bluuebunny/crossref_metadata_2025 huggingface dataset:
Carbamate Stabilities of Sterically Hindered Amines from Quantum Chemical Methods: Relevance for CO2 Capture
Authors: Gangarapu Satesh , Marcelis Antonius T. M. , Zuilhof Han
Published: November 2013

The influence of electronic and steric effects on the stabilities of carbamates formed from the reaction of CO2 with a wide range of alkanolamines was investigated by quantum chemical methods. For the calculations, B3LYP, M11‐L, MP2, and spin‐component‐scaled MP2 (SCS‐MP2) methods were used, coupled with SMD and SM8 solvation models. A reduction in carbamate stability leads to an increased CO2 absorption capacity of the amine and a reduction of the energy required for solvent regeneration. Important factors for the reduction of the carbamate stability were an increase in steric hindrance around the nitrogen atom, charge on the N atom and intramolecular hydrogen bond strength. The present study indicates that secondary ethanolamines with sterically hindering groups near the N atom show significant potential as candidates for industrial CO2‐capture solvents.
Oxidative Coupling of 1‐Naphthols over Noble and Base Metal Catalysts
Authors: Maphoru Mabuatsela V. , Heveling Josef , Pillai Sreejarani K.
Published: November 2013

Bismuth‐promoted platinum catalysts were tested for the oxidative coupling of 2‐ and 4‐substituted 1‐naphthols at different temperatures and ambient pressure. The principal final products are the 3,3′‐substituted 1,1′‐binaphthalenylidene‐4,4′‐diones and the 4,4′‐substituted 2,2′‐binaphthalenylidene‐1,1′‐diones, respectively. Hydrogen peroxide was used as the oxidant. Only naphthols with electron‐donating substituents reacted. The corresponding binaphthalenyl diols can be considered as reaction intermediates. Yields of up to 99 % were obtained from 2‐methyl‐1‐naphthol as the starting material within 20 minutes. Probably for steric reasons, the diol is the final product obtained from 2‐ethyl‐1‐naphthol. For 4‐methoxy‐1‐naphthol the outcome is determined by the reaction temperature. At 25 °C the expected 1,1′‐dione is the major product, whereas at 60 °C 1′‐hydroxy‐4′‐methoxy‐2,2′‐binaphthalenyl‐1,4‐dione is formed; the loss of one methoxy unit and the preservation of the hydroxy group can be explained by the competitive cleavage of one of the two OMe bonds at higher temperature. Unpromoted platinum and a range of other metallic catalysts, including gold and Raney nickel, were also found to be active. The products obtained are brightly colored solids that could be used as dyes. The method described is truly catalytic and environmentally benign. The potential of the technique justifies further research to expand on the applicability of this novel method.
Analysis of cooperative and competitive spectrum sharing for heterogeneous networks based on differential dynamics model
Authors: Zhu Xiaorong , Dianati Mehrdad , Zhu Hongbo
Published: November 2013

The heterogeneous networks belonging to different service providers form a coalition system for maximizing the profit, where they may either compete or cooperate with each other. In this paper, we introduce the Lokta–Volterra model, a differential dynamics model, to build the competitive and cooperative mechanisms of heterogeneous networks. It considers the natural growth rate of the network itself and competitive and cooperative effects among networks. Then, according to the ordinary differential principle, the stability of the proposed model and its equilibrium points are analyzed. And finally, system performances are evaluated by Vensim that is used for developing, analyzing, and packaging dynamic feedback models. Analysis and simulation results show that the natural growth rate of the network cannot increase its profit, but effective cooperative mechanism among heterogeneous networks can increase the profit of each network. Copyright © 2013 John Wiley & Sons, Ltd.
Proof of cannabis administration by sensitive detection of 11‐nor‐Delta(9)‐tetrahydrocannabinol‐9‐carboxylic acid in hair using selective methylation and application of liquid chromatography‐ tandem and multistage mass spectrometry
Authors: Thieme Detlef , Sachs Hans , Uhl Michael
Published: November 2013

The identification of 11‐nor‐Δ9‐tetrahydrocannabinol‐9‐carboxylic acid (THCCOOH) in hair represents an exceptional forensic analytical challenge due to low target concentrations in a complex matrix. Several dedicated techniques [gas chromatography – negative chemical ionization‐ tandem mass spectrometry (GC‐NCI‐MS/MS) or GC‐GC‐MS couplings] were specifically introduced into forensic toxicology aiming to a selective and sensitive identification of THCCOOH in hair. The combination of liquid‐chromatography (LC) and MS/MS gained an outstanding relevance in forensic toxicology (including the detection of cannabinoids). However, its application to hair matrix is characterized by a lack of specificity which is due to the unspecific decarboxylation as most abundant fragmentation reaction.

Therefore, various chemical modifications of the carboxyl and/or phenolic hydroxyl groups were examined to improve the selectivity. The selective methylation of the 9‐carboxyl‐group proved to be the most efficient derivatization procedure. Hair extracts were redissolved in acetonitrile and after addition of few milligrams of solid sodium carbonate derivatized with 25 μL methyl iodide. The resulting THC‐9‐carboxymethylester was separated by conventional reverse phase LC and selectively detected using negative electrospray ionization by recording the fragmentation reactions 357➔325 and 357➔297. Resulting limits of quantification were below 100 fg/mg. A further significant improvement was achieved by application of the multistage MS3 fragmentation 357➔325➔297. To verify the validity of this procedure, a systematic quantitative comparison of THCCOOH concentrations in hair with data from a well established GC‐NCI‐MS/MS technique was performed. Both techniques proved to be in good accordance (R2 =0.647, p = <0.001) and equally suitable for hair testing of THCCOOH. Copyright © 2013 John Wiley & Sons, Ltd.
Relationship between photosynthetic phosphorus‐use efficiency and foliar phosphorus fractions in tropical tree species
Authors: Hidaka Amane , Kitayama Kanehiro
Published: November 2013

