bluuebunny/crossref_metadata_2025 huggingface dataset:
Covalent and Ionic States of Strong Acids at the Ice Surface
Authors: Devlin J. Paul , Uras Nevin , Rahman Mohammed , Buch Victoria
Published: November 2013

The relationship between the degree of ionization and the environment of a strong acid is of basic scientific interest. Often this relationship reduces to the interdependence of ion/acid hydration and proton transfer. Despite the presence of pure water, the surface of crystalline ice, particularly at cryogenic temperatures, is one of limited (controlled?) availability of water of hydration. Here, the detailed nature of the ice surface and the states of strong acids adsorbed to ice at cryogenic temperatures are examined. These subjects are of special current interest since the ability to model the complex chemistry that occurs on the surfaces of water‐rich particles in the atmosphere, particularly in the stratosphere over the polar regions, requires a valid concept of the acid‐ice interface. Our combined spectroscopic and simulation studies have identified the surface of free‐standing ice particles as badly disordered, with a range of water‐ring sizes and an increased level of H‐bond saturation relative to an ordered ice surface. FT‐IR results are reported for the interaction of the surface of such ice particles with submonolayer amounts of adsorbed DCl, DBr, and HNO3 and for multilayer exposure to DCl. The DCl and DBr adsorbed states demonstrate behavior familiar from observations on strongly bound molecular adsorbates. Two methods have been devised for exposure of the nanocrystals to HNO3 One gives an ionic state initially, while the initial state of the other approach is molecular. In both instances, the system is observed to evolve, with time/warming, towards a common mixed molecular–ionic adsorbed state.
Femtosecond Intramolecular Double Proton Transfer in Solution
Authors: Glasbeek Max
Published: November 2013

A review is given of our recent femtosecond fluorescence upconversion studies of photoexcited [2,2′‐bipyridyl]‐3,3′‐diol (BP(OH)2), and a few derivative compounds thereof. For BP(OH)2 in liquid solution, concerted and consecutive intramolecular double proton transfers are found to occur concurrently. The concerted (one‐step) process takes place in less than 100 fs. The consecutive two‐step process (with a first step in less than 100 fs and a second step of a few picoseconds) is solvent and excitation wavelength dependent. From the results we infer that the excited‐state double proton transfer in BP(OH)2 is promoted by low‐frequency vibrational stretching and bending modes. Proton transfer dynamics was also studied for BP(OH)2 in sol‐gel glasses. Residual amounts of methanol and water in the pores of the sol‐gel glass are found to still solvate the probe molecule and to affect the proton transfer dynamics. Finally, some results of fluorescence upconversion experiments for 6‐Me‐BPOH (6‐methyl‐[2,2′‐bipyridyl]‐3′‐ol) and BP(OH)2‐6‐COOMe (methyl‐3,3′‐dihydroxy‐[2,2′‐bipyridyl]‐6‐carboxylate) are presented for comparison. It appears that the latter compound in the excited state exhibits a single proton transfer only.
Excited‐State Proton Transfer in Bifunctional Compounds
Authors: Bardez Elisabeth
Published: November 2013

When the acidic and basic groups of an amphoteric compound become stronger on excitation, excited‐state proton transfers (ESPT) are driven by the photoinduced synergy between the two functions. This is exemplified here by 7‐ and 8‐hydroxyquinolines (7‐ and 8‐HQ), whatever the initially excited form. For instance, the ‐OH group of the 7‐hydroxyquinolinium form undergoes photoinduced deprotonation even in 8M HClO4! This reveals its outstanding photoacidity, confirmed by the value of the deprotonation rate constant k1 at infinite dilution, 5.5 × 1010 s−1. The decrease of k1 on increasing the ionic strength pointed out the key number of 4 water molecules as proton acceptors. In neutral medium, a very efficient photoinduced tautomerization is observed. For 7‐HQ in water, a mechanism consisting of three competitive paths was established: A proton translocation via a bridge of water molecules within less than 10 ps for the cis‐isomer, and two stepwise competitive reactions for the trans‐isomer. Concerning the weakly fluorescent 8‐HQ, the photoinduced tautomerization occurs even in organic media. In most solvents, an intrinsic ESPT takes place within intramolecularly H‐bonded molecules, but preferential solvation by residual water of the solvent may lead to open structures where ESPT is impaired. In alkanes, a biprotonic ESPT is expected to occur within very stable dimers (Kdim= 7.0 × 107). In all cases, the coupling between proton transfers and an intramolecular electron transfer leads to the ketonic structure of the tautomer. This might be a general feature in phototautomerization reactions.
Theoretical Studies of the Grotthuss Mechanism in Biological Proton Wires
Authors: Pomès Régis
Published: November 2013

