bluuebunny/crossref_metadata_2025_split huggingface dataset:
N‐Methyl Inversion and Accurate Equilibrium Structures in Alkaloids: Pseudopelletierine
Authors: Vallejo‐López Montserrat , Écija Patricia , Vogt Natalja , Demaison Jean , Lesarri Alberto , Basterretxea Francisco J. , Cocinero Emilio J. 
Published: July 2017

AbstractA rotational spectroscopy investigation has resolved the conformational equilibrium and structural properties of the alkaloid pseudopelletierine. Two different conformers, which originate from inversion of the N‐methyl group from an axial to an equatorial position, have been unambiguously identified in the gas phase, and nine independent isotopologues have been recorded by Fourier‐transform microwave spectroscopy in a jet expansion. Both conformers share a chair–chair configuration of the two bridged six‐membered rings. The conformational equilibrium is displaced towards the axial form, with a relative population in the supersonic jet of Naxial/Nequatorial≈2/1. An accurate equilibrium structure has been determined by using the semiexperimental mixed‐estimation method and alternatively computed by quantum‐chemical methods up to the coupled‐cluster level of theory. A comparison with the N‐methyl inversion equilibria in related tropanes is also presented.
Design and scale‐up of an alkylated Minisci reaction to produce ethionamide with 4‐cyanopyridine as raw materials
Authors: Liang Zhongrui , He Lichao , Wang Wenchao , Zhou Zhiyong , Ren Zhongqi 
Published: August 2017

AbstractTuberculosis is a serious bacterial infection in developing countries, especially in areas with drug resistance. The development of the anti‐tuberculosis drug ethionamide (ETA) is therefore particularly important. We have designed a new route for ETA synthesis and considered the drug's amenability to large‐scale manufacture. We evaluated different routes for the synthesis of ETA and selected the most suitable process for the industrial production of this material, which involved the Minisci reaction of 4‐cyanopyridine with propionic acid using a AgNO3/(NH4)2S2O8 catalyst system under acidic conditions. The effects of different parameters on the reaction were studied, and the production of the intermediate of 2‐ethyl‐4‐cyanopyridine was twice recrystallized from methanol to obtain pure ETA. In the Minisci reaction, the system was stirred for an additional 20 min at 80 °C after the addition of ammonium persulphate solution. The subsequent formation of thioamide was conducted at 40 °C to 60 °C for 1.5 h with a 1:5:2 molar ratio of 4‐cyanopyridine, propionic acid, and ammonium sulphide. The purity of the crude ETA reached 98.77  % after two recrystallization steps. This process could be scaled up on a much larger scale (1 kg), leading to the yield of alkylation reaction and overall yield of the production process as 44.06 % and 31.26 %, respectively.
Health care disparities among octogenarians and nonagenarians with stage II and III rectal cancer
Authors: Cassidy Richard J. , Switchenko Jeffrey M. , Cheng En , Jiang Renjian , Jhaveri Jaymin , Patel Kirtesh R. , Tanenbaum Daniel G. , Russell Maria C. , Steuer Conor E. , Gillespie Theresa W. , McDonald Mark W. , Landry Jerome C. 
Published: July 2017

BACKGROUNDOctogenarians and nonagenarians with stage II/III rectal adenocarcinomas are underrepresented in the randomized trials that have established the standard‐of‐care therapy of preoperative chemoradiation followed by definitive resection (ie, chemoradiation and then surgery [CRT+S]). The purpose of this study was to evaluate the impact of therapies on overall survival (OS) for patients with stage II/III rectal cancers and determine predictors of therapy within the National Cancer Data Base (NCDB).METHODSIn the NCDB, patients who were 80 years old or older and had clinical stage II/III rectal adenocarcinoma from 2004 to 2013 were queried. Kaplan‐Meier analysis, log‐rank testing, logistic regression, Cox proportional hazards regression, interaction effect testing, and propensity score–matched analysis were conducted.RESULTSThe criteria were met by 2723 patients: 14.9% received no treatment, 29.7% had surgery alone, 5.0% underwent short‐course radiation and then surgery (RT+S), 45.3% underwent CRT+S, and 5.1% underwent surgery and then chemoradiation (S+CRT). African American race and residence in a less educated county were associated with not receiving treatment. Male sex, older age, worsening comorbidities, and receiving no treatment or undergoing surgery alone were associated with worse OS. There was no statistical difference in OS between RT+S, S+CRT, and CRT+S. Interaction testing found that CRT+S improved OS independently of age, comorbidity status, sex, race, and tumor stage. In the propensity score–matched analysis, CRT+S was associated with improved OS in comparison with surgery alone.CONCLUSIONSA significant portion of octogenarians and nonagenarians with stage II/III rectal adenocarcinomas do not receive treatment. African American race and living in a less educated community are associated with not receiving therapy. This series suggests that CRT+S is a reasonable strategy for elderly patients who can tolerate therapy. Cancer 2017;123:4325‐36. © 2017 American Cancer Society.
Feasibility and preliminary effects of resistance training and nutritional supplements during versus after radiotherapy in patients with head and neck cancer: A pilot randomized trial
Authors: Sandmæl Jon Arne , Bye Asta , Solheim Tora Skeidsvoll , Stene Guro Birgitte , Thorsen Lene , Kaasa Stein , Lund Jo‐Åsmund , Oldervoll Line Merethe 
Published: July 2017

