possessing peripheral crowded quinodimethanes have been prepared. While the compounds adopt a closed‐shell butterfly‐shaped structure in the ground state, a curved‐to‐planar fluxional inversion is accessible with a low energy barrier through a biradicaloid transition state. Inversion is primarily driven by the release of strain associated with steric hindrance at the peri position of the anthanthrone core; a low‐lying diradical state is accessible through planarization of the core, which is attained in solution at moderate temperatures. The most significant aspect of this transformation is that planarization is also achieved by application of mild pressure in the solid state, wherein the diradical remains kinetically trapped. Complementary information from quantum chemistry, 1H NMR, and Raman spectroscopies, together with magnetic experiments, is consistent with the formation of a nanographene‐like structure that possesses radical centers localized at the exo‐anthanthrone carbons bearing phenyl substituents.
Azido‐Functionalized 5′ Cap Analogues for the Preparation of Translationally Active mRNAs Suitable for Fluorescent Labeling in Living Cells
Authors: Mamot Adam , Sikorski Pawel J. , Warminski Marcin , Kowalska Joanna , Jemielity Jacek 
Published: October 2017

AbstractThe 7‐methylguanosine (m7G) cap structure is a unique feature present at the 5′ ends of messenger RNAs (mRNAs), and it can be subjected to extensive modifications, resulting in alterations to mRNA properties (e.g. translatability, susceptibility to degradation). It also can provide molecular tools to study mRNA metabolism. We developed new mRNA 5′ cap analogues that enable the site‐specific labeling of RNA at the 5′ end using strain‐promoted azide–alkyne cycloaddition (SPAAC) without disrupting the basic function of mRNA in protein biosynthesis. Some of these azide‐functionalized compounds are equipped with additional modifications to augment mRNA properties. The application of these tools was demonstrated by labeling translationally active mRNAs in living cells.
Interrogating Membrane Protein Conformational Dynamics within Native Lipid Compositions
Authors: Reading Eamonn , Hall Zoe , Martens Chloe , Haghighi Tabasom , Findlay Heather , Ahdash Zainab , Politis Argyris , Booth Paula J. 
Published: October 2017

AbstractThe interplay between membrane proteins and the lipids of the membrane is important for cellular function, however, tools enabling the interrogation of protein dynamics within native lipid environments are scarce and often invasive. We show that the styrene–maleic acid lipid particle (SMALP) technology can be coupled with hydrogen–deuterium exchange mass spectrometry (HDX‐MS) to investigate membrane protein conformational dynamics within native lipid bilayers. We demonstrate changes in accessibility and dynamics of the rhomboid protease GlpG, captured within three different native lipid compositions, and identify protein regions sensitive to changes in the native lipid environment. Our results illuminate the value of this approach for distinguishing the putative role(s) of the native lipid composition in modulating membrane protein conformational dynamics.
A Nickel‐Catalyzed Carbonyl‐Heck Reaction
Authors: Vandavasi Jaya Kishore , Hua XiYe , Halima Hamdi Ben , Newman Stephen G. 
Published: October 2017

AbstractThe use of transition‐metal catalysis to enable the coupling of readily available organic molecules has greatly enhanced the ability of chemists to access complex chemical structures. In this work, an intermolecular coupling reaction that unites organotriflates and aldehydes is presented. A unique catalyst system is identified to enable this reaction, featuring a Ni0 precatalyst, a tridentate Triphos ligand, and a bulky amine base. This transformation provides access to a variety of ketone‐containing products without the selectivity‐ and reactivity‐related challenges associated with more traditional Friedel–Crafts reactions. A Heck‐type mechanism is postulated, wherein the π bond of the aldehyde takes the role of the olefin in the insertion/elimination steps.
Visible‐Light‐Driven Palladium‐Catalyzed Radical Alkylation of C−H Bonds with Unactivated Alkyl Bromides
Authors: Zhou Wen‐Jun , Cao Guang‐Mei , Shen Guo , Zhu Xing‐Yong , Gui Yong‐Yuan , Ye Jian‐Heng , Sun Liang , Liao Li‐Li , Li Jing , Yu Da‐Gang 
Published: October 2017

