bluuebunny/crossref_metadata_2025 huggingface dataset:
Association of Polymyalgia Rheumatica With Socioeconomic Status in Primary Care: A Cross‐Sectional Observational Study
Authors: Hayward Richard A. , Rathod Trishna , Muller Sara , Hider Samantha L. , Roddy Edward , Mallen Christian D.
Published: January 2014

Objective

Polymyalgia rheumatica (PMR) is an inflammatory musculoskeletal condition predominantly diagnosed and managed in the community. Socioeconomic status (SES) is known to be associated with many inflammatory rheumatologic conditions, but has not been investigated in relation to PMR. This study aimed to investigate the association between PMR and SES at both the area and individual levels.

Methods

Patients ages >50 years registered with 8 general practices in North Staffordshire were sent a questionnaire requesting details of their general health, SES, and lifestyle. Individual SES was measured using occupation, educational level, and perceived adequacy of income. Area‐level SES was measured using the Index of Multiple Deprivation, derived from respondents' postcodes. Electronic primary care medical records were searched for Read code diagnoses of PMR 2 years before and after the survey.

Results

Of the 13,831 respondents, 141 had a recorded PMR diagnosis in their electronic medical records, a prevalence of 10 per 1,000 patients. No association between PMR and SES was seen at either the individual or area level.

Conclusion

No association was found between PMR and SES at either the area or individual level. Unlike several of the inflammatory arthritides that are more common in the more deprived areas, PMR shows no such association. In part this may be due to PMR affecting an older population. Although socioeconomic factors are important for clinicians and researchers to consider, in patients with PMR, further epidemiologic work is needed to fully characterize this disabling disorder.
Gold‐Catalyzed Carboalkoxylations of 2‐Ethynylbenzyl Ethers to form 1‐ and 2‐Indanones Chemoselectively: Effects of Ligands and Solvents
Authors: Wang Chiou‐Dong , Hsieh Yi‐Feng , Liu Rai‐Shung
Published: January 2014

The selective syntheses of 1‐ and 2‐indanone compounds from 2‐ethynylbenzyl ethers have been achieved with suitable catalysts and solvents. The highly acidic [tris(pentafluorophenyl)phosphine]gold hexafluoroantimonate [P(C6F5)3AuSbF6] in nitromethane (MeNO2) preferably gives 1‐indanones whereas [(ortho‐biphenyl)di(tert‐butyl)phosphine]gold triflimide [P(tBu)2(o‐biphenyl)AuNTf2] in dichloroethane tends to form 2‐indanone derivatives. For 2‐indanone products, we isolated two indenyl methyl ethers for deuterium labeling analyses, providing evidence for π‐alkyne activation.

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Systematic Comparison of Peptidic Proteasome Inhibitors Highlights the α‐Ketoamide Electrophile as an Auspicious Reversible Lead Motif
Authors: Stein Martin L. , Cui Haissi , Beck Philipp , Dubiella Christian , Voss Constantin , Krüger Achim , Schmidt Boris , Groll Michael
Published: January 2014

The ubiquitin–proteasome system (UPS) has been successfully targeted by both academia and the pharmaceutical industry for oncological and immunological applications. Typical proteasome inhibitors are based on a peptidic backbone endowed with an electrophilic C‐terminus by which they react with the active proteolytic sites. Although the peptide moiety has attracted much attention in terms of subunit selectivity, the target specificity and biological stability of the compounds are largely determined by the reactive warheads. In this study, we have carried out a systematic investigation of described electrophiles by a combination of in vitro, in vivo, and structural methods in order to disclose the implications of altered functionality and chemical reactivity. Thereby, we were able to introduce and characterize the class of α‐ketoamides as the most potent reversible inhibitors with possible applications for the therapy of solid tumors as well as autoimmune disorders.
Whole Blood Gene Expression Profiling Predicts Therapeutic Response at Six Months in Patients With Polyarticular Juvenile Idiopathic Arthritis
Authors: Jiang Kaiyu , Sawle Ashley D. , Frank M. Barton , Chen Yanmin , Wallace Carol A. , Jarvis James N.
Published: January 2014

Objective

To determine whether gene expression profiles identified in peripheral whole blood samples could be used to determine therapeutic outcome in a cohort of children with newly diagnosed polyarticular juvenile idiopathic arthritis (JIA).

Methods

Whole blood samples from the Trial of Early Aggressive Therapy (TREAT) in JIA patients were analyzed on Illumina microarrays, and differential gene expression was compared to expression in healthy controls. Microarray results were validated by real‐time quantitative polymerase chain reaction in an independent cohort of samples. Pathway analysis software was used to characterize gene expression profiles. Support vector machines were used to develop predictive models for different patient classes.

Results

Differential gene expression profiles for rheumatoid factor (RF)–positive and RF‐negative patients were remarkably similar. Pathway analysis revealed a broad range of affected pathways, consistent with current mechanistic theories. Modeling showed that the prognosis at 6 months was strongly linked to gene expression at presentation, irrespective of treatment.