How plants develop adaptive strategies to efficiently use nutrients on infertile soils is an important topic in plant ecology. It has been suggested that, with decreasing phosphorus (P) availability, plants increase photosynthetic P‐use efficiency (PPUE) (i.e., the ratio of instantaneous photosynthetic carbon assimilation rate per unit foliar P). However, the mechanism to increase PPUE remains unclear. In this study, we tested whether high PPUE is explained by an optimized allocation of P in cells among P‐containing biochemical compounds (i.e., foliar P fractions). We investigated the relationships among mass‐based photosynthetic carbon assimilation rate (Amass), PPUE, total foliar P concentration, and foliar P fractions in 10 tree species in two tropical montane rain forests with differing soil P availability (five species on sedimentary soils and five species on P‐poorer ultrabasic serpentine soils) on Mount Kinabalu, Borneo. We chemically fractionated foliar P into the following four fractions: metabolic P, lipid P, nucleic acid P, and residual P. Amass was positively correlated with the concentrations of total foliar P and of metabolic P across 10 tree species. Mean Amass and mean concentrations of total foliar P and of each foliar P fraction were lower on the P‐poorer ultrabasic serpentine soils than on the sedimentary soils. There was a negative relationship between the proportion of metabolic P per total P and the proportion of lipid P per total P. PPUE was positively correlated with the ratio of metabolic P to lipid P. High PPUE is explained by the net effect of a relatively greater investment of P into P‐containing metabolites and a relatively lesser investment into phospholipids in addition to generally reduced concentrations of all P fractions. We conclude that plants optimize the allocation of P among foliar P fractions for maintaining their productivity and growth and for reducing demand for P as their adaptation to P‐poor soils.
Preparation of Diversely Substituted Triarylmethyl Radicals by the Quenching of Tris(2,3,5,6‐tetrathiaaryl)methyl Cations with C‐, N‐, P‐, and S‐Nucleophiles
Authors: Tormyshev Victor M. , Rogozhnikova Olga Yu. , Bowman Michael K. , Trukhin Dmitry V. , Troitskaya Tatiana I. , Vasiliev Vladimir G. , Shundrin Leonid A. , Halpern Howard J.
Published: November 2013

C‐, N‐, P‐, and S‐nucleophiles reacted with symmetrical tris(2,3,5,6‐tetrathiaaryl)methyl cations, generated from the corresponding triarylmethanols by strong acids, to give a variety of asymmetrical monosubstituted persistent triarylmethyl (TAM) radicals as the major products. The only byproducts were symmetrical TAMs.
Fas (CD95) expression in myeloid cells promotes obesity‐induced muscle insulin resistance
Authors: Wueest Stephan , Mueller Rouven , Blüher Matthias , Item Flurin , Chin Annie S H , Wiedemann Michael S F , Takizawa Hitoshi , Kovtonyuk Larisa , Chervonsky Alexander V , Schoenle Eugen J , Manz Markus G , Konrad Daniel
Published: November 2013

Low‐grade inflammation in adipose tissue and liver has been implicated in obesity‐associated insulin resistance and type 2 diabetes. Yet, the contribution of inflammatory cells to the pathogenesis of skeletal muscle insulin resistance remains elusive. In a large cohort of obese human individuals, blood monocyte Fas (CD95) expression correlated with systemic and skeletal muscle insulin resistance. To test a causal role for myeloid cell Fas expression in the development of skeletal muscle insulin resistance, we generated myeloid/haematopoietic cell‐specific Fas‐depleted mice. Myeloid/haematopoietic Fas deficiency prevented the development of glucose intolerance in high fat‐fed mice, in ob/ob mice, and in mice acutely challenged by LPS. In vivo, ex vivo and in vitro studies demonstrated preservation of muscle insulin responsiveness with no effect on adipose tissue or liver. Studies using neutralizing antibodies demonstrated a role for TNFα as mediator between myeloid Fas and skeletal muscle insulin resistance, supported by significant correlations between monocyte Fas expression and circulating TNFα in humans. In conclusion, our results demonstrate an unanticipated crosstalk between myeloid cells and skeletal muscle in the development of obesity‐associated insulin resistance.
Synthesis of Bis‐ and Tris(3‐H‐1,3‐azaphospholo)benzenes
Authors: Marchenko Anatoliy , Koidan Heorgiy , Huryeva Anastasiya , Smaliy Radomyr , Vlasenko Yurii , Gutov Oleksii , Kostyuk Aleksandr
Published: November 2013

The previously developed intramolecular cyclocondensation of C‐phosphanyl(N‐aryl)formamidines into 3‐H‐1,3‐benzazaphospholes has been successfully extended to 1,3‐diaminobenzene and 1,3,5‐triaminobenzene. Its condensation presents the way to tricyclic and tetracyclic azaphospholes. Their structures were confirmed by spectroscopic methods and key tricyclic and tetracyclic compounds were further characterized by single crystal X‐ray diffraction.
C10X polymorphism in the CARD8 gene is associated with bacteraemia
Authors: Asfaw Idosa Berhane , Sahdo Berolla , Balcha Ermias , Kelly Anne , Söderquist Bo , Särndahl Eva
Published: November 2013