The structural, dynamic, and thermodynamic properties of proton wires are examined. Detailed molecular aspects of both hop and turn steps of the Grotthuss mechanism for proton conduction along single‐file chains of water molecules in model nonpolar pores and in the gramicidin A channel are reviewed, and new simulation results are presented. The Grotthuss mechanism is discussed and analyzed in terms of hydrogen‐bonded network structure and connectivity, and the properties of proton wires are contrasted to those of bulk water. General considerations regarding the biological relevance of such studies are proposed.
Highly aligned porous Ti scaffold coated with bone morphogenetic protein‐loaded silica/chitosan hybrid for enhanced bone regeneration
Authors: Jung Hyun‐Do , Yook Se‐Won , Han Cheol‐Min , Jang Tae‐Sik , Kim Hyoun‐Ee , Koh Young‐Hag , Estrin Yuri
Published: November 2013

Porous Ti has been widely investigated for orthopedic and dental applications on account of their ability to promote implant fixation via bone ingrowth into pores. In this study, highly aligned porous Ti scaffolds coated with a bone morphogenetic protein (BMP)‐loaded silica/chitosan hybrid were produced, and their bone regeneration ability was evaluated by in vivo animal experiments. Reverse freeze casting allowed for the creation of highly aligned pores, resulting in a high compressive strength of 254 ± 21 MPa of the scaffolds at a porosity level of ∼51 vol %. In addition, a BMP‐loaded silica/chitosan hybrid coating layer with a thickness of ∼1 μm was uniformly deposited on the porous Ti scaffold, which enabled the sustained release of the BMP over a prolonged period of time up to 26 days. The cumulative amount of the BMP released was ∼4 μg, which was much higher than that released from the specimen without a hybrid coating layer. In addition, the bone regeneration ability of the porous Ti scaffold with a BMP‐loaded silica/chitosan coating layer was examined by in vivo animal testing using a rabbit calvarial defect model and compared with those of the as‐produced porous Ti scaffold and porous Ti scaffold with a silica/chitosan coating layer. After 4 weeks of healing, the specimen coated with a BMP‐loaded silica/chitosan hybrid showed a much higher bone regeneration volume (∼36%) than the as‐produced specimen (∼15%) (p < 0.005) and even the specimen coated with a silica/chitosan hybrid (∼25%) (p < 0.05). © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 913–921, 2014.
Multidimensional umbrella sampling and replica‐exchange molecular dynamics simulations for structure prediction of transmembrane helix dimers
Authors: Li Pai‐Chi , Miyashita Naoyuki , Im Wonpil , Ishido Satoshi , Sugita Yuji
Published: November 2013

Structural information of a transmembrane (TM) helix dimer is useful in understanding molecular mechanisms of important biological phenomena such as signal transduction across the cell membrane. Here, we describe an umbrella sampling (US) scheme for predicting the structure of a TM helix dimer in implicit membrane using the interhelical crossing angle and the TM–TM relative rotation angles as the reaction coordinates. This scheme conducts an efficient conformational search on TM–TM contact interfaces, and its robustness is tested by predicting the structures of glycophorin A (GpA) and receptor tyrosine kinase EphA1 (EphA1) TM dimers. The nuclear magnetic resonance (NMR) structures of both proteins correspond to the global free‐energy minimum states in their free‐energy landscapes. In addition, using the landscape of GpA as a reference, we also examine the protocols of temperature replica‐exchange molecular dynamics (REMD) simulations for structure prediction of TM helix dimers in implicit membrane. A wide temperature range in REMD simulations, for example, 250–1000 K, is required to efficiently obtain a free‐energy landscape consistent with the US simulations. The interhelical crossing angle and the TM–TM relative rotation angles can be used as reaction coordinates in multidimensional US and be good measures for conformational sampling of REMD simulations. © 2013 Wiley Periodicals, Inc.
A Facile and Efficient Synthesis of 2‐(5‐(4‐Substitutedphenyl)‐4, 5‐dihydro‐3‐phenylpyrazol‐1‐yl)‐6‐Substitutedbenzothiazoles and Their Biological Studies
Authors: Munirajasekhar D. , Himaja M. , Mali Sunil V.
Published: November 2013