BACKGROUNDPatients with head and neck cancer (HNC) experience involuntary weight loss that has a negative impact on physical function, morbidity, and survival. The objective of the current study was to evaluate the feasibility of an exercise and nutrition intervention during radiotherapy (RT) compared with after RT, and to examine preliminary effects on skeletal muscle mass.METHODSPatients with HNC were randomized to an exercise and nutrition intervention during RT (EN‐DUR) or after RT (EN‐AF). The EN‐DUR intervention was conducted at a hospital and the EN‐AF intervention took place at a rehabilitation center. The interventions consisted of progressive resistance training (PRT) and oral nutritional supplements (ONS). Feasibility outcomes were tracked weekly and muscle mass was measured by computed tomography scans before and after RT and at 2 months follow‐up.RESULTSOf the 50 eligible patients, 41 (82%) agreed to participate. 90% of patients completed the EN‐DUR intervention and the adherence to PRT and ONS was 81% and 57%, respectively. 52% of patients attended the EN‐AF intervention and adherence to PRT and ONS was 94% and 76%, respectively. The EN‐DUR demonstrated a trend toward mitigating loss of muscle mass during RT and the EN‐AF demonstrated a similar trend after RT. No difference in muscle mass was detected between the groups from baseline to week 14.CONCLUSIONSAn exercise and nutrition intervention is feasible for patients with HNC during RT, and the intervention is potentially effective in mitigating loss of muscle mass both during and after RT. Future trials should assess the feasibility and effects of extended interventions during and after treatment. Cancer 2017;123:4440‐8. © 2017 American Cancer Society.
Nanocrystal–Dye Interactions: Studying the Feasibility of Co‐Sensitization of Dyes with Semiconductor Nanocrystals
Authors: Mittal Mona , Sapra Sameer 
Published: July 2017

AbstractOne of the recent developments in enhancing the performance of quantum dot sensitized solar cells (QDSSCs) is to combine QDs with dyes in order to overcome the drawbacks of QDSSCs. However, implementation of this requires a detailed investigation of the interaction between QDs and dye. Here, we have studied the effect of size and surface ligands in the interaction of CdSe nanocrystals (NCs) with Ru N‐719 dye. The interaction mechanism is investigated by steady‐state and time‐resolved photoluminescence spectroscopy, indicating the involvement of apparent static as well as dynamic quenching. Further analysis of dynamic quenching reveals the contribution of Förster resonance energy transfer and electron transfer from NCs to the dye. The Marcus model of electron transfer rationalizes the random trends of experimental electron transfer rates, which depend on the energetic offsets between the two species and the reorganizational energy. For understanding the kinetics of energy/charge transfer from CdSe NCs to Ru N‐719 dye, a Poisson binding model has been proposed that assumes a Poisson distribution of dye molecules around CdSe NCs. The variation of quenching rate constants and PL quenching rate both follow the same trend, supporting the main contribution of kinetics in the interaction of CdSe NCs with the dye.
Site‐Specific Protein Labeling via Sortase‐Mediated Transpeptidation
Authors: Antos John M. , Ingram Jessica , Fang Tao , Pishesha Novalia , Truttmann Matthias C. , Ploegh Hidde L. 
Published: August 2017