AbstractReported herein is a novel visible‐light photoredox system with Pd(PPh3)4 as the sole catalyst for the realization of the first direct cross‐coupling of C(sp3)−H bonds in N‐aryl tetrahydroisoquinolines with unactivated alkyl bromides. Moreover, intra‐ and intermolecular alkylations of heteroarenes were also developed under mild reaction conditions. A variety of tertiary, secondary, and primary alkyl bromides undergo reaction to generate C(sp3)−C(sp3) and C(sp2)−C(sp3) bonds in moderate to excellent yields. These redox‐neutral reactions feature broad substrate scope (>60 examples), good functional‐group tolerance, and facile generation of quaternary centers. Mechanistic studies indicate that the simple palladium complex acts as the visible‐light photocatalyst and radicals are involved in the process.
Organoiridium Photosensitizers Induce Specific Oxidative Attack on Proteins within Cancer Cells
Authors: Zhang Pingyu , Chiu Cookson K. C. , Huang Huaiyi , Lam Yuko P. Y. , Habtemariam Abraha , Malcomson Thomas , Paterson Martin J. , Clarkson Guy J. , O'Connor Peter B. , Chao Hui , Sadler Peter J. 
Published: October 2017

AbstractStrongly luminescent iridium(III) complexes, [Ir(C,N)2(S,S)]+ (1) and [Ir(C,N)2(O,O)] (2), containing C,N (phenylquinoline), O,O (diketonate), or S,S (dithione) chelating ligands, have been characterized by X‐ray crystallography and DFT calculations. Their long phosphorescence lifetimes in living cancer cells give rise to high quantum yields for the generation of 1O2, with large 2‐photon absorption cross‐sections. 2 is nontoxic to cells, but potently cytotoxic to cancer cells upon brief irradiation with low doses of visible light, and potent at sub‐micromolar doses towards 3D multicellular tumor spheroids with 2‐photon red light. Photoactivation causes oxidative damage to specific histidine residues in the key proteins in aldose reductase and heat‐shock protein‐70 within living cancer cells. The oxidative stress induced by iridium photosensitizers during photoactivation can increase the levels of enzymes involved in the glycolytic pathway.
C3‐Symmetric Tricyclo[2.2.1.02,6]heptane‐3,5,7‐triol
Authors: Kozel Volodymyr , Daniliuc Constantin‐Gabriel , Kirsch Peer , Haufe Günter 
Published: October 2017

AbstractA straightforward access to a hitherto unknown C3‐symmetric tricyclic triol both in racemic and enantiopure forms has been developed. Treatment of 7‐tert‐butoxynorbornadiene with peroxycarboxylic acids provided mixtures of C1‐ and C3‐symmetric 3,5,7‐triacyloxynortricyclenes via transannular π‐cyclization and replacement of the tert‐butoxy group. By refluxing in formic acid, the C1‐symmetric esters were converted to the C3‐symmetric formate. Hydrolysis gave diastereoisomeric triols, which were separated by recrystallization. Enantiomer resolution via diastereoisomeric tri(O‐methylmandelates) delivered the target triols on a gram scale. The pure enantiomers are useful as core units of dopants for liquid crystals.
Chemically functionalized silica nanoparticles‐based solid‐phase extraction for effective pre‐concentration of highly toxic metal ions from food and water samples
Authors: Rajabi Maryam , Rahimi Mohtarameh , Hemmati Maryam , Najafi Farhood 
Published: October 2017

AbstractIn this research study, an efficient solid‐phase extraction procedure based on a new organometallic, effective, eco‐friendly and bio‐degradable nanoadsorbent was firstly introduced for influential pre‐concentration of Cu(II), Zn(II), Pb(II), Cd(II) and Mn(II) ions from food and water samples followed by flame atomic absorption spectrophotometric determination. This safe adsorbent consisted of silica nanoparticles chemically functionalized with di‐ethylen tri‐amine (SiO2@NH2NPs); easily prepared via an effective and simple approach. Characterization of SiO2@NH2NPs was subsequently implemented via SEM, FT‐IR and XRD; certifying high quality of the modified nanoadsorbent in terms of size, shape and surface functional groups. The effects of the main factors on the extraction efficiency were then optimized. Efficient extraction of the analytes of interest at neutral media accompanied with the aid of a bio‐compatible organometallic nanoadsorbent can be considered as valuable advantages of the proposed approach. In the optimum conditions, calibration graphs were linear in the range of 4–700 μg l−1, with higher correlation coefficients than 0.997 and limits of detection of 1.45–4.10 ng ml−1. The enrichment factor values were found to be in the span of 120–400. The resultant extraction recovery values were satisfactory; possessing the proper relative standard deviation (%, n  =  5) values of 2.05–4.28%.
Subjective Complaints as the Main Reason for Biosimilar Discontinuation After Open‐Label Transition From Reference Infliximab to Biosimilar Infliximab
Authors: Tweehuysen Lieke , van den Bemt Bart J. F. , van Ingen Iris L. , de Jong Alphons J. L. , van der Laan Willemijn H. , van den Hoogen Frank H. J. , den Broeder Alfons A. 
Published: October 2017