Conclusion

Gene expression is linked to therapeutic outcome, and gene expression in the peripheral blood may be a suitable target for a prognostic test.
Dauerhaftes Brettschichtholz aus acetylierter Radiata Kiefer
Authors: Frese Matthias , Blaß Hans Joachim
Published: January 2014

Seit dem Jahr 2007 ist modifizierte Radiata Kiefer auf dem Markt verfügbar. Gegenüber unbehandelter Radiata Kiefer sind deren Dauerhaftigkeit und Formstabilität mit einem patentierten Acetylierungsverfahren verbessert. Die auf diese Weise modifizierte Radiata Kiefer ist eine Alternative zu dauerhaften Tropenhölzern und eignet sich in Form von Brettschichtholz für frei bewitterte tragende Holzkonstruktionen. Das belegen erste realisierte Brückenbauwerke. Der Aufsatz berichtet über die Ergebnisse einer Forschungsarbeit, in der die wissenschaftliche Basis für eine in Deutschland zukünftig geltende baurechtliche Regelung von Brettschichtholz aus acetylierter Radiata Kiefer geschaffen wurde. Diese Arbeit umfasst experimentelle und numerische Untersuchungen zur Biegefestigkeit von Brettschichtholz aus acetylierter Radiata Kiefer und zahlreiche Versuche mit Verbindungsmitteln, auf deren Grundlage differenzierte Brettschichtholz‐Festigkeitsklassen entwickelt bzw. Kennwerte für die Bemessung von stiftförmigen Verbindungsmitteln hergeleitet wurden. Der Aufsatz zeigt Möglichkeiten und Grenzen auf, die bei der Bemessung von tragenden Bauteilen aus Brettschichtholz aus acetylierter Radiata Kiefer zu erwarten sind.

Durabel timber structures made of acetylated Radiata pine

Acetylated Radiata pine is available in the marked since 2007. Compared to the untreated wood, it has an improved durability and dimensional stability due to a patented acetylation process. Acetylated Radiata pine is, therefore, an alternative to durable tropical woods and is suitable for timber structures exposed to weather. The first bridge constructions made out of acetylated Radiata pine and without structural cover give proof of this. The article reports results of a research project that created the scientific basis for a future building regulation in Germany of glulam made out of acetylated Radiata pine. The article covers experimental and numerical investigations of the bending strength of glulam of acetylated Radiata pine and numerous tests with dowel‐type fasteners. The results obtained are the basis for specific glulam strength classes as well as characteristic values for the embedding strength and for the withdrawal parameter of self‐tapping screws. The article aims at showing possibilities and limits regarding structural design with glulam made out of acetylated Radiata pine.
Diagnostic performance of plasma biomarkers in patients with acute intestinal ischaemia
Authors: Matsumoto S , Sekine K , Funaoka H , Yamazaki M , Shimizu M , Hayashida K , Kitano M
Published: January 2014

Background

The aim of this study was to evaluate the use of intestinal fatty acid binding protein (I-FABP) and traditional biomarkers in the early diagnosis of acute intestinal ischaemia of different causes.

Methods

I-FABP, white blood cell (WBC) count, C-reactive protein, base deficit, lactate, lactate dehydrogenase, aspartate aminotransferase, creatine kinase and D-dimer were measured prospectively in consecutive patients suspected of having acute intestinal ischaemia. Biomarker levels were compared in patients with vascular and non-vascular ischaemia.

Results

Two hundred and eight patients with a clinical suspicion of acute intestinal ischaemia were enrolled. Vascular intestinal ischaemia was diagnosed in 24 patients (11·5 per cent), non-vascular ischaemia in 62 (29·8 per cent) and non-ischaemic disease in 122 (58·7 per cent). The levels of most biomarkers (except WBC count and creatine kinase) were significantly higher in the vascular ischaemia group than in the other groups (P < 0·010). However, none of the biomarker levels differed between patients with non-vascular intestinal ischaemia and those with non-ischaemic disease. Receiver operating characteristic (ROC) curve analysis suggested that I-FABP was best at diagnosing vascular intestinal ischaemia (area under the curve 0·88).

Conclusion

Serum biomarkers may be useful in the diagnosis of vascular, but not non-vascular, intestinal ischaemia. Among them, I-FABP shows promise for detecting vascular ischaemia.
Feasibility and safety of a virtual 3‐Fr sheathless‐guiding system for percutaneous coronary intervention
Authors: Tonomura Daisuke , Shimada Yoshihisa , Yano Kentaro , Ito Kazato , Takehara Kosuke , Kino Naoto , Furubayashi Keiichi , Kurotobi Toshiya , Tsuchida Takao , Fukumoto Hitoshi
Published: January 2014

Objectives

To evaluate the feasibility and safety of a virtual 3‐Fr system [5‐Fr sheathless‐guiding catheter (GC)] for percutaneous coronary intervention (PCI).

Background

The use of miniaturized devices for PCI is gaining popularity because of increased patient comfort and decreased risk of access site complications.

Methods

From July 2010 to December 2012, consecutive patients who underwent elective PCI (planned or ad hoc PCI) at our hospital were enrolled. PCI using the virtual 3‐Fr system was attempted as our initial strategy, unless a 6‐Fr or larger GC was considered to be suitable [lesions with heavy calcification, large (>2 mm) side branches, or chronic total occlusion].

Results

Five hundred sixty‐six patients underwent elective PCI during the study period, and 132 patients who met the criteria underwent PCI using the virtual 3‐Fr system. Procedures using the virtual 3‐Fr system were successful in 126 patients (95%); 111 (84%) were performed using the transradial approach, 110 (83%) were ad hoc procedures, and 45 (31%) were complex coronary lesions (type B2 or C). Six patients required conversion to a conventional 5‐ or 6‐Fr sheath and catheter system. No intraoperative complications occurred, and radial artery patency was achieved in all patients who underwent transradial procedures.