AbstractStrategies for site‐specific protein modification are highly desirable for the construction of conjugates containing non‐genetically‐encoded functional groups. Ideally, these strategies should proceed under mild conditions, and be compatible with a wide range of protein targets and non‐natural moieties. The transpeptidation reaction catalyzed by bacterial sortases is a prominent strategy for protein derivatization that possesses these features. Naturally occurring or engineered variants of sortase A from Staphylococcus aureus catalyze a ligation reaction between a five‐amino‐acid substrate motif (LPXTG) and oligoglycine nucleophiles. By pairing proteins and synthetic peptides that possess these ligation handles, it is possible to install modifications onto the protein N‐ or C‐terminus in site‐specific fashion. As described in this unit, the successful implementation of sortase‐mediated labeling involves straightforward solid‐phase synthesis and molecular biology techniques, and this method is compatible with proteins in solution or on the surface of live cells. © 2017 by John Wiley & Sons, Inc.
Altered theta oscillations in resting EEG of fibromyalgia syndrome patients
Authors: Fallon N. , Chiu Y. , Nurmikko T. , Stancak A. 
Published: July 2017

AbstractBackgroundFibromyalgia syndrome (FM) is a chronic pain disorder characterized by widespread pain, sleep disturbance, fatigue and cognitive/affective symptoms. Functional imaging studies have revealed that FM and other chronic pain syndromes can affect resting brain activity. This study utilized electroencephalographic (EEG) recordings to investigate the relative power of ongoing oscillatory activity in the resting brain.MethodsA 64‐channel EEG was recorded at rest in 19 female FM patients and 18 healthy, age‐matched, control subjects. The Manual Tender Point Scale (MTPS) examination was performed to quantify tonic pain and tenderness on the day of testing along with measures of mood, arousal and fatigue. Oscillations in delta, theta, alpha, beta and gamma frequency bands were analysed using Standardised Low‐Resolution Brain Electromagnetic Tomography to evaluate sources of spectral activity throughout the whole brain.ResultsFM patients exhibited greater pain, tiredness and tension on the day of testing relative to healthy control participants and augmented theta activity in prefrontal and anterior cingulate cortices. No significant differences were seen in other frequency bands. Augmented frontal theta activity in FM patients significantly correlated with measures of tenderness and mean tiredness scores.ConclusionsThe findings indicate that alterations to resting‐state oscillatory activity may relate to ongoing tonic pain and fatigue in FM, and manifest in brain regions relevant for cognitive‐attentional aspects of pain processing and endogenous pain inhibition. Enhanced low‐frequency oscillations were previously seen in FM and other chronic pain syndromes, and may relate to pathophysiological mechanisms for ongoing pain such as thalamocortical dysrhythmia.SignificanceIncreased prefrontal theta activity may contribute to persistent pain in fibromyalgia or represent the outcome of prolonged symptoms. The findings point to the potential for therapeutic interventions aimed at normalizing neural oscillations, while further research utilizing quantitative analysis of resting EEG could benefit our understanding of fibromyalgia pathophysiology.
Cable tray fire tests in a confined and mechanically ventilated facility
Authors: Zavaleta Pascal , Audouin Laurent 
Published: July 2017

AbstractCable fires are one of the main fire hazards in nuclear power plants. As part of the cable fire spreading (CFS) campaign of the OECD PRISME‐2 programme, 3 real‐scale cable tray fire tests were performed in open atmosphere (1 CFS support test, named CFSS‐2) and in a confined and mechanically ventilated facility (2 CFS tests, named CFS‐3 and CFS‐4). This study aims at investigating the effects of confined and ventilated conditions on cable tray fires that used a halogen‐free flame retardant cable‐type. The CFS‐3 and CFS‐4 tests involved 2 ventilation renewal rates of 4 and 15 h−1, respectively. The confined conditions lead to decrease the fire growth rate and the peaks of mass loss rate and heat release rate, compared with open atmosphere. The reductions are larger for the lower ventilation renewal rate. Furthermore, it is shown that the CFS‐4 test may be classified as a well‐ventilated fire and the CFS‐3 test as an under‐ventilated fire. For this last one, its fire characteristics and its consequences in the fire room highlight an oscillatory behaviour, with the same low frequency, for about 30 minutes. These oscillations arise from successive combustions of unburnt gases.
Innovative geophysical technologies for the exploration of faults, karst structures and cavities in tunnelling
Authors: Schmidt Markus , Richter Thomas , Lehmann Paul 
Published: August 2017