The NLRP3 inflammasome is an intracellular multi‐protein complex that triggers caspase‐1 mediated maturation of interleukin‐1β (IL‐1β); one of the most potent mediators of inflammation and a major cytokine produced during severe infections, like sepsis. However, the excessive cytokine levels seem to stage for tissue injury and organ failure, and high levels of IL‐1β correlates with severity and mortality of sepsis. Instead, recent data suggest caspase‐1 to function as a guardian against severe infections. CARD8 has been implied to regulate the synthesis of IL‐1β via interaction to caspase‐1. In recent years, polymorphism of CARD8 (C10X) per se or in combination with NLRP3 (Q705K) has been implicated with increased risk of inflammation. The aim was to investigate the correlation of these polymorphisms with severe blood stream infection. Human DNA was extracted from blood culture bottles that were found to be positive for microbial growth (i.e. patients with bacteraemia). Polymorphisms Q705K in the NLRP3 gene and C10X in the CARD8 gene were genotyped using TaqMan genotyping assay. The results were compared to healthy controls and to samples from patients with negative cultures. The polymorphism C10X was significantly over‐represented among patients with bacteraemia as compared to healthy controls, whereas patients with negative blood culture were not associated with a higher prevalence. No association was observed with polymorphism Q705K of NLRP3 in either group of patients. Patients carrying polymorphism C10X in the CARD8 gene are at increased risk of developing bacteraemia and severe inflammation.
Analgesic and anti‐hyperalgesic effects of muscle injections with lidocaine or saline in patients with fibromyalgia syndrome
Authors: Staud R. , Weyl E.E. , Bartley E. , Price D.D. , Robinson M.E.
Published: November 2013

Background

Patients with musculoskeletal pain syndrome including fibromyalgia (FM) complain of chronic pain from deep tissues including muscles. Previous research suggests the relevance of impulse input from deep tissues for clinical FM pain. We hypothesized that blocking abnormal impulse input with intramuscular lidocaine would decrease primary and secondary hyperalgesia and FM patients' clinical pain.

Methods

We enrolled 62 female patients with FM into a double‐blind controlled study of three groups who received 100 or 200 mg of lidocaine or saline injections into both trapezius and gluteal muscles. Study variables included pressure and heat hyperalgesia as well as clinical pain. In addition, placebo factors like patients' anxiety and expectation for pain relief were used as predictors of analgesia.

Results

Primary mechanical hyperalgesia at the shoulders and buttocks decreased significantly more after lidocaine than saline injections (p = 0.004). Similar results were obtained for secondary heat hyperalgesia at the arms (p = 0.04). After muscle injections, clinical FM pain significantly declined by 38% but was not statistically different between lidocaine and saline conditions. Placebo‐related analgesic factors (e.g., patients' expectations of pain relief) accounted for 19.9% of the variance of clinical pain after the injections. Injection‐related anxiety did not significantly contribute to patient analgesia.

Conclusion

These results suggest that muscle injections can reliably reduce clinical FM pain, and that peripheral impulse input is required for the maintenance of mechanical and heat hyperalgesia of patients with FM. Whereas the effects of muscle injections on hyperalgesia were greater for lidocaine than saline, the effects on clinical pain were similar for both injectates.
Development and verification of a new wind speed forecasting system using an ensemble Kalman filter data assimilation technique in a fully coupled hydrologic and atmospheric model
Authors: Williams John L. , Maxwell Reed M. , Monache Luca Delle
Published: November 2013

Wind power is rapidly gaining prominence as a major source of renewable energy. Harnessing this promising energy source is challenging because of the chaotic nature of wind and its inherently intermittent nature. Accurate forecasting tools are critical to support the integration of wind energy into power grids and to maximize its impact on renewable energy portfolios. We have adapted the Data Assimilation Research Testbed (DART), a community software facility which includes the ensemble Kalman filter (EnKF) algorithm, to expand our capability to use observational data to improve forecasts produced with a fully coupled hydrologic and atmospheric modeling system, the ParFlow (PF) hydrologic model and the Weather Research and Forecasting (WRF) mesoscale atmospheric model, coupled via mass and energy fluxes across the land surface, and resulting in the PF.WRF model. Numerous studies have shown that soil moisture distribution and land surface vegetative processes profoundly influence atmospheric boundary layer development and weather processes on local and regional scales. We have used the PF.WRF model to explore the connections between the land surface and the atmosphere in terms of land surface energy flux partitioning and coupled variable fields including hydraulic conductivity, soil moisture, and wind speed and demonstrated that reductions in uncertainty in these coupled fields realized through assimilation of soil moisture observations propagate through the hydrologic and atmospheric system. The sensitivities found in this study will enable further studies to optimize observation strategies to maximize the utility of the PF.WRF‐DART forecasting system.
A factorial analysis of the combined effects of hydrogel fabrication parameters on the in vitro swelling and degradation of oligo(poly(ethylene glycol) fumarate) hydrogels
Authors: Lam Johnny , Kim Kyobum , Lu Steven , Tabata Yasuhiko , Scott David W. , Mikos Antonios G. , Kurtis Kasper F.
Published: November 2013