A series of new 1‐substituted 3, 5‐diarylpyrazolines (10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25) were synthesized in good yield by both conventional and microwave‐assisted synthesis from α, β‐ unsaturated ketones (6, 7, 8, 9) in n‐butanol and benzothiazole hydrazines (2, 3, 4, 5). All the new compounds were characterized by IR, NMR, and mass spectral data. The synthesized compounds (10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25) were evaluated for antibacterial and anthelmintic activities. The compounds showed potent anthelmintic activity against earthworm species (Eudrilus eugeniae) and moderate antibacterial activity against bacterial strains such as Gram positive bacteria, Enterococcus faecalis, Staphylococcus aureus, and Bacillus subtilis, and Gram negative bacteria, Escherichia coli and Proteus mirabilis.
99mTc‐Doxycycline hyclate: a new radiolabeled antibiotic for bacterial infection imaging
Authors: İlem‐Özdemir Derya , Asikoglu Makbule , Ozkilic Hayal , Yilmaz Ferda , Hosgor‐Limoncu Mine , Ayhan Semin
Published: November 2013

Radiolabeled antibiotics are promising radiopharmaceuticals for the precise diagnosis and detection of infectious lesions. Doxycycline Hyclate (DOX) was chosen to investigate new 99mTc‐labeled antibacterial agent. Ready to use freeze dry kits were formulated with optimum labeling conditions. Human serum stability, sterility, and pyrogenicity of kits were estimated, and gamma scintigraphy, in vivo biodistribution, and histopathological studies with bacterial infected rats were performed.

DOX were successfully labeled by 99mTc with high radiochemical purity, and the labeled compound was stable in human serum. Kits were sterile, pyrogen‐free, and stable up to 6 months.

Static images depicted rapid distribution throughout the body and high uptake in bacterial infected thigh muscle. The uptake ratios of radiopharmaceuticals in infected thigh muscle were found above 2 up to 5 h.

Five hours after injection, the rats were sacrificed, and biodistribution was determined. Samples of bacterial infected muscle, healthy muscle, blood, liver, spleen, lung, kidney, stomach, intestine, urine and heart were weighed, and the radioactivity was measured by using a gamma counter. The %ID/g of 99mTc‐DOX was found 0.23 ± 0.06 for infected thigh muscle.

According to the imaging, biodistribution, and histopathological studies, the promising characteristics of 99mTc‐DOX make the new radiopharmaceutical valuable to examine for future studies. Copyright © 2013 John Wiley & Sons, Ltd.
MR imaging of urinary bladder cancer for T‐staging: A review and a pictorial essay of diffusion‐weighted imaging
Authors: Takeuchi Mitsuru , Sasaki Shigeru , Naiki Taku , Kawai Noriyasu , Kohri Kenjiro , Hara Masaki , Shibamoto Yuta
Published: November 2013

Treatment decisions for bladder cancer patients are mainly based on the depth of bladder wall invasion by the tumor. In this article, we review the conventional MRI and exhibit a recently emerged diffusion‐weighted imaging (DWI) of urinary bladder cancer for T‐staging. We discuss limitations of conventional MRI, scanning protocols of DWI, normal pelvic findings on DWI, determination of T‐stage using DWI, and pitfalls of DWI. DWI provides high contrast between bladder cancer and background tissue because the cancer shows markedly high SI. DWI has high sensitivity for detecting the stalk seen in stage Ta or T1. An inflammatory change or fibrosis surrounding the tumor mimics the invasion of bladder cancer on T2‐weighted imaging or enhanced MRI and could lead to over‐staging, but DWI could differentiate them clearly because these benign changes do not show high SI on DWI. DWI is also useful for detecting ureteral, urethral, and prostatic extension by means of the urethra. DWI provides more accurate information on the extent of bladder cancer and contributes to determination of the treatment strategy. J. Magn. Reson. Imaging 2013;38:1299–1309. © 2013 Wiley Periodicals, Inc.
Direct observation of p,p′‐dimercaptoazobenzene produced from p‐aminothiophenol and p‐nitrothiophenol on Cu2O nanoparticles by surface‐enhanced Raman spectroscopy
Authors: You Tingting , Jiang Li , Yin Penggang , Shang Yang , Zhang Dongfeng , Guo Lin , Yang Shihe
Published: November 2013