ObjectiveTo evaluate drug survival, effectiveness, pharmacokinetics, immunogenicity, and safety in daily practice after transitioning treatment from original reference infliximab (Remicade [REM]) to a biosimilar infliximab (CT‐P13 [Remsima; Inflectra]) in patients with rheumatoid arthritis, psoriatic arthritis, or ankylosing spondylitis.MethodsOf the initial 222 REM‐treated patients, 192 agreed to transition to CT‐P13 and were included in this multicenter prospective cohort study. Changes in the Disease Activity Score in 28 joints using the C‐reactive protein level (DAS28‐CRP) and the Bath Ankylosing Spondylitis Disease Activity Index (BASDAI) and changes in the CRP levels, infliximab trough levels, and anti‐infliximab antibody levels were assessed after 6 months, and adverse events (AEs) were documented. Drug survival and prognostic factors were analyzed using Kaplan‐Meier and Cox regression analyses.ResultsDuring 6 months follow‐up, 24% of the patients (n = 47) discontinued CT‐P13. Thirty‐seven patients restarted REM, 7 switched to another biologic drug, and 3 continued without a biologic drug. The DAS28‐CRP remained stable from baseline to month 6, with a mean ± SD score of 2.2 ± 0.9 at baseline to 2.2 ± 0.8 at 6 months (difference of 0.0 [95% confidence interval (95% CI) –0.1, 0.2]). The BASDAI increased from a mean ± SD of 3.8 ± 2.0 at baseline to 4.3 ± 2.1 at 6 months (difference of +0.5 [95% CI 0.1, 0.9]). The CRP levels, infliximab trough levels, and anti‐infliximab antibody levels did not change. Just prior to CT‐P13 discontinuation, the DAS28‐CRP components tender joint count and patient's global assessment of disease activity, as well as the BASDAI were increased compared to baseline. The most frequently reported AEs were arthralgia, fatigue, pruritus, and myalgia. A shorter REM infusion interval (hazard ratio: 0.77 [95% CI 0.62, 0.95]) at baseline was predictive of discontinuing CT‐P13.ConclusionIn our cohort, one‐fourth of patients discontinued CT‐P13 during 6 months of follow‐up, mainly due to an increase in the subjective features of the tender joint count and the patient's global assessment of disease activity and/or subjective AEs, possibly explained by nocebo effects and/or incorrect causal attribution effects.
Formate‐assisted pyrolysis of biomass: an economic and modeling analysis
Authors: AlMohamadi Hamad , Gunukula Sampath , DeSisto William J. , Wheeler M. Clayton 
Published: October 2017

AbstractAn economic analysis was performed to determine the economic potential and commercialization barriers of producing renewable gasoline and diesel (RGD) fuel blendstocks via formate‐assisted pyrolysis (FAsP) followed by hydrodeoxygenation processes. A process model was simulated using Aspen Plus® to estimate material and energy balances for the conversion of 2000 dry MT per day of pine sawdust. Scenarios were considered for the regeneration of formate salts from either ‐biomass‐derived and natural‐gas‐derived carbon monoxide. The material and energy balances were used to calculate capital and operating costs of RGD fuel production. An economic model was built using capital and operating costs to estimate the minimum selling price (MSP) of RGD fuel. The MSP of RGD fuels were estimated at $4.58 per gallon of gasoline equivalent (GGE) and $4.80 per GGE for natural gas and biomass‐derived CO scenarios, respectively. The total capital investments of these plants were $448 million and $497 million. The feedstock cost was found to be the major cost contributor to the MSP of RGD fuel. Improving FAsP process yields will significantly reduce the production cost of RGD fuel. It has been learned that an increase in deoxygenation of bio‐oil in pyrolysis reactor decreases the capital and operating costs of bio‐oil upgrading to RGD fuel. © 2017 Society of Chemical Industry and John Wiley & Sons, Ltd
Colorimetric detection of oxalate in aqueous solution by a pyrogallol red‐based Cu2+ complex
Authors: Inoue Koshiro , Aikawa Shunichi , Fukushima Yasumasa 
Published: October 2017