Conclusions

PCI using the virtual 3‐Fr system is a feasible and viable alternative to conventional procedures that use a sheath and GC in appropriately selected patients. This small‐caliber system may minimize endovascular trauma, particularly during transradial coronary procedures. © 2014 Wiley Periodicals, Inc.
Serial optical coherence tomography images of trapped balloon catheter after bailout stenting
Authors: Kawamoto Hiroyoshi , Takagi Kensuke , Nakamura Sunao
Published: January 2014

The increased use of endovascular interventions has resulted in a growing number of complications pertaining to unretrievable devices. We report a case of balloon dislodgement in a coronary artery during percutaneous coronary intervention (PCI) with bailout stenting using bare metal stent (BMS). We could not retrieve the remnant despite several attempts and techniques. Thereafter, we deployed BMS to bail out thrombus to recover the coronary flow. Emergency surgery was not considered because of high perioperative mortality (EuroSCORE II 55.91%). We did careful follow‐up with frequency domain optical coherence tomography images, which revealed thick neointima hyperplasia that completely covered the BMS over the balloon. On the other hand, relevant amounts of thrombus remained on the proximal shaft. In cases where remnants are difficult to retrieve using a percutaneous transcatheter technique and the patients are high‐risk for surgery, sealing whole remnants with a BMS is a feasible treatment option. © 2014 Wiley Periodicals, Inc.
Percutanous closure of left ventricular aneurysms in a patient with Loeys–Dietz syndrome
Authors: Chi Lam Simon Cheung , Bertog Stefan , Sievert Horst
Published: January 2014

We report a case of percutaneous closure of multiple left ventricular aneurysms in a patient with inherited aortic‐aneurysm syndrome—the Loeys–Dietz syndrome. One aneurysm was a true aneurysm in the subaortic region and the second one was a pseudoaneurysm at the left ventricular apex. The patient was a high‐risk candidate for repeated operations. Both aneurysms were closed successfully percutaneously in staged procedures. There were no complications. The patient remained clinically well with stable echocardiographic results upon reassessment. This case illustrated that catheter‐based closure of left ventricular aneurysms is a feasible approach in the context of connective tissue abnormalities related to the Loeys–Dietz syndrome. © 2014 Wiley Periodicals, Inc.
Transcatheter aortic valve implantation through a transcarotid approach under local anesthesia
Authors: Rajagopal Rajinikanth , More Ranjit S. , Roberts David H.
Published: January 2014

Aims: We report the first experience of transcatheter aortic valve implantation through a transcarotid approach under local anesthesia. Methods and Results: An 81‐year‐old gentleman with severe symptomatic aortic stenosis was referred for TAVI. He was not suitable for transfemoral, transapical, subclavian, or direct aortic approach. He had severe lung disease and was considered unsuitable for general anesthesia. We, therefore, performed the procedure under local anesthesia though the right common carotid artery (CCA) approach. Superficial cervical block was achieved with Levobupivacaine, and in addition, he also had a target controlled infusion of Remifentanil. Cerebral oximetry was monitored throughout the procedure. The CCA was accessed through surgical cut‐down. Aortic valvuloplasty was performed through a 12‐F sheath, and the CoreValve was deployed successfully through an 18‐F sheath. Conclusion: TAVI is commonly performed through femoral access under local anesthesia. The right carotid artery approach under local anesthesia requires careful monitoring of cerebral oxygen levels but allowed us to perform successful TAVI in this high risk patient when all conventional approaches were contra‐indicated. Compared with a right subclavian or left carotid access, the right carotid offers more direct angle of approach allowing precise valve placement with minimal readjustment during deployment. © 2014 Wiley Periodicals, Inc.
Contribution of Raman Spectroscopy to In Situ Monitoring of a High‐Impact Polystyrene Process
Authors: Brun Nadège , Chevrel Marie‐Claire , Falk Laurent , Hoppe Sandrine , Durand Alain , Chapron David , Bourson Patrice
Published: January 2014

A high‐impact polystyrene (HIPS) process has been studied using Raman spectroscopy as a monitoring technique for the first time. Thermal polymerization of styrene was carried out in the presence of polybutadiene. A Raman probe with a short focal distance, immersed into the reaction medium, allowed in situ monitoring of styrene consumption over the whole reaction progress. A Raman probe with a long focal distance set outside the glass reactor was applied to detect phase separation and phase inversion. Finally, coupling Raman spectroscopy and flow rheometry into a single experimental setup allowed in situ monitoring of both phase behavior and viscosity variation during the HIPS process. Results obtained from Raman spectroscopy were correlated to those from laser granulometry and gravimetric analysis.
Quench Pool Boiling with Temporary Crystalline Enhancers
Authors: Ladizhensky Izhak , Korin Eli , Mazor Gedalia , Nemirovsky Dmitry , Goldkin Evgeny
Published: January 2014

In some industrial activities, the use of permanent heat transfer enhancements such as metal coating, pins, and grooves in cryogenic treatment is quite problematic. Such permanent heat transfer enhancers were replaced with temporary enhancers made of different crystalline materials, here focusing on NaCl, MgSO4·7H2O, CaCl2·2H2O, and C6H5Na3O7·2H2O, which were used during quenching of the sample in the cryogenic liquid, i.e., nitrogen. The time required for sample cooling until the liquid nitrogen saturation temperature is reached decreases significantly when a crystalline coating is applied. The dependence of the cooling time on temporary coating creation parameters such as solution concentration, initial temperature of the sample, and solution spreading time is discussed.
A New Approach for the Photosynthetic Antenna–Reaction Center Complex with a Model Organized Around an s‐Triazine Linker
Authors: Kuhri Susanne , Charalambidis Georgios , Angaridis Panagiotis A. , Lazarides Theodore , Pagona Georgia , Tagmatarchis Nikos , Coutsolelos Athanassios G. , Guldi Dirk M.
Published: January 2014