AbstractIn rock formations prone to karstification, there are no or only limited geological/hydrological principles that enable safe prognosis of the existence and location of karst and fault structures. The application of geophysical methods offers a high efficiency of detection and localisation of faults, cavities and karst structures, and when combined with targeted verification drillings, provides an extensive three‐dimensional structural investigation of rock formations. Four examples of geophysical karst and fault investigations in German tunnelling are presented here to demonstrate the innovative technologies and their respective survey results that in all cases contributed to a safe excavation process and later operation of the tunnels.
Engineering brown fat into skeletal muscle using ultrasound‐targeted microbubble destruction gene delivery in obese Zucker rats: Proof of concept design
Authors: Bastarrachea Raul A. , Chen Jiaxi , Kent Jack W. , Nava‐Gonzalez Edna J. , Rodriguez‐Ayala Ernesto , Daadi Marcel M. , Jorge Barbara , Laviada‐Molina Hugo , Comuzzie Anthony G. , Chen Shuyuan , Grayburn Paul A. 
Published: August 2017

AbstractUltrasound‐targeted microbubble destruction (UTMD) is a novel means of tissue‐specific gene delivery. This approach systemically infuses transgenes precoupled to gas‐filled lipid microbubbles that are burst within the microvasculature of target tissues via an ultrasound signal resulting in release of DNA and transfection of neighboring cells within the tissue. Previous work has shown that adenovirus containing cDNA of UCP‐1, injected into the epididymal fat pads in mice, induced localized fat depletion, improving glucose tolerance, and decreasing food intake in obese diabetic mice. Our group recently demonstrated that gene therapy by UTMD achieved beta cell regeneration in streptozotocin (STZ)‐treated mice and baboons. We hypothesized that gene therapy with BMP7/PRDM16/PPARGC1A in skeletal muscle (SKM) of obese Zucker diabetic fatty (fa/fa) rats using UTMD technology would produce a brown adipose tissue (BAT) phenotype with UCP‐1 overexpression. This study was designed as a proof of concept (POC) project. Obese Zucker rats were administered plasmid cDNA contructs encoding a gene cocktail with BMP7/PRDM16/PPARGC1A incorporated within microbubbles and intravenously delivered into their left thigh. Controls received UTMD with plasmids driving a DsRed reporter gene. An ultrasound transducer was directed to the thigh to disrupt the microbubbles within the microcirculation. Blood samples were drawn at baseline, and after treatment to measure glucose, insulin, and free fatty acids levels. SKM was harvested for immunohistochemistry (IHC). Our IHC results showed a reliable pattern of effective UTMD‐based gene delivery in enhancing SKM overexpression of the UCP‐1 gene. This clearly indicates that our plasmid DNA construct encoding the gene combination of PRDM16, PPARGC1A, and BMP7 reprogrammed adult SKM tissue into brown adipose cells in vivo. Our pilot established POC showing that the administration of the gene cocktail to SKM in this rat model of genetic obesity using UTMD gene therapy, engineered a BAT phenotype with UCP‐1 over‐expression. © 2017 IUBMB Life, 69(9):745–755, 2017
Rotator cuff repair with a novel mesh suture: An ex vivo assessment of mechanical properties
Authors: Zhang Tao , Hatta Taku , Thoreson Andrew R. , Lu ChengChang , Steinmann Scott P. , Moran Steven L. , Zhao Chunfeng 
Published: August 2017

ABSTRACTSurgical repair is a common treatment for rotator cuff tear; however, the retear rate is high. A high degree of suture repair strength is important to ensure rotator cuff integrity for healing. The purpose of this study was to compare the mechanical performance of rotator cuffs repaired with a mesh suture versus traditional polydioxanone suture II and FiberWire sutures in a canine in vitro model. Seventy‐two canine shoulders were harvested. An infraspinatus tendon tear was created in each shoulder. Two suture techniques—simple interrupted sutures and two‐row suture bridge—were used to reconnect the infraspinatus tendon to the greater tuberosity, using three different suture types: Mesh suture, polydioxanone suture II, or FiberWire. Shoulders were loaded to failure under displacement control at a rate of 20 mm/min. Failure load was compared between suture types and techniques. Ultimate failure load was significantly higher in the specimens repaired with mesh suture than with polydioxanone suture II or FiberWire, regardless of suture technique. There was no significant difference in stiffness among the six groups, with the exception that FiberWire repairs were stiffer than polydioxanone suture II repairs with the simple interrupted technique. All specimens failed by suture pull‐out from the tendon. Based on our biomechanical findings, rotator cuff repair with the mesh suture might provide superior initial strength against failure compared with the traditional polydioxanone suture II or FiberWire sutures. Use of the mesh suture may provide increased initial fixation strength and decrease gap formation, which could result in improved healing and lower re‐tear rates following rotator cuff repair. © 2017 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 36:987–992, 2018.
Application of new insoluble dietary fibres from triticale as supplement in yoghurt – effects on physico‐chemical, rheological and quality properties
Authors: Miocinovic Jelena , Tomic Nikola , Dojnov Biljana , Tomasevic Igor , Stojanovic Sanja , Djekic Ilija , Vujcic Zoran 
Published: July 2017