AbstractThe pyrogallol red (PR)‐based Cu2+ complex was proven to be an effective and selective colorimetric chemosensing ensemble for recognition of oxalate over other anions in a perfect aqueous solution. The addition of oxalate to the PR–Cu2+ complex resulted in a colour change from purple to orange colour due to the regeneration of PR by the chelation of oxalate with Cu2+, while other anions did not induce any significant colour change. Moreover, it was revealed that no obvious interference was observed during the titrations with oxalate into each other anion. Therefore, the PR–Cu2+ complex can be used as a simple and practical colorimetric chemosensor for detecting oxalate.
Retention behavior of flavonoids on immobilized artificial membrane chromatography and correlation with cell‐based permeability
Authors: Tsopelas Fotios , Tsagkrasouli Maria , Poursanidis Pavlos , Pitsaki Maria , Vasios George , Danias Panagiotis , Panderi Irene , Tsantili‐Kakoulidou Anna , Giaginis Constantinos 
Published: October 2017

AbstractThe aim of the study was to investigate the immobilized artificial membrane (IAM) retention mechanism for a set of flavonoids and to evaluate the potential of IAM chromatography to model Caco‐2 permeability. For this purpose, the retention behavior of 41 flavonoid analogs on two IAM stationary phases, IAM.PC.MG and IAM.PC.DD2, was investigated. Correlations between retention factors, logkw(IAM) and octanol–water partitioning (logP) were established and the role of hydroxyl groups of flavonoids to the underlying retention mechanism was explored. IAM retention and logP values were used to establish sound linear models with Caco‐2 permeability (logPapp) taken from the literature. Both stepwise regression and multivariate analysis confirmed the contribution of hydrogen bond descriptors, as additional parameters in the either logkw(IAM) or logP models. Retention factors on both IAM stationary phases showed comparable performance with n‐octanol–water partitioning towards Caco‐2 permeability.
Longer recurrence‐free survival in a patient with metastatic renal cell carcinoma treated with temsirolimus
Authors: Satoh Tendo , Koie Takuya , Horiguchi Hirotaka , Tokui Noriko , Narita Satoshi , Ohyama Chikara 
Published: October 2017

Key Clinical MessageTemsirolimus did not demonstrate an efficacy advantage compared with sorafenib as second‐line therapy in patients with metastatic renal cell carcinoma (mRCC). Only a few patients achieved complete responses, and the median progression‐free survival rate remains short. We report one patient with mRCC who had a continuing response to temsirolimus.
Thrombocytopenia and disseminated histoplasmosis in immunocompetent adults
Authors: Kutkut Issa , Vater Laura , Goldman Mitchell , Czader Magdalena , Swenberg Jessica , Fulkerson Zachary , Mehta Rakesh 
Published: October 2017

Key Clinical MessageDisseminated histoplasmosis among immunocompetent patients is rare, but may be associated with clinically significant refractory thrombocytopenia. Platelet counts often return to normal levels following antifungal therapy. Therefore, the most important management of this refractory thrombocytopenia is the recognition and treatment of histoplasmosis infection.
Supermicrosurgical replantation of a small amputated nasal tissue in a child
Authors: Tee Richard , Woodfield Michael 
Published: October 2017

Key Clinical MessageThis study reports a case of an 8‐year‐old boy who suffered from a dog bite injury to the nose. The amputated nasal tissue measured approximately 1.0 × 1.5 cm and included part of the tip, alar, and soft triangle subunits. Both ends of an artery of less than 0.5 mm were found, and replantation was performed. Chemical leeching was performed postoperatively. At 5‐year follow‐up, a good aesthetic result was achieved.
Nanoscale Metal–Organic Frameworks Decorated with Graphene Oxide for Magnetic Resonance Imaging Guided Photothermal Therapy
Authors: Meng Jing , Chen Xiujin , Tian Yang , Li Zhongfeng , Zheng Qingfeng 
Published: October 2017

AbstractImaging‐guided photothermal therapy (PTT) provides an attractive way to treat cancer. A composite material of a nanoscale metal–organic framework (NMOF) and graphene oxide (GO) has been prepared for potential use in tumor‐guided PTT with magnetic resonance imaging (MRI). The NMOFs containing Fe3+ were prefabricated with an octahedral morphology through a solvothermal reaction to offer a strong T2‐weighted contrast in MRI. Then the NMOFs were decorated with GO nanosheets, which had good photothermal properties. After decoration, zeta‐potential characterization shows that the aqueous stability of the composite material is enhanced, UV/Vis and near‐infrared (NIR) spectra confirm that NIR absorption is also increased, and photothermal experiments reveal that the composite materials express higher photothermal conversion effects and conversion stability. The fabricated NMOF/GO shows low cytotoxicity, effective T2‐weighted contrast of MRI, and positive PTT behavior for a tumor model in vitro. The performance of the composite NMOF/GO for MRI and PTT was also tested upon injection into A549 tumor‐bearing mice. The studies in vivo revealed that the fabricated NMOF/GO was efficient in T2‐weighted imaging and ablation of the A549 tumor with low cytotoxicity, which implied that the prepared composite contrast agent was a potential multifunctional nanotheranostic agent.
New Generation Agent Defeat Weapons: Energetic N,N′‐Ethylene‐Bridged Polyiodoazoles
Authors: Zhao Gang , Kumar Dheeraj , He Chunlin , Hooper Joseph P. , Imler Gregory H. , Parrish Damon A. , Shreeve Jean'ne M. 
Published: October 2017