Two new artificial mimics of the photosynthetic antenna‐reaction center complex have been designed and synthesized (BDP‐H2P‐C60 and BDP‐ZnP‐C60). The resulting electron‐donor/acceptor conjugates contain a porphyrin (either in its free‐base form (H2P) or as Zn‐metalated complex (ZnP)), a boron dipyrrin (BDP), and a fulleropyrrolidine possessing, as substituent of the pyrrolidine nitrogen, an ethylene glycol chain terminating in an amino group C60‐X‐NH2 (X=spacer). In both cases, the three different components were connected by s‐triazine through stepwise substitution reactions of cyanuric chloride. In addition to the facile synthesis, the star‐type arrangement of the three photo‐ and redox‐active components around the central s‐triazine unit permits direct interaction between one another, in contrast to reported examples in which the three components are arranged in a linear fashion. The energy‐ and electron‐transfer properties of the resulting electron‐donor/acceptor conjugates were investigated by using UV/Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. Comparison of the absorption spectra and cyclic voltammograms of BDP‐H2P‐C60 and BDP‐ZnP‐C60 with those of BDP‐H2P, BDP‐ZnP and BDP‐C60, which were used as references, showed that the spectroscopic and electrochemical properties of the individual constituents are basically retained, although some appreciable shifts in terms of absorption indicate some interactions in the ground state. Fluorescence lifetime measurements and transient absorption experiments helped to elucidate the antenna function of BDP, which upon selective excitation undergoes a rapid and efficient energy transfer from BDP to H2P or ZnP. This is then followed by an electron transfer to C60, yielding the formation of the singlet charge‐separated states, namely BDP‐H2P.+‐C60.− and BDP‐ZnP.+‐C60.−. As such, the sequence of energy transfer and electron transfer in the present models mimics the events of natural photosynthesis.
Phenylene‐Coated Magnetic Nanoparticles that Boost Aqueous Asymmetric Transfer Hydrogenation Reactions
Authors: Gao Xiaoshuang , Liu Rui , Zhang Dacheng , Wu Meng , Cheng Tanyu , Liu Guohua
Published: January 2014

Phenylene‐coated organorhodium‐functionalized magnetic nanoparticles are developed through co‐condensation of chiral 4‐(trimethoxysilyl)ethyl)phenylsulfonyl‐1,2‐diphenylethylene‐diamine and 1,4‐bis(triethyoxysilyl)benzene onto Fe3O4 followed complexation with [{Cp*RhCl2}2]. This magnetic catalyst exhibits excellent catalytic activity and high enantioselectivity in asymmetric transfer hydrogenation in aqueous medium. Such activity is attributed to the high hydrophobicity and the confined nature of the chiral organorhodium catalyst. The magnetic catalyst can be easily recovered by using a small external magnet and it can be reused for at least 10 times without loss of its catalytic activity. This characteristic makes it an attractive catalyst for environmentally friendly organic syntheses.
Polytwistane
Authors: Barua Shiblee R. , Quanz Henrik , Olbrich Martin , Schreiner Peter R. , Trauner Dirk , Allen Wesley D.
Published: January 2014

Twistane, C10H16, is a classic D2‐symmetric chiral hydrocarbon that has been studied for decades due to its fascinating stereochemical and thermodynamic properties. Here we propose and analyze in detail the contiguous linear extension of twistane with ethano (ethane‐1,2‐diyl) bridges to create a new chiral, C2‐symmetric hydrocarbon nanotube called polytwistane. Polytwistane, (CH)n, has the same molecular formula as polyacetylene but is composed purely of C(sp3)H units, all of which are chemically equivalent. The polytwistane nanotube has the smallest inner diameter (2.6 Å) of hydrocarbons considered to date. A rigorous topological analysis of idealized polytwistane and a C236H242 prototype optimized by B3LYP density functional theory reveals that the polymer has a nonrepeating, alternating σ‐helix, with an irrational periodicity parameter and an instantaneous rise (or lead) angle near 15 °. A theoretical analysis utilizing homodesmotic equations and explicit computations as high as CCSD(T)/cc‐pVQZ yields the enthalpies of formation ${{\rm{\Delta }}_f H_0^ \circ }$(twistane)=−1.7 kcal mol−1 and ${{\rm{\Delta }}_f H_0^ \circ }$(polytwistane)= +1.28 kcal (mol CH)−1, demonstrating that the hypothetical formation of polytwistane from acetylene is highly exothermic. Hence, polytwistane is synthetically viable both on thermodynamic grounds and also because no obvious pathways exist for its rearrangement to lower‐lying isomers. The present analysis should facilitate the preparation and characterization of this new chiral hydrocarbon nanotube.
Evolution of Actinyl Peroxide Clusters U28 in Dilute Electrolyte Solution: Exploring the Transition from Simple Ions to Macroionic Assemblies
Authors: Li Dong , Simotwo Silas , Nyman May , Liu Tianbo
Published: January 2014

Actinyl peroxide clusters, a unique class of uranyl‐containing nanoclusters discovered in recent years, are crucial intermediates between the (UO2)2+ aqua‐ion monomer and bulk uranyl minerals. Herein, two actinyl polyoxometalate nanoclusters of Cs15[(Ta(O2)4)Cs4K12(UO2(O2)1.5)28]⋅20 H2O (CsKU28) and Na6K9[(Ta(O2)4)Rb4Na12(UO2(O2)1.5)28]⋅20 H2O (RbNaU28) were synthesized by incorporating a central Ta(O2)43− anion that templates a hollow shell of 28 uranyl peroxide polyhedra. When dissolved in aqueous solutions with additional electrolytes, those 1.8 nm‐size macroanions self‐assembled into spherical, hollow, blackberry‐type supramolecular structures, as was characterized by laser‐light scattering (LLS) and TEM techniques. These clusters are the smallest macroions reported to date that form blackberry structures in solution, therefore, can be treated as valuable models for investigating the transition from simple ions to macroions. Kinetic studies showed an unusually long lag phase in the initial self‐assembly process, which is followed by a rapid formation of the blackberry structures in solution. The small cluster size and high surface‐charge density are essential in regulating the supramolecular structure formation, as was shown from the high activation energy barrier of 51.2±2 kJ mol−1. Different countercations were introduced into the system to investigate the effect of ion binding to the length of the lag phase. The current research provides yet another scale of self‐assembly of uranyl peroxide complexes in aqueous media.
Oxidation of Benzyl Alcohol and Carbon Monoxide Using Gold Nanoparticles Supported on MnO2 Nanowire Microspheres
Authors: Alhumaimess Mosaed , Lin Zhongjie , He Qian , Lu Li , Dimitratos Nickolaos , Dummer Nicholas F. , Conte Marco , Taylor Stuart H. , Bartley Jonathan K. , Kiely Christopher J. , Hutchings Graham J.
Published: January 2014