In this study, a full factorial approach was used to investigate the effects of poly(ethylene glycol) (PEG) molecular weight (MW; 10,000 vs. 35,000 nominal MW), crosslinker‐to‐macromer carbon–carbon double bond ratio (DBR; 40 vs. 60), crosslinker type (PEG‐diacrylate (PEGDA) vs. N,N′‐methylene bisacrylamide (MB)), crosslinking extent of incorporated gelatin microparticles (low vs. high), and incubation medium composition (with or without collagenase) on the swelling and degradation characteristics of oligo[(poly(ethylene glycol) fumarate)] (OPF) hydrogel composites as indicated by the swelling ratio and the percentage of mass remaining, respectively. Each factor consisted of two levels, which were selected based on previous in vitro and in vivo studies utilizing these hydrogels for various tissue engineering applications. Fractional factorial analyses of the main effects indicated that the mean swelling ratio and the mean percentage of mass remaining of OPF composite hydrogels were significantly affected by every factor. In particular, increasing the PEG chain MW of OPF macromers significantly increased the mean swelling ratio and decreased the mean percentage of mass remaining by 5.7 ± 0.3 and 17.2 ± 0.6%, respectively. However, changing the crosslinker from MB to PEGDA reduced the mean swelling ratio and increased the mean percentage of mass remaining of OPF composite hydrogels by 4.9 ± 0.2 and 9.4 ± 0.9%, respectively. Additionally, it was found that the swelling characteristics of hydrogels fabricated with higher PEG chain MW or with MB were more sensitive to increases in DBR. Collectively, the main and cross effects observed between factors enables informed tuning of the swelling and degradation properties of OPF‐based hydrogels for various tissue engineering applications. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 102A: 3477–3487, 2014.
Photofunctionalization increases the bioactivity and osteoconductivity of the titanium alloy Ti6Al4V
Authors: Minamikawa Hajime , Ikeda Takayuki , Att Wael , Hagiwara Yoshiyuki , Hirota Makoto , Tabuchi Masako , Aita Hideki , Park Wonhee , Ogawa Takahiro
Published: November 2013

This study examined the effect of photofunctionalization on bioactivity and osteoconductivity of titanium alloy Ti6Al4V. We also tested a hypothesis that the effect of photofunctionalization is as substantial as the one of surface roughening. Two different surface morphology, a roughened surface (sandblasted and acid‐etched surface) and relatively smooth surface (machined surface), was tested. Ti6Al4V samples were photofunctionalized with UV light for 15 min using a photo device. Photofunctionalization converted Ti6Al4V surfaces from hydrophobic to superhydrophilic. The attachment, spread, proliferation, and the expression of functional phenotype of bone marrow‐derived osteoblasts were promoted on photofunctionalized Ti6Al4V surfaces. The strength of bone‐implant integration examined using a biomechanical push‐in test in a rat femur model was at least 100% greater for photofunctionalized implants than for untreated implants. These effects were seen on both surface types. The strength of bone‐implant integration for photofunctionalized machined implants was greater than that for untreated roughened implants, indicating that the impact of photofunctionalization may be greater than that of surface roughening. Newly prepared Ti alloy was hydrophilic, whereas the hydrophilic status degraded with time and was converted to hydrophobic in 4 weeks. This finding uncovered biological aging of Ti alloy and allowed us to consider photofunctionalization as a countermeasure for aging. These results suggest that photofunctionalization accelerates and enhances bone‐implant integration of Ti6Al4V regardless of smooth and roughened surface features, supporting photofunctionalization as an effective and viable measure for improving efficacy of a wide range of Ti6Al4V‐based materials used in dental and orthopedic medicine. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 102A: 3618–3630, 2014.
Role of vascular networks in extending glucose sensor function: Impact of angiogenesis and lymphangiogenesis on continuous glucose monitoring in vivo
Authors: Klueh Ulrike , Antar Omar , Qiao Yi , Kreutzer Donald L.
Published: November 2013

The concept of increased blood vessel (BV) density proximal to glucose sensors implanted in the interstitial tissue increases the accuracy and lifespan of sensors is accepted, despite limited existing experimental data. Interestingly, there is no previous data or even conjecture in the literature on the role of lymphatic vessels (LV) alone, or in combination with BV, in enhancing continuous glucose monitoring (CGM) in vivo. To investigate the impact of inducing vascular networks (BV and LV) at sites of glucose sensor implantation, we utilized adenovirus based local gene therapy of vascular endothelial cell growth factor‐A (VEGF‐A) to induce vessels at sensor implantation sites. The results of these studies demonstrated that (1) VEGF‐A based local gene therapy increases vascular networks (blood vessels and lymphatic vessels) at sites of glucose sensor implantation; and (2) this local increase of vascular networks enhances glucose sensor function in vivo from 7 days to greater than 28 days postsensor implantation. This data provides “proof of concept” for the effective usage of local angiogenic factor (AF) gene therapy in mammalian models in an effort to extend CGM in vivo. It also supports the practice of a variety of viral and nonviral vectors as well as gene products (e.g. anti‐inflammatory and anti‐fibrosis genes) to engineer “implant friendly tissues” for the usage with implantable glucose sensors as well as other implantable devices. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 102A: 3512–3522, 2014.
CD99 Drives Terminal Differentiation of Osteosarcoma Cells by Acting as a Spatial Regulator of ERK 1/2
Authors: Sciandra Marika , Marino Maria Teresa , Manara Maria Cristina , Guerzoni Clara , Grano Maria , Oranger Angela , Lucarelli Enrico , Lollini Pier-Luigi , Dozza Barbara , Pratelli Loredana , Di Renzo Maria Flavia , Colombo Mario Paolo , Picci Piero , Scotlandi Katia
Published: November 2013