Surface‐enhanced Raman scattering of p‐aminothiophenol and p‐nitrothiophenol were obtained on the surface of Cu2O nanoparticles, showing novel spectral changes with morphology‐dependent and time‐dependent characteristics. The measured Raman signals were believed to partly originate from the newly produced surface species p,p′‐dimercaptoazobenzene. The nature of surface chemisorption status during Raman measurement was investigated experimentally and theoretically via combined surface‐enhanced Raman scattering and density functional theory study, indicating that surface catalytic reaction of p‐aminothiophenol and p‐nitrothiophenol could take place on the surface of oxide nanostructures as well as coinage metal material. Copyright © 2013 John Wiley & Sons, Ltd.
Simultaneous Polymerization‐Induced Self‐Assembly (PISA) and Guest Molecule Encapsulation
Authors: Karagoz Bunyamin , Boyer Cyrille , Davis Thomas P.
Published: November 2013

Nanoparticles with various morphologies such as micelles, worm‐like/rod‐like and spherical vesicles are made using a polymerization‐induced self‐assembly (PISA) approach via a one‐pot RAFT dispersion polymerization. On polymerization/self‐assembly, we report a concurrent highly efficient loading of guest molecules within the nanoparticle structures. Different nanoparticle morphologies, such as spherical micelles, worm‐like, rod‐like, and spherical vesicles, are achieved by gradually increasing the number‐average degree of polymerization (DPn) of the PST block via increasing polymerization times (in a poor solvent) as determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. In parallel, a guest molecule (Nile Red) is encapsulated during the polymerization without disturbing the morphology or the polymerization kinetics.

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Evaluation of highly accelerated real‐time cardiac cine MRI in tachycardia
Authors: Bassett Elwin C. , Kholmovski Eugene G. , Wilson Brent D. , DiBella Edward V. R. , Dosdall Derek J. , Ranjan Ravi , McGann Christopher J. , Kim Daniel
Published: November 2013

Electrocardiogram (ECG)‐gated breath‐hold cine MRI is considered to be the gold standard test for the assessment of cardiac function. However, it may fail in patients with arrhythmia, impaired breath‐hold capacity and poor ECG gating. Although ungated real‐time cine MRI may mitigate these problems, commercially available real‐time cine MRI pulse sequences using parallel imaging typically yield relatively poor spatiotemporal resolution because of their low image acquisition efficiency. As an extension of our previous work, the purpose of this study was to evaluate the diagnostic quality and accuracy of eight‐fold‐accelerated real‐time cine MRI with compressed sensing (CS) for the quantification of cardiac function in tachycardia, where it is challenging for real‐time cine MRI to provide sufficient spatiotemporal resolution. We evaluated the performances of eight‐fold‐accelerated cine MRI with CS, three‐fold‐accelerated real‐time cine MRI with temporal generalized autocalibrating partially parallel acquisitions (TGRAPPA) and ECG‐gated breath‐hold cine MRI in 21 large animals with tachycardia (mean heart rate, 104 beats per minute) at 3T. For each cine MRI method, two expert readers evaluated the diagnostic quality in four categories (image quality, temporal fidelity of wall motion, artifacts and apparent noise) using a Likert scale (1–5, worst to best). One reader evaluated the left ventricular functional parameters. The diagnostic quality scores were significantly different between the three cine pulse sequences, except for the artifact level between CS and TGRAPPA real‐time cine MRI. Both ECG‐gated breath‐hold cine MRI and eight‐fold accelerated real‐time cine MRI yielded all four scores of ≥ 3.0 (acceptable), whereas three‐fold‐accelerated real‐time cine MRI yielded all scores below 3.0, except for artifact (3.0). The left ventricular ejection fraction (LVEF) measurements agreed better between ECG‐gated cine MRI and eight‐fold‐accelerated real‐time cine MRI (mean difference, –1.6%) than between ECG‐gated cine MRI and three‐fold‐accelerated real‐time cine MRI (mean difference, –5.7%). Eight‐fold‐accelerated real‐time cine MRI with CS yields acceptable diagnostic quality and relatively accurate LVEF measurements in the challenging setting of tachycardia. Copyright © 2013 John Wiley & Sons, Ltd.
Nature of molecular network in thermal shrinkage behavior of oriented high‐density polyethylene
Authors: Fu Lianlian , Jiang Zhiyong , Enderle Hans‐Friedrich , Lilge Dieter , Li Xiuhong , Funari Sérgio S. , Men Yongfeng
Published: November 2013