MnO2 was synthesised as a catalyst support material using a hydrothermal method. This involved reacting MnSO4⋅H2O and (NH4)2S2O8 at 120 °C for a range of crystallisation times, which affords control over the morphology and phase composition of the MnO2 formed. Gold was deposited on these supports using sol‐immobilisation, impregnation and deposition precipitation methods, and the resultant materials were used for the oxidation of benzyl alcohol and carbon monoxide. The effect of the support morphology on the dispersion of the gold nanoparticles and the consequent effect on the catalytic performance is described and discussed.
Enantioselective Copper(I/II)‐Catalyzed Conjugate Addition of Nitro Esters to β,γ‐Unsaturated α‐Ketoesters
Authors: Zhang Sheng , Xu Kun , Guo Fengfeng , Hu Yanbin , Zha Zhenggen , Wang Zhiyong
Published: January 2014

A highly enantioselective Michael addition of nitroacetates to β,γ‐unsaturated α‐ketoesters was developed by using chiral copper catalysts. The Michael addition products can be obtained in high yields with up to 99 % ee. With these densely functionalized products, the chiral cyclic nitrones, which are important synthetic intermediates, can be obtained in one step.
Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, meso‐ or rac‐Bis[(diphenylphosphinomethyl)phenylphosphino]methane
Authors: Tanase Tomoaki , Otaki Risa , Nishida Tomoko , Takenaka Hiroe , Takemura Yukie , Kure Bunsho , Nakajima Takayuki , Kitagawa Yasutaka , Tsubomura Taro
Published: January 2014

A series of tetragold(I) complexes supported by tetraphosphine ligands, meso‐ and rac‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (meso‐ and rac‐dpmppm) were synthesized and characterized to show that the tetranuclear AuI alignment varies depending on syn‐ and anti‐arrangements of the two dpmppm ligands with respect to the metal chain. The structures of syn‐[Au4(meso‐dpmppm)2X]X′3 (X=Cl; X′=Cl (4 a), PF6 (4 b), BF4 (4 c)) and syn‐[Au4(meso‐dpmppm)2]X4 (X=PF6 (4 d), BF4 (4 e), TfO (4 f); TfO=triflate) involved a bent tetragold(I) core with a counter anion X incorporated into the bent pocket. Complexes anti‐[Au4(meso‐dpmppm)2]X4 (X=PF6 (5 d), BF4 (5 e), TfO (5 f)) contain a linearly ordered Au4 string and complexes syn‐[Au4(rac‐dpmppm)2X2]X′2 (X=Cl, X′=Cl (6 a), PF6 (6 b), BF4 (6 c)) and syn‐[Au4(rac‐dpmppm)2]X4 (X=PF6 (6 d), BF4 (6 e), TfO (6 f)) consist of a zigzag tetragold(I) chain supported by the two syn‐arranged rac‐dpmppm ligands. Complexes 4 d–f, 5 d–f, and 6 d–f with non‐coordinative large anions are strongly luminescent in the solid state (λmax=475–515 nm, Φ=0.67–0.85) and in acetonitrile (λmax=491–520 nm, Φ=0.33–0.97); the emission was assigned to phosphorescence from 3[dσ*σ*σ*pσσσ] excited state of the Au4 centers on the basis of DFT calculations as well as the long lifetime (a few μs). The emission energy is predominantly determined by the HOMO and LUMO characters of the Au4 centers, which depend on the bent (4), linear (5), and zigzag (6) alignments. The strong emissions in acetonitrile were quenched by chloride anions through simultaneous dynamic and static quenching processes, in which static binding of chloride ions to the Au4 excited species should be the most effective. The present study demonstrates that the structures of linear tetranuclear gold(I) chains can be modified by utilizing the stereoisomeric tetraphosphines, meso‐ and rac‐dpmppm, which may lead to fine tuning of the strongly luminescent properties intrinsic to the AuI4 cluster centers.
Synthesis of Heterodinuclear Hemisalen Complexes on a Hexaarylbenzene Scaffold and their Application for the Cross‐Pinacol Coupling Reaction
Authors: Miyasaka Akihiro , Amaya Toru , Hirao Toshikazu
Published: January 2014

Intermolecular cross‐pinacol coupling reaction between aliphatic and aromatic aldehydes by using heterodinuclear hemisalen complexes 1cis with vanadium(V) and titanium(IV) on a hexaarylbenzene scaffold is reported. Our ligand design is based on the individual activation of two aldehydes by vanadium and titanium, which are positioned with a suitable space on the rigid scaffold. Ligands such as 1cis were synthesized by Diels–Alder addition and decarbonylation reaction, followed by condensation of dialdehyde 3cis with various aminophenols. The influence of the substituents on the ligands on the pinacol coupling reaction was investigated. As a result, the reductive coupling reaction between aliphatic and aromatic aldehydes by using a catalytic amount of 1cis in the presence of Me3SiCl and Zn provided the corresponding cross‐coupled 1,2‐diol in good yields with high cross‐selectivity.
Synthesis and Reactivity of Mononuclear Iron Models of [Fe]‐Hydrogenase that Contain an Acylmethylpyridinol Ligand
Authors: Hu Bowen , Chen Dafa , Hu Xile
Published: January 2014