Differentiation therapy is an attractive treatment for osteosarcoma (OS). CD99 is a cell surface molecule expressed in mesenchymal stem cells and osteoblasts that is maintained during osteoblast differentiation while lost in OS. Herein, we show that whenever OS cells regain CD99, they become prone to reactivate the terminal differentiation program. In differentiating conditions, CD99-transfected OS cells express osteocyte markers, halt proliferation, and largely die by apoptosis, resembling the fate of mature osteoblasts. CD99 induces ERK activation, increasing its membrane-bound/cytoplasmic form rather than affecting its nuclear localization. Through cytoplasmic ERK, CD99 promotes activity of the main osteogenic transcriptional factors AP1 and RUNX2, which in turn enhance osteocalcin and p21WAF1/CIP1, leading to G0/G1 arrest. These data underscore the alternative positions of active ERK into distinct subcellular compartments as key events for determining OS fate. © 2014 The Authors. Journal of Bone and Mineral Research published by Wiley Periodicals, Inc. on behalf of the American Society for Bone and Mineral Research.
Statistical analysis of the quantal basis of secretory granule formation
Authors: Křepelová‐DROR Marika , Hammel Ilan , Meilijson Isaac
Published: November 2013

ABSTRACT

The size distribution of vesicles exocytosed from secretory cells displays quantal nature, vesicle volume is periodic multi‐modal, suggesting that these heterogeneous vesicles are aggregate sums of a variable number of homogeneous basic granules. Whether heterogeneity is a lumping‐together artifact of the measurement or an inherent intra‐cell feature of the vesicles is an unresolved question. Recent empirical evidence will be provided for the quantal nature of intra‐cell vesicle volume, supporting the controversial paradigm of homotypic fusion: basic cytoplasmic granules fuse with each other to create heterogeneously sized vesicles. An EM‐algorithm‐based method is presented for the conversion of multi‐modal to quantal data that provides as by‐product estimates of means and variances of basic granule packaging.Microsc. Res. Tech. 77:1–10, 2014. © 2013 Wiley Periodicals, Inc.
Detailed in vitro study of the photosensitization reaction of extracellular talaporfin sodium in rat myocardial cells
Authors: Ogawa Emiyu , Ito Arisa , Arai Tsunenori
Published: November 2013

Background and Objective

We proposed a new non‐thermal treatment for tachyarrhythmia that employs an extracellular photosensitization reaction. Oxygen depletion may easily occur in in vitro studies of this reaction because the photosensitizing agent is often highly concentrated in such studies. The aim of the current study was to examine the progress of the extracellular photosensitization reaction and the photocytotoxicity of extracellular Talaporfin sodium on myocardial cells for application in tachyarrhythmia therapy.

Materials and Methods

Photosensitization reactions were performed in single wells of 96‐well plates; Talaporfin sodium solution concentrations from 5 to 40 µg/ml, radiant exposures up to 40 J/cm2, and irradiance of 0.29 W/cm2 from a continuous wave (CW) red diode laser (wavelength: 663 nm) were used. We measured transient changes of temperature, photosensitizer fluorescence, dissolved oxygen pressure, and photosensitizer solution absorbance to monitor the progress of the photosensitization reaction in the system during laser irradiation. Rat myocardial cells were cultured in 96‐well plates, and the drug‐light interval was set to 15 minutes. We used a WST assay to measure cell lethality 2 hours after laser irradiation.

Results

A strong photosensitization reaction occurred several seconds after initiation of laser irradiation; this initial reaction depended upon dissolved oxygen. A gentler continuous photosensitization reaction followed the initial reaction, and was associated with temperature increases of less than 10°C. The oxygen pressure was kept in approximately 40 mmHg of the myocardial tissue oxygen pressure in the gentle photosensitization reaction phase. At radiant exposures from 10 to 40 J/cm2, a photosensitizer concentration of approximately 15 µg/ml was the threshold for myocardial cell necrosis in this in vitro system. The dependencies of photocytotoxicity on radiant exposure were separated into two distinct groups based on the molecular density ratio between Talaporfin sodium and albumin.

Conclusions

This in vitro system for the extracellular photosensitization reaction may reflect the situation in live myocardial tissue. We found that the extracellular photosensitization reaction progressed in two distinctive phases; the first phase depended upon dissolved oxygen, and the second upon the molar density ratio between Talaporfin sodium and albumin. Cell lethality due to the extracellular photosensitization reaction was influenced by both of these factors in our in vitro system. We suggest that a photosensitizer concentration of 25 µg/ml might be necessary to treat myocardial tissue with therapies involving the extracellular photosensitization reaction. Lasers Surg. Med. 45:660–667, 2013. © 2013 Wiley Periodicals, Inc.
Repertoire Conventionality in Major US Symphony Orchestras: Factors Influencing Management's Programming Choices
Authors: Tamburri Lawrence , Munn Johnathan , Pompe Jeffrey
Published: November 2013

We examined the relationship between funding sources and programming for major US symphony orchestras for the 2001 through 2007 seasons. We find that increased levels of funding from the federal government and businesses encourage more nonconventional programming, and increased levels of funding from local government and endowments encourage more conventional programming. In addition, yearly events such as a composer's anniversary and higher unemployment influence programming decisions. Given the challenging financial environment for symphony orchestras, we discussed programming choices that managers could implement to reduce budget deficits. Copyright © 2013 John Wiley & Sons, Ltd.
Direct and Indirect Exporting and Productivity: Evidence from Firm‐Level Data
Authors: Yaşar Mahmut
Published: November 2013

This paper examines the separate productive impacts of direct and indirect exporting to further our understanding of the mechanisms underlying learning‐by‐exporting effects by utilizing a method that allows us to check the robustness of the results to the selection on unobservables. We found that the productivity effects of exporting are mainly associated with direct exporting, indicating that knowledge spillover, and thus, productive impact of exporting grows with increased interaction with international firms and consumers. Indirect exporters are unlikely to be able to efficiently exploit the productive capacity of foreign technology and knowledge. Copyright © 2013 John Wiley & Sons, Ltd.
Large‐eddy simulation of an offshore Mediterranean area
Authors: Rizza Umberto , Miglietta Mario M. , Sempreviva Anna M. , Grasso Fabio , Schiano M. Elisabetta
Published: November 2013