Shrinkage and structural evolution of oriented high‐density polyethylene on heating were investigated by a combination of thermomechanical analysis (TMA) and synchrotron small angle X‐ray scattering (SAXS) techniques. Under varying load conditions, TMA study was performed to record the continuous length changes as a function of temperature. The value of shrinkage without any load could be evaluated by a linear extrapolation method, which eliminated the influence of the required tension by traditional TMA approach. In addition, the apparent modulus of network was used to describe the nature of entangled molecular network in detail during the shrinkage process. Importantly, it was found that the apparent modulus decreased gradually with increasing temperature. Furthermore, the SAXS data provided a direct evidence for the variation trend of shrinkage stress obtained by the tensile testing stage, and the results confirmed that the shrinkage force mainly originates from interfibrillar networks. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 368–376
Tandem mass spectrometry for the study of glyoxal‐derived advanced glycation end‐products (AGEs) in peptides
Authors: Lopez‐Clavijo Andrea F. , Duque‐Daza Carlos A. , O'Connor Peter B.
Published: November 2013

RATIONALE

The post‐translational modification known as glycation affects the physiological properties of peptides and proteins. Glycation is particularly important during hyperglycaemia where α‐dicarbonyl compounds are generated. These compounds react with proteins to generate α‐dicarbonyl‐derived glycation products, which are correlated with diabetic complications such as nephropathy, retinopathy, and neuropathy, among others. One of these α‐dicarbonyl compounds is ethanedial, also known as glyoxal. Thereby, glyoxal binding to protein/peptides is studied by electron capture dissociation (ECD) and collisionally activated dissociation (CAD).

METHODS

Acetylated and non‐acetylated undecapeptides containing one lysine and one arginine susceptible of glycation were reacted with glyoxal under pseudo‐physiological and MeOH/H2O (50:50) conditions. Two types of glyoxal‐derived AGEs were fragmented by ECD and CAD using 12 Tesla Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS).

RESULTS

Reaction with glyoxal under different reaction conditions showed the addition of C2O and C2H2O2, which corresponded to a net increase on the peptide mass of 39.9949 Da and 58.0055 Da, respectively. The binding site was assigned within an error <1 ppm, using ECD and CAD. The results indicated that both types of glyoxal‐derived AGEs are formed at the side chain of arginine located in position 3.

CONCLUSIONS

Types and binding sites of glyoxal‐derived AGEs were investigated in peptides containing one arginine‐one lysine using FTICRMS. Two net mass additions to the mass of the peptide were assigned as C2O and C2H2O2, which were located at the arginine side chain. In addition, these mass additions (C2O and C2H2O2) observed in the peptides were unaffected by different reaction conditions. Copyright © 2013 John Wiley & Sons, Ltd.
Compound‐specific δ13C and δ15N analysis of amino acids: a rapid, chloroformate‐based method for ecological studies
Authors: Walsh Robert G. , He Shaoneng , Yarnes Christopher T.
Published: November 2013

RATIONALE

Compound‐specific stable isotope analysis of amino acids has proven informative to many ecological systems, but only a handful of analytical methods are routinely employed. We evaluated a simple, rapid procedure in which biological samples undergo short‐duration acid hydrolysis and the resulting amino acids are derivatized with methyl chloroformate for gas chromatography/combustion/isotope‐ratio mass spectrometry (GC/C/IRMS).