[Fe]‐hydrogenase has a single iron‐containing active site that features an acylmethylpyridinol ligand. This unique ligand environment had yet to be reproduced in synthetic models; however the synthesis and reactivity of a new class of small molecule mimics of [Fe]‐hydrogenase in which a mono‐iron center is ligated by an acylmethylpyridinol ligand has now been achieved. Key to the preparation of these model compounds is the successful CO cleavage of an alkyl ether moiety to form the desired pyridinol ligand. Reaction of solvated complex [(2‐CH2CO‐6‐HOC5H3N)Fe(CO)2(CH3CN)2]+(BF4)− with thiols or thiophenols in the presence of NEt3 yielded 5‐coordinate iron thiolate complexes. Further derivation produced complexes [(2‐CH2CO‐6‐HOC5H3N)Fe(CO)2(SCH2CH2OH)] and [(2‐CH2CO‐6‐HOC5H3N)Fe(CO)2(CH3COO)], which can be regarded as models of FeGP cofactors of [Fe]‐hydrogenase extracted by 2‐mercaptoethanol and acetic acid, respectively. When the derivative complexes were treated with HBF4⋅Et2O, the solvated complex was regenerated by protonation of the thiolate ligands. The reactivity of several models with CO, isocyanide, cyanide, and H2 was also investigated.
Physicochemical Characterization and Use of Heat Pretreated Commercial Instant Dry Baker's Yeast as a Potential Biosorbent for Cu(II) Removal
Authors: Stanescu Ana‐Maria , Stoica Ligia , Constantin Carolina , Lacatusu Ioana , Oprea Ovidiu , Miculescu Florin
Published: January 2014

Cu(II) is a naturally occurring microelement, essential for many biochemical pathways but its excess causes serious toxicological problems. This study evaluates the ability of heat pretreated commercial instant dry baker's yeast Saccharomyces cerevisiae (HPIBY) to remove Cu(II) ions from aqueous solutions. The importance of the biosorbent properties in the adsorption process was examined by scanning electron microscopy/energy dispersive X‐ray spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry/thermogravimetric analysis, and zeta potential analysis. In order to establish the optimum operating parameters, the influence of pH, biosorbent dosage, and initial metal concentration was investigated. The equilibrium adsorption data were analyzed by using Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption models. The desorption efficiency and the regeneration potential of the HPIBY were evaluated by performing successive biosorption/desorption cycles. The monolayer adsorption capacity (Qm) determined from Langmuir model was 19.53 mg g−1. The maximum removal efficiency, 71.12% was obtained at pH 4.5, for a biosorbent dosage of 0.5% w/v and an initial metal concentration of 50 mg L−1. The zeta potential results suggested that the heat pretreatment enhanced the quantity of organic functional groups with negative charge present on the biosorbent cell walls. The physicochemical characteristics of the biosorbent after metal adsorption and the isotherm data suggested that Cu(II) immobilization by the HPIBY was simultaneously accomplished via electrostatic interactions and chemisorption.
Mitochondrial Fragmentation Is an Important Cellular Event Induced by Ruthenium(II) Polypyridyl Complexes in Osteosarcoma Cells
Authors: Du Yanxin , Fu Xiaoyan , Li Hong , Chen Bolai , Guo Yuhai , Su Guoyi , Zhang Hu , Ning Feipeng , Lin Yongpeng , Mei Wenjie , Chen Tianfeng
Published: January 2014

A series of ruthenium(II) polypyridyl complexes were synthesized and evaluated for their in vitro anticancer activities. The results showed that ruthenium polypyridyl complexes, especially [Ru(bpy)2(p‐tFPIP)]2+ (2 a; bpy=bipyridine, tFPIP=2‐(2‐trifluoromethane phenyl)imidazole[4,5‐f][1,10]phenanthroline), exhibited novel anticancer activity against human cancer cell lines, but with less toxicity to a human normal cell line. The results of flow cytometry and caspase activities analysis indicated that the 2 a‐induced growth inhibition against MG‐63 osteosarcoma cells was mainly caused by mitochondria‐mediated apoptosis. DNA fragmentation and nuclear condensation as detected by TUNEL–DAPI co‐staining further confirmed 2 a‐induced apoptotic cell death. Further, fluorescence imaging revealed that ruthenium(II) polypyridyl complexes could target mitochondria to induce mitochondrial fragmentation, accompanied by depletion of mitochondrial membrane potential. Taken together, these findings suggest a potential application of theses ruthenium(II) complexes in the treatment of cancers.
Heteronuclear Cross‐Relaxation Effects in the NMR Spectroscopy of Hyperpolarized Targets
Authors: Donovan Kevin J. , Lupulescu Adonis , Frydman Lucio
Published: January 2014