The aim of this study is to gain further understanding of the structure of the marine atmospheric boundary layer (MABL) and its interaction with synoptic‐scale forcing. A possible application of this study is to simulate mean and turbulent spatial and temporal structure of the marine boundary layer in order to optimize the structural design of offshore large wind turbines that today reach heights up to 200 m. Large‐eddy simulations (LESs) have been performed and compared with offshore experimental data collected during the LASIE campaign performed in the Mediterranean during summer 2007. Two simulations are performed: one where the LES is left free to evolve without any external forcing, and one where a force restoration nudging technique has been implemented in LES in order to force the model to the evolving large‐scale situation. Model results have been compared against experimental soundings. Results show that for all the calculated fields the nudged LES outperforms the simulation without nudging, demonstrating that incorporating changes in the large‐scale features is necessary in order to provide a realistic evolution of the modelled meteorological fields at local scale. Thus, appropriately nudged LES appears as a promising technique to be applied to the simulation of offshore cases, particularly suitable for wind energy applications.
Kisspeptin/KISS1R signaling potentiates extravillous trophoblast adhesion to type‐I collagen in a PKC‐ and ERK1/2‐dependent manner
Authors: Taylor Jay , Pampillo Macarena , Bhattacharya Moshmi , Babwah Andy V.
Published: November 2013

During the first trimester of human pregnancy, cytotrophoblasts proliferate within the tips of the chorionic villi to form cell columns that anchor the placenta to the uterus. This migration coincides with a widespread change in the adhesion molecule repertoire of these trophoblasts. Kisspeptin and its receptor, KISS1R, are best known as potent triggers of gonadotropin‐releasing hormone secretion. The kisspeptin/KISS1R signaling system is also highly expressed in the human placenta, where it was demonstrated to inhibit extra‐villous trophoblast (EVT) migration and invasion in vitro. Here we show that kisspeptin, in a dose‐ and time‐dependent manner, induces increased adhesion of human EVTs to type‐I collagen, a major component of the human placenta. This increased adhesion was both rapid and transient, suggesting that it likely occurred through the activation of KISS1R secondary effectors such as PKC and ERK, which underwent rapid and transient kisspeptin‐dependent activation in EVTs. We then showed that inhibition of both PKC and ERK1/2 attenuated the kisspeptin‐dependent increase in EVT adhesion, suggesting that these molecules are key positive regulators of trophoblast adhesion. We therefore propose that kisspeptin/KISS1R signaling potentiates EVT adhesion to type‐I collagen via “inside‐out signaling.” Furthermore, kisspeptin treatment increased mouse blastocyst adhesion to collagen I, suggesting that kisspeptin signaling is a key regulator of trophoblast function during implantation as well as early placentation. Mol. Reprod. Dev. 81: 42–54, 2014. © 2013 Wiley Periodicals, Inc.
Freistunde für Chemiker
Authors: Osterath Brigitte
Published: November 2013

Ideen einfach ausprobieren — warum eigentlich nicht? Viele Unternehmen räumen ihren Mitarbeitern Zeit zum Experimentieren ein, Fehlschläge sind ausdrücklich erlaubt. So entstehen Produkte, auf die in der Marketingabteilung niemand gekommen wäre.
Partially renewable copolyesters prepared from acetalized d‐glucitol by solid‐state modification of poly(butylene terephthalate)
Authors: Gubbels Erik , Lavilla Cristina , de Ilarduya Antxon Martínez , Noordover Bart A. J. , Koning Cor E. , Muñoz‐Guerra Sebastián
Published: November 2013

The backbone of poly(butylene terephthalate) (PBT) was modified with 2,4:3,5‐di‐O‐methylene‐D‐glucitol (Glux) using solid‐state modification (SSM). The obtained copolyesters proved to have a non‐random overall chemical microstructure. The thermal properties of these semicrystalline, block‐like, Glux‐based materials were extraordinary, showing higher melting points, and glass transition temperatures compared with other sugar‐based copolyesters prepared by SSM. These remarkable thermal properties were a direct result of the inherently rigid structure of Glux and the relatively slow randomization of the block‐like chemical microstructure of the Glux‐based copolyesters in the melt. SSM proved to be a versatile tool for preparing partially biobased copolyesters with superior thermal properties. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 164–177
Multiscale Simulation on the Influence of Dimethyl Hydantoin on Mechanical Properties of GAP/RDX Propellants
Authors: Lan Yanhua , Zhai Jinxian , Li Dinghua , Yang Rongjie
Published: November 2013

The influence of dimethyl hydantoin (DMH) on the mechanical properties of GAP/RDX propellant was studied by molecular dynamics (MD) and dissipative particle dynamics (DPD) simulation. The results showed that the binding energies (Ebinding) between GAP and different surfaces of RDX were in the order of (010)>(001)>(100). Compared to GAP/RDX, GAP grafted with DMH (GAP‐DMH) exhibits higher binding energies with RDX, and the sequence of Ebinding turns to (001)>(010)>(100). Radial distribution simulations demonstrated that GAP‐DMH is more close to the surfaces of RDX, increasing the van der Waals energies between GAP‐DMH and RDX. The stress and strain of GAP‐DMH/RDX excel those of GAP/RDX. DPD simulations showed that GAP‐DMH was able to restrain the agglomeration of RDX, to improve the dispersibility and to enlarge the contact surface with RDX, which also increased the mechanical properties of GAP/RDX propellant.
Outcomes of childhood conduct problem trajectories in early adulthood: findings from the ALSPAC study
Authors: Kretschmer Tina , Hickman Matthew , Doerner Rita , Emond Alan , Lewis Glyn , Macleod John , Maughan Barbara , Munafò Marcus R. , Heron Jon
Published: November 2013