AbstractSodium salts of iodine‐rich pyrazole and imidazole with 1‐(2‐bromoethyl)‐5‐aminotetrazole are useful precursors for energetic N,N′‐ethylene‐bridged polyiodoazoles. Compounds 1–3 were characterized with IR, and 1H and 13C NMR spectroscopy as well as elemental analyses. The molecular structures of 1 and 2 were confirmed by using single crystal X‐ray diffraction. Heats of formation were calculated using Gaussian 03 and detonation properties and biocidal efficiency were calculated with CHEETAH 7. The decomposition products of 1–3 destroy microbes more effectively than some previously reported biocides since the thermal decomposition occurs at below 400 °C without addition of oxidizer or combustion adjuvant.
Matchmaker Exchange
Authors: Sobreira Nara L. M. , Arachchi Harindra , Buske Orion J. , Chong Jessica X. , Hutton Ben , Foreman Julia , Schiettecatte François , Groza Tudor , Jacobsen Julius O.B. , Haendel Melissa A. , Boycott Kym M. , Hamosh Ada , Rehm Heidi L. ,   on behalf of the Matchmaker Exchange Consortium
Published: October 2017

AbstractIn well over half of the individuals with rare disease who undergo clinical or research next‐generation sequencing, the responsible gene cannot be determined. Some reasons for this relatively low yield include unappreciated phenotypic heterogeneity; locus heterogeneity; somatic and germline mosaicism; variants of uncertain functional significance; technically inaccessible areas of the genome; incorrect mode of inheritance investigated; and inadequate communication between clinicians and basic scientists with knowledge of particular genes, proteins, or biological systems. To facilitate such communication and improve the search for patients or model organisms with similar phenotypes and variants in specific candidate genes, we have developed the Matchmaker Exchange (MME). MME was created to establish a federated network connecting databases of genomic and phenotypic data using a common application programming interface (API). To date, seven databases can exchange data using the API (GeneMatcher, PhenomeCentral, DECIPHER, MyGene2, matchbox, Australian Genomics Health Alliance Patient Archive, and Monarch Initiative; the latter included for model organism matching). This article guides usage of the MME for rare disease gene discovery. © 2017 by John Wiley & Sons, Inc.
Direct Coupling of Thermo‐ and Photocatalysis for Conversion of CO2–H2O into Fuels
Authors: Zhang Li , Kong Guoguo , Meng Yaping , Tian Jinshu , Zhang Lijie , Wan Shaolong , Lin Jingdong , Wang Yong 
Published: October 2017

AbstractPhotocatalytic CO2 reduction into renewable hydrocarbon solar fuels is considered as a promising strategy to simultaneously address global energy and environmental issues. This study focused on the direct coupling of photocatalytic water splitting and thermocatalytic hydrogenation of CO2 in the conversion of CO2–H2O into fuels. Specifically, it was found that direct coupling of thermo‐ and photocatalysis over Au−Ru/TiO2 leads to activity 15 times higher (T=358 K; ca. 99 % CH4 selectivity) in the conversion of CO2–H2O into fuels than that of photocatalytic water splitting. This is ascribed to the promoting effect of thermocatalytic hydrogenation of CO2 by hydrogen atoms generated in situ by photocatalytic water splitting.
Experimentally approved generalized model for circuit applications
Authors: Bilgehan Bülent , Özyapıcı Ali , Sensoy Zehra B. 
Published: October 2017

SummaryIn this paper, generalized model based on the multiplicative least square method presented and showed that it is convenient to approximate observation in the electrical system analysis. The introduced model is exponential based and relies on parametric values. The advantage of the method is due to exponential derivation process within multiplicative calculus and has the flexibility to represent widely used functions such as Gaussian and exponentials. In spite of numerous results on the best fitting model, we study the robustness of the method by making direct comparisons with Matlab built‐in functions. The presented model is challenging because modern electrical circuits and systems are faced with different types of inputs that require near exact representation for accurate processing. Some real applications of exponential‐based data were selected to demonstrate the applicability and efficiency of the proposed representation.