METHODS

Amino acid derivatives were separated on a polar gas chromatography column, combusted, and δ13C and δ15N values were measured. Tests of reproducibility and accuracy were conducted for amino acid reference mixtures and biological samples. A brief case study of turtles was used to assess whether isotopic data were consistent with a priori ecological expectations.

RESULTS

The methyl chloroformate based reaction successfully converted 15 amino acids from acid hydrolysates of biological materials into separable derivatives. The δ13C and δ15N values had high average measurement precision (σ <1 ‰). Reference materials were measured accurately, with good agreement between EA/IRMS and GC/C/IRMS determinations. Analysis of turtle blood samples yielded data consistent with their trophic ecology.

CONCLUSIONS

This derivatization method is a rapid means of determining carbon and nitrogen isotopic ratios of amino acids present in the biological materials often sampled for ecological studies. While amino acids with charged or polar side chains do not have uniformly high recoveries, the average precision of measurements is comparable with that of other, more established methods. Batches of samples may be prepared from many raw materials in less than a day, representing a significant reduction in preparation time over prevailing methods. Copyright © 2013 John Wiley & Sons, Ltd.
Electrospray ionization mass spectrometry probing of binding affinity of berbamine, a flexible cyclic alkaloid from traditional Chinese medicine, with G‐quadruplex DNA
Authors: Tan Wei , Zhou Jiang , Yuan Gu
Published: November 2013

RATIONALE

Classic G‐quadruplex binders typically have a large aromatic core and interact with G‐quadruplexes through π–π stacking with the quartets. There are rather few reports on natural flexible cyclic molecule from traditional Chinese medicine which has high binding affinity with G‐quadruplex.

METHODS

Electrospray ionization mass spectrometry (ESI‐MS) experiments were performed to evaluate the binding affinities of a natural alkaloid, berbamine, with seven G‐quadruplexes. Furthermore, we utilized autodock4 analysis to uncover the binding mode of berbamine with the G‐quadruplex.

RESULTS

ESI‐MS experiments showed that berbamine has the best binding affinity toward the (GGA)8 G‐quadruplex compared with the other six G‐quadruplexes. Autodock4 analysis indicated that berbamine interacted with the (GGA)8 G‐quadruplex through hydrogen bonding and van der Waals forces with a binding site at the lateral groove formed by DG8‐DA9‐DA15‐DG16.

CONCLUSIONS

In this study, we discovered a novel G‐quadruplex binder, berbamine, which has high binding affinity toward the (GGA)8 G‐quadruplex. This study provided important clues regarding the probing of small molecule from traditional Chinese medicine which can target the G‐quadruplex with high affinity. Copyright © 2013 John Wiley & Sons, Ltd.
Is superoptimization viable for VM instruction sets?
Authors: Hume Tom , Watson Des
Published: November 2013

The technique of superoptimization attempts to ensure true optimality of a code (according to predefined criteria) through an exhaustive search of all potentially viable programs. Implementations have demonstrated that superoptimizers are capable of finding shorter programs than those hand optimized for size by experts or produced by conventional compilers. Superoptimizers have been developed for many machine architectures and used for diverse purposes including automating peephole optimization and binary translation of instruction sets. The output of superoptimizers is frequently surprising to human experts and often takes advantage of side effects or obscure characteristics of the targeted hardware. Virtual machines (VMs) are increasingly popular in implementations of programming languages, because they can provide a common platform across heterogeneous hardware architectures. This paper examines whether superoptimization could be a viable technique for VMs. A superoptimizer for the Java VM (JVM) has been developed and used to generate demonstrably size‐optimized versions of some simple mathematical functions, implemented in a Java bytecode. We have shown that these versions are shorter than both implementations shipped with the Java software development kit and those generated by the Java compiler. We also have some useful observations concerning techniques to allow larger programs to be optimized in a reasonable time by this approach. Copyright © 2013 John Wiley & Sons, Ltd.
Tools for Supporting Responsible Decision‐Making?
Authors: Vriens Dirk , Achterbergh Jan
Published: November 2013