Dissolution dynamic nuclear polarization (DNP) enables high‐sensitivity solution‐phase NMR experiments on long‐lived nuclear spin species such as 15N and 13C. This report explores certain features arising in solution‐state 1H NMR upon polarizing low‐γ nuclear species. Following solid‐state hyperpolarization of both 13C and 1H, solution‐phase 1H NMR experiments on dissolved samples revealed transient effects, whereby peaks arising from protons bonded to the naturally occurring 13C nuclei appeared larger than the typically dominant 12C‐bonded 1H resonances. This enhancement of the satellite peaks was examined in detail with respect to a variety of mechanisms that could potentially explain this observation. Both two‐ and three‐spin phenomena active in the solid state could lead to this kind of effect; still, experimental observations revealed that the enhancement originates from 13C→1H polarization‐transfer processes active in the liquid state. Kinetic equations based on modified heteronuclear cross‐relaxation models were examined, and found to well describe the distinct patterns of growth and decay shown by the 13C‐bound 1H NMR satellite resonances. The dynamics of these novel cross‐relaxation phenomena were determined, and their potential usefulness as tools for investigating hyperpolarized ensembles and for obtaining enhanced‐sensitivity 1H NMR traces was explored.
Phosphatation of Zeolite H‐ZSM‐5: A Combined Microscopy and Spectroscopy Study
Authors: van der Bij Hendrik E. , Aramburo Luis R. , Arstad Bjørnar , Dynes James J. , Wang Jian , Weckhuysen Bert M.
Published: January 2014

A variety of phosphated zeolite H‐ZSM‐5 samples are investigated by using a combination of Fourier transfer infrared (FTIR) spectroscopy, single pulse 27Al, 29Si, 31P, 1H‐31P cross polarization (CP), 27Al‐31P CP, and 27Al 3Q magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, scanning transmission X‐ray microscopy (STXM) and N2 physisorption. This approach leads to insights into the physicochemical processes that take place during phosphatation. Direct phosphatation of H‐ZSM‐5 promotes zeolite aggregation, as phosphorus does not penetrate deep into the zeolite material and is mostly found on and close to the outer surface of the zeolite, acting as a glue. Phosphatation of pre‐steamed H‐ZSM‐5 gives rise to the formation of a crystalline tridymite AlPO4 phase, which is found in the mesopores of dealuminated H‐ZSM‐5. Framework aluminum species interacting with phosphorus are not affected by hydrothermal treatment. Dealuminated H‐ZSM‐5, containing AlPO4, retains relatively more framework Al atoms and acid sites during hydrothermal treatment than directly phosphated H‐ZSM‐5.
Joint channel assignment and routing in multiradio multichannel wireless mesh networks with directional antennas
Authors: Sadeghianpour Nasrin , Chuah Teong Chee , Tan Su Wei
Published: January 2014

The aggregate capacity of a wireless mesh network (WMN) is severely affected by interflow interference. In this paper, we propose a network architecture that incorporates directional antennas with multiple orthogonal channels to effectively enhance the performance of WMNs. First, a sectored connectivity graph is introduced to model multiradio multichannel WMNs with directional antennas. Next we formulate the topology design, directional interface assignment, channel allocation, and routing mathematically as a mixed integer linear programming problem. This problem is solved using an iterated local search algorithm to obtain optimized network resource allocation. Simulation results indicate that the proposed architecture can achieve higher packet delivery ratio while providing better network fairness. Copyright © 2014 John Wiley & Sons, Ltd.
Microwave‐Assisted Synthesis of Substituted Pyrrolo[2,3‐d]pyrimidines
Authors: Prieur Vanessa , Rubio‐Martínez Jaime , Font‐Bardia Mercè , Guillaumet Gérald , Pujol M. Dolors
Published: January 2014

A new synthetic route to triaryl pyrrolo[2,3‐d]pyrimidines from common 4,6‐dichloropyrimidine has been developed. The triarylated compounds are synthesized by three cross‐coupling reactions using three different catalysts. The introduction of a C‐6 aryl group was achieved in a two‐step process under Sonogashira conditions [Pd(dba)2/CuI] followed by intramolecular cyclization, and application of Suzuki–Miyaura conditions [Pd(PPh3)4; PdCl2(PPh3)2] led to C‐4 and C‐5 diarylation. This sequence allows a flexible synthetic approach to highly arylated pyrrolopyrimidines containing different aryl groups.
Organylzinc Chalcogenolate Promoted Michael‐Type Addition of α,β‐Unsaturated Carbonyl Compounds
Authors: Lóren Nunes Vanessa , de Oliveira Ingryd Cristina , Soares do Rêgo Barros Olga
Published: January 2014

We present the chemo‐, regio‐, and stereoselective synthesis of vinyl chalcogenide compounds promoted by organylzinc chalcogenolates. In this protocol, reductive cleavage of diorganyl dichalcogenide bonds by the Zn/NH4OH system led to organylzinc chalcogenolates. The reaction was performed with propiolic acids and esters and afforded β‐organochalcogenacrylic acids and esters under mild basic conditions. The stereochemistry corresponded to anti‐Markovnikov addition of the organyl chalcogenolate constituents across the triple bond.
N‐Benzoyl‐L‐Threonine‐Isopropyl‐Ester‐Mediated Crystallization‐Induced Dynamic Resolution of α‐Bromo Arylacetates for the Asymmetric Synthesis of α‐Thio and α‐Oxy Arylacetates
Authors: Park Kon Ji , Kim Yelim , Lee Myung‐su , Park Yong Sun
Published: January 2014

N‐Benzoyl‐L‐threonine‐isopropyl‐ester‐mediated crystallization‐induced dynamic resolution (CIDR) of configurationally labile α‐bromo arylacetates has been investigated. The CIDR was successfully used for the asymmetric preparation of these compounds with up to 98:2 dr, under solution and solvent‐free conditions. Subsequent nucleophilic substitution reactions with sulfur and oxygen nulceophiles gave α‐thio and α‐oxy arylacetates with up to 98:2 dr. The method was further developed for the preparation of highly enantioenriched 2‐phenylthio‐2‐arylethanols with up to 97:3 er, and 1,4‐benzoxazin‐3‐ones with up to 94:6 er.
Tuberculosis drug discovery in the post‐post‐genomic era
Authors: Lechartier Benoit , Rybniker Jan , Zumla Alimuddin , Cole Stewart T
Published: January 2014