Although conduct problems in childhood are stably associated with problem outcomes, not every child who presents with conduct problems is at risk. This study extends previous studies by testing whether childhood conduct problem trajectories are predictive of a wide range of other health and behavior problems in early adulthood using a general population sample. Based on 7,218 individuals from the Avon longitudinal study of parents and children, a three-step approach was used to model childhood conduct problem development and identify differences in early adult health and behavior problems. Childhood conduct problems were assessed on six occasions between age 4 and 13 and health and behavior outcomes were measured at age 18. Individuals who displayed early-onset persistent conduct problems throughout childhood were at greater risk for almost all forms of later problems. Individuals on the adolescent-onset conduct problem path consumed more tobacco and illegal drugs and engaged more often in risky sexual behavior than individuals without childhood conduct problems. Levels of health and behavior problems for individuals on the childhood-limited path were in between those for stable low and stable high trajectories. Childhood conduct problems are pervasive and substantially affect adjustment in early adulthood both in at-risk samples as shown in previous studies, but also in a general population sample. Knowing a child’s developmental course can help to evaluate the risk for later maladjustment and be indicative of the need for early intervention.
Biomarkers of muscle quality: N‐terminal propeptide of type III procollagen and C‐terminal agrin fragment responses to resistance exercise training in older adults
Authors: Fragala Maren S. , Jajtner Adam R. , Beyer Kyle S. , Townsend Jeremy R. , Emerson Nadia S. , Scanlon Tyler C. , Oliveira Leonardo P. , Hoffman Jay R. , Stout Jeffrey R.
Published: November 2013

Background

N‐terminal peptide of procollagen type III (P3NP) and C‐terminal agrin fragment (CAF) are circulating biomarkers that are related to lean body mass in older adults. P3NP is a circulating marker reflective of muscular structural remodeling while CAF is a circulating marker of neuromuscular remodeling. As resistance exercise is an established intervention that can effectively improve muscle quality, we sought to evaluate circulating biomarker changes corresponding to a resistance exercise intervention in older adults.

Methods

Twenty‐three older adults (aged 61 to 85 years) were randomized into an intervention (6‐week resistance training) or control group. Resting circulating P3NP, CAF, lean body mass (LBM), muscle cross‐sectional area (CSA), muscle strength, and muscle quality were determined at baseline and after the intervention or control period by enzyme‐linked immunosorbent assay, dual‐energy X‐ray absorptiometry, ultrasound, leg extension, and relative strength, respectively. Changes in circulating biomarkers and measures of muscle mass and quality were evaluated with repeated‐measures analysis of variance; clinical interpretations were made with magnitude‐based inferences, and relationships between variables were evaluated with bivariate correlations.

Results

The short‐term resistance exercise intervention was effective at improving muscle quality by 28 % (p < 0.001) despite no significant changes in lean body mass. Baseline circulating P3NP was somewhat lower in older women (4.15 ± 1.9 ng/mL) compared with older men (4.81 ± 2.1 ng/mL). The exercise intervention tended to increase circulating P3NP (baseline = 4.53 ± 1.80 to post = 4.88 ± 1.86) and was significantly correlated with changes in LBM (r = 0.422, p = 0.045). At baseline, women (3.91 ± 1.12 pg/mL) had somewhat higher circulating CAF than men (3.47 ± 1.37 pg/mL). Circulating CAF increased by 10.4 % (3.59 to 4.00 pg/ml) in older adults following 6 weeks of resistance exercise training. Changes in circulating CAF were significantly related to changes in CSA of the vastus lateralis (r = 0.542, p = 0.008).

Conclusions

Assessment of P3NP and CAF from blood samples may provide minimally invasive and clinically informative measures of skeletal muscle status in older adults. Circulating CAF appears to increase in response to short‐term resistance exercise training in older adults to a clinically meaningful magnitude. Changes in circulating P3NP in response to the intervention were less clear but appear to reflect muscle hypertrophy. Further research is needed to elucidate whether P3NP, CAF, or other biomarkers can reflect muscle qualitative adaptations with larger and longer studies.
Differential calmodulin‐modulatory and electron transfer properties of neuronal nitric oxide synthase mu compared to the alpha variant
Authors: Panda Satya P. , Li Wenbing , Venkatakrishnan Priya , Chen Li , Astashkin Andrei V. , Masters Bettie Sue S. , Feng Changjian , Roman Linda J.
Published: November 2013

Neuronal nitric oxide synthase μ (nNOSμ) contains 34 additional residues in an autoregulatory element compared to nNOSα. Cytochrome c and flavin reductions in the absence of calmodulin (CaM) were faster in nNOSμ than nNOSα, while rates in the presence of CaM were smaller. The magnitude of stimulation by CaM is thus notably lower in nNOSμ. No difference in NO production was observed, while electron transfer between the FMN and heme moieties and formation of an inhibitory ferrous‐nitrosyl complex were slower in nNOSμ. Thus, the insert affects electron transfer rates, modulation of electron flow by CaM, and heme–nitrosyl complex formation.
Eukaryotic translation initiation is controlled by cooperativity effects within ternary complexes of 4E‐BP1, eIF4E, and the mRNA 5′ cap
Authors: Modrak-Wojcik Anna , Gorka Michal , Niedzwiecka Katarzyna , Zdanowski Konrad , Zuberek Joanna , Niedzwiecka Anna , Stolarski Ryszard
Published: November 2013