AbstractBACKGROUNDThe need to increase the daily intake of dietary fibres opens a new chapter in the research of functional foods enriched with fibres. The potential application of an innovative product – insoluble dietary fibres from triticale in yoghurts – was deployed by characterising their food application and evaluating physico‐chemical, rheological and sensory properties and was the aim of this research.RESULTSDetailed characterisations of these fibres are presented for the first time and showed very good hydration properties, optimal pH (slightly acidic), optimal chemical composition, high antioxidant capacity which was proven by phenolics contents. Besides, these fibres showed negligible calorific value, with no phytates and high antioxidant capacity, mainly from ferulic acid. Therefore they could be successfully added to yoghurt. Enrichment of yoghurt having different milk fat content (1.5 and 2.8% w/w) with triticale insoluble fibre (1.5% and 3.0% w/w) significantly influenced the syneresis level, its apparent viscosity, yield stress and thixotropic behaviour. The overall sensory quality scores indicated that yoghurt enriched with 1.5% triticale insoluble fibres was recognised as ‘excellent’ and had enhanced antioxidant activity.CONCLUSIONSInsoluble triticale fibre could therefore be used as a supplement to produce functional yoghurt. © 2017 Society of Chemical Industry
Changes in rheological properties of wheat due to storage
Authors: Kamboj Uma , Guha Paramita , Mishra Sunita 
Published: July 2017

AbstractBACKGROUNDThe present study aimed to investigate changes in the fundamental rheological properties of dough prepared from wheat grains stored for 6 months at 20 °C, at ambient temperature (temperature varied with time) and at 4 °C. Stress/shear rate ramp, oscillation and creep‐recovery tests were performed to assess the changes in rheological properties as a result of storage.RESULTSSamples were observed to be non‐Newtonian; thus, the Bingham model estimated the yield stress, which was maximum for the wheat stored under ambient conditions and minimum for wheat stored at 20 °C. The stress required to break the bonds was maximum for wheat‐dough stored under ambient conditions and minimum for wheat stored at 20 °C. Wheat stored at 20 °C also had the highest maximum creep and recovery strain. The viscoelastic properties of the three wheat‐dough samples were compared.CONCLUSIONThe results obtained in the present study show that the wheat‐dough prepared under ambient conditions behaves as a rigid and stiff material. The dough prepared from wheat stored at 20 °C had the maximum elasticity. © 2017 Society of Chemical Industry
Direct online extraction and determination by supercritical fluid extraction with chromatography and mass spectrometry of targeted carotenoids from red Habanero peppers (Capsicum chinense Jacq.)
Authors: Zoccali Mariosimone , Giuffrida Daniele , Dugo Paola , Mondello Luigi 
Published: July 2017

AbstractRecently, supercritical fluid chromatography coupled to mass spectrometry has gained attention as a fast and useful technology applied to the carotenoids analysis. However, no reports are available in the literature on the direct online extraction and determination by supercritical fluid extraction with chromatography and mass spectrometry. The aim of this research was the development of an online method coupling supercritical fluid extraction and supercritical fluid chromatography for a detailed targeted native carotenoids characterization in red habanero peppers. The online nature of the system, compared to offline approaches, improves run‐to‐run precision, enables the setting of batch‐type applications, and reduces the risks of sample contamination. The extraction has been optimized using different temperatures, starting from 40°C up to 80°C. Multiple extractions, until depletion, were performed on the same sample to evaluate the extraction yield. The range of the first extraction yield, carried out at 80°C, which was the best extraction temperature, was 37.4–65.4%, with a %CV range of 2–12. Twenty‐one targeted analytes were extracted and identified by the developed methodology in less than 17 min, including free, monoesters, and diesters carotenoids, in a very fast and efficient way. Quantification of the β‐carotene was carried out by using the optimized conditions.