The expectation that genomics would result in new therapeutic interventions for infectious diseases remains unfulfilled. In the post‐genomic era, the decade immediately following the availability of the genome sequence of Mycobacterium tuberculosis, tuberculosis (TB) drug discovery relied heavily on the target‐based approach but this proved unsuccessful leading to a return to whole cell screening. Genomics underpinned screening by providing knowledge and many enabling technologies, most importantly whole genome resequencing to find resistance mutations and targets, and this resulted in a selection of leads and new TB drug candidates that are reviewed here. Unexpectedly, many new targets were found to be ‘promiscuous’ as they were inhibited by a variety of different compounds. In the post‐post‐genomics era, more advanced technologies have been implemented and these include high‐content screening, screening for inhibitors of latency, the use of conditional knock‐down mutants for validated targets and siRNA screens. In addition, immunomodulation and pharmacological manipulation of host functions are being explored in an attempt to widen our therapeutic options.
Constructing valid spatial processes on the sphere using kernel convolutions
Authors: Heaton M.J. , Katzfuss M. , Berrett C. , Nychka D.W.
Published: January 2014

Remotely sensed data products are now routinely used to study various aspects of the Earth's atmosphere. These remote sensing datasets are typically very high dimensional, have near global coverage and exhibit nonstationary spatial correlation structures. Proper statistical analysis of these datasets should be sufficiently flexible to account for all these aspects. To this end, we develop a kernel convolution construction of spatial processes on a sphere. As is the case with kernel convolution constructions on the plane, we establish a link between stationary kernels and a stationary covariance function on the sphere via the spherical harmonic decomposition of the kernel. We also introduce the Kent distribution as an appropriate kernel with interpretable parameters to be used in the kernel convolution construction. We demonstrate the discrete kernel convolution model using a dataset of remotely sensed CO2concentrations over the globe. Copyright © 2014 John Wiley & Sons, Ltd.
HOW IS DISASTER AID ALLOCATED WITHIN POOR COMMUNITIES? RISK SHARING AND SOCIAL HIERARCHY
Authors: Takasaki Yoshito
Published: January 2014

How disaster aid is allocated within poor communities is little understood. Using original post‐disaster survey data in rural Fiji that capture household‐level traditional kin status, cyclone damage and aid allocations over post‐disaster phases, this paper demonstrates that allocations are driven by informal risk‐sharing institutions and social hierarchies. On one hand, in response to a disaster with moderate severity, private risk sharing can strongly make up limited aid, making targeting aid on damage appear weak as a result. On the other hand, local elites can dominate not only aid allocation for given damage but also the targeting on damage. Copyright © 2014 John Wiley & Sons, Ltd.
Optimized three‐dimensional fast‐spin‐echo MRI
Authors: Mugler John P.
Published: January 2014

Spin‐echo‐based acquisitions are the workhorse of clinical MRI because they provide a variety of useful image contrasts and are resistant to image artifacts from radio‐frequency or static field inhomogeneity. Three‐dimensional (3D) acquisitions provide datasets that can be retrospectively reformatted for viewing in freely selectable orientations, and are thus advantageous for evaluating the complex anatomy associated with many clinical applications of MRI. Historically, however, 3D spin‐echo‐based acquisitions have not played a significant role in clinical MRI due to unacceptably long acquisition times or image artifacts associated with details of the acquisition method. Recently, optimized forms of 3D fast/turbo spin‐echo imaging have become available from several MR‐equipment manufacturers (for example, CUBE [GE], SPACE [Siemens], and VISTA [Philips]). Through specific design strategies and optimization, including short non–spatially selective radio‐frequency pulses to significantly shorten the echo spacing and variable flip angles for the refocusing radio‐frequency pulses to suppress blurring or considerably lengthen the useable duration of the spin‐echo train, these techniques permit single‐slab 3D imaging of sizeable volumes in clinically acceptable acquisition times. These optimized fast/turbo spin‐echo pulse sequences provide a robust and flexible approach for 3D spin‐echo‐based imaging with a broad range of clinical applications. J. Magn. Reson. Imaging 2014;39:745–767. © 2014 Wiley Periodicals, Inc.
Die deutsche Braunkohlenindustrie im Jahr 2012
Authors: Maaßen Uwe , Schiffer Hans‐Wilhelm
Published: January 2014

185,4 Mill. t Braunkohle hat die deutsche Braunkohlenindustrie hat im Jahr 2012 gefördert. Dies entspricht einem Energiegehalt von 56,1 Mill. t SKE. Die Braunkohlenförderung deckt damit rund 12 % des gesamten inländischen Energiebedarfs. Der vorliegende Beitrag gibt einen Überblick über den Braunkohlenbergbau sowie die Verwendung von Braunkohle und fasst die aktuellen Entwicklungen auf den Gebieten der Braunkohlenverstromung und stofflichen Verwertung zusammen.

The German lignite industry in 2012

185.4 mill. t of lignite were extracted by the German lignite industry in 2012. This corresponds to an energy content of 56.1 mill. t SKE (coal units). Lignite extraction thus covers about 12 % of total German energy demand. The current article gives an overview of the mining and applications of lignite and summarises current developments in the areas of electricity generation and other applications of lignite.
125 Jahre Staatlicher Geologischer Dienst in Baden
Authors: Watzel Ralph
Published: January 2014

Am 21. Dezember 2013 jährt sich die formale Gründung der Großherzoglich badischen geologischen Landesanstalt durch Großherzog Friedrich I. von Baden zum 125. Mal. Sie war der erste Staatliche Geologische Dienst auf der Fläche des heutigen Bundeslands Baden‐Württemberg. Am 7. August 1903 folgte der Gründungserlass der Geologischen Abteilung beim Statistischen Landesamt des Königreichs Württemberg.