Initiation is the rate‐limiting step during mRNA 5′ cap‐dependent translation, and thus a target of a strict control in the eukaryotic cell. It is shown here by analytical ultracentrifugation and fluorescence spectroscopy that the affinity of the human translation inhibitor, eIF4E‐binding protein (4E‐BP1), to the translation initiation factor 4E is significantly higher when eIF4E is bound to the cap. The 4E‐BP1 binding stabilizes the active eIF4E conformation and, on the other hand, can facilitate dissociation of eIF4E from the cap. These findings reveal the particular allosteric effects forming a thermodynamic cycle for the cooperative regulation of the translation initiation inhibition.
Quality control of a molybdoenzyme by the Lon protease
Authors: Redelberger David , Genest Olivier , Arabet Dallel , Méjean Vincent , Ilbert Marianne , Iobbi-Nivol Chantal
Published: November 2013

Molybdoenzymes contain a molybdenum cofactor in their active site to catalyze various redox reactions in all domains of life. To decipher crucial steps during their biogenesis, the TorA molybdoenzyme of Escherichia coli had played a major role to understand molybdoenzyme maturation process driven by specific chaperones. TorD, the specific chaperone of TorA, is also involved in TorA protection. Here, we show that immature TorA (apoTorA) is degraded in vivo and in vitro by the Lon protease. Lon interacts with apoTorA but not with holoTorA. Lon and TorD compete for apoTorA binding but TorD binding protects apoTorA against degradation. Lon is the first protease shown to eliminate an immature or misfolded molybdoenzyme probably by targeting its inactive catalytic site.
Characterization of patients with ostomy treated at a public municipal and regional reference center
Authors: Melotti Luis Fernando , Bueno Ivy Mendes , Silveira Gleci Vieira , Silva Maria Elizete Nunes Da , Fedosse Elenir
Published: November 2013

Objective to characterize patients with ostomy treated at a municipal and regional reference center in the state of Rio Grande do Sul.

Methods this is a retrospective and descriptive study, based on the records of patients with ileostomy or colostomy recorded in this service between 2000 and 2010.

Results a total of 273 patients were studied, of which 145 were females. The mean age was 64.5 years. Patients with incomplete elementary education (43.6%) and retirees/pensioners (44.7%) were the most prevalent. The main cause for the stoma was neoplastic disease, with 45.8% of colorectal cancer and 5.5% of cancers at other sites. Other causes were: diverticular disease (7%), bowel obstruction (7%), functional bowel disorders (4.8%), abdominal trauma (2.9%), non-traumatic bowel perforation (2.6%), inflammatory bowel diseases (1.8%) and intestinal polyposis (0.7%). Regarding the type of ostomy, 85.7% were performed by colostomy and 15.8% by ileostomy.

Conclusions the study population consisted mainly of patients older than 60 and females. The main intervention performed was permanent colostomy and the most important cause for the procedure performance was colorectal cancer.
Applying Qualitative Comparative Analysis (QCA) to evaluate a public health policy initiative in the North East of England
Authors: Warren Jon , Wistow Jonathan , Bambra Clare
Published: November 2013

This paper presents a Qualitative Comparative Analysis (QCA) analysis of data produced as part of the evaluation a Nation Health Service commissioned intervention in the North East of England. QCA is a case-oriented method that allows systematic comparison of cases as configurations of set memberships based on their attributes and the relationship of these to particular outcomes. QCA provides an alternative to conventional quantitative approaches which are generally concerned with isolating the independent effect of one variable whilst controlling the influence of others. Instead, QCA allows for interactions between multiple attributes and recognises that the same outcomes may be generated by different configurations of attributes.

The intervention evaluated provided case management for individuals who were out of work due to ill health, and had been for three years or more. It aimed to improve the health of individuals and move them closer to the labour market. The intervention and a comparison group were assessed at base line (T1), after 3 months — (T2) after 6 months (end of the intervention — T3) and after 9 months (three months post intervention — T4). The size of the respective populations at each time point were, Intervention group at T1, N = 131, T2, N = 44, T3, N = 79, T4, N = 95. Comparison group at T1, N = 229, T2, N = 188, T3, N = 166, T4, N = 154.

General health was measured using EQ5-D (a standardised instrument for use as a measure of general health outcome) and SF-8. Two condition specific measures were included: the Hospital Anxiety and Depression Scale (HADS) and the Nordic Musculoskeletal questionnaire.

Data was also collected on socio demographics (gender, age, housing tenure), social capital (contact with family and friends and participation with the wider community), and work history (previous jobs, time spent in the job, time spent on sickness absence).

The aim of the QCA analysis was to identify whether individuals with certain characteristics or combinations of characteristics benefited from the intervention. In order to do this the cases were sorted according to whether their EQ-5D VAS (Visual Analogue Scale) scores (a self rated measure of general health) narrowed or did not narrow towards the population norm for the measure between baseline (T1) and (T4) 9 months (three months post intervention — T4). Cases which narrowed towards the UK population norm of 82.48 were judged to be experiencing a health improvement whilst those whose scores did not narrow towards the norm were judged to not have experienced a health improvement. A crisp set (cs) QCA analysis was then performed.

The paper assesses the benefits of using QCA, and asks whether it can provide a viable and practical tool for social policy evaluations.