In this paper, we assess the characteristics decision support tools should have in order to support “responsible decision‐making”. To this end, we first describe responsible decision‐making. We argue that responsibility relates to both the outcome and the process of decision‐making. On the basis of this description, we discuss which conditions should be in place so as to increase the possibility of responsible decision‐making. Next, we discuss the characteristics of tools supporting responsible decision‐making in terms of their ability to support the realization of the required conditions for responsible decision‐making. We use these characteristics to identify three types of tools: “responsible”, “neutral”, and “irresponsible” tools. We illustrate the assessment of the responsibility of support tools by looking at group model building. Copyright © 2013 John Wiley & Sons, Ltd.
Wide Resection of Inguinal Nerves versus Simple Section to Prevent Postoperative Pain after Prosthetic Inguinal Hernioplasty: Our Experience
Authors: Zannoni M. , Luzietti E. , Viani L. , Nisi P. , Caramatti C. , Sianesi M.
Published: November 2013

Background

In the literature, chronic groin pain (i.e. lasting >3 months) occurs in about 10 % of patients who undergo inguinal hernioplasty with prosthesis; it is characterized by a broad range of symptoms, and is relative to individual perceptions of pain. In 2–5 % of cases, the painful symptomatology is so intense that it interferes with daily activities, and can be debilitating in 0.5–6 % of cases. The best known cause of inguinodynia is neuropathy, due to implication of one or more inguinal nerves (iliohypogastric, ilioinguinal, and genitofemoral nerves) into fibroblastic processes; or from nervous stimulation caused by prosthetic material on adjacent nervous trunks. Many therapeutic strategies have been proposed to treat chronic groin pain, including intra‐operative prophylactic neurectomy.

Objective

The purpose of our study was to perform a comparative analysis between outcomes from wide resections of inguinal nerves versus those from simple nervous section (or minimal resection).

Patients and methods

We considered 350 patients who had undergone inguinal prosthetic hernioplasty with Trabucco’s technique between 2004 and 2010. Wide nervous resection (removal of nerve segments 3–8 cm in length) was performed in 180. The other 170 patients underwent simple section or minimal resection. All patients were checked 1 week, 1 month, and 1 year after surgery.

Results

Group 1: At 1‐week follow‐up, 63 patients (35 %) reported no pain, 113 (63 %) reported moderate pain, and 4 (2 %) intense pain; 1 month after the procedure, 152 patients (84.4 %) reported no pain, 25 (14 %) complained of moderate pain, and 3 (1.6 %) of severe pain; 1 year after surgery, only 1 patient (0.5 %) complained of constant pain. Group 2: At 1 week follow‐up, 48 patients (28 %) reported no pain, 101 (59 %) reported moderate pain, and 21 (13 %) intense pain; 1 month after the procedure, 81 patients (47.6 %) had no pain, 72 (42.4 %) complained of moderate pain, and 17 (10 %) of severe pain; 1 year after surgery, 11 patients (6.5 %) had constant pain, and two of them were re‐admitted for surgery. The lower incidence of chronic pain after long nervous resection is statistically significant (0.5 vs. 6.5 %; p = 0.006); the incidence of moderate pain 1 month after operation is also lower (14 vs. 42.4 %; p < 0.0001); patients who underwent a long resection experienced faster resolution of pain symptomatology, during a month. Also noteworthy is the lower incidence of intense pain in the short and medium term (after 1 week, 13 vs. 2 %, p = 0.0005; after 1 month, 10 vs. 1.6 %, p = 0.0018).

Conclusions

The prophylactic wide resection of selected segments of inguinal nerves, despite the apparent paradox of greater tissue damage, appears more effective than simple section at preventing postoperative inguinodynia, given both the lower incidence and the faster resolution of painful symptomatology.
Changes in Tissue Lipid and Fatty Acid Composition of Farmed Rainbow Trout in Response to Dietary Camelina Oil as a Replacement of Fish Oil
Authors: Hixson Stefanie M. , Parrish Christopher C. , Anderson Derek M.
Published: November 2013

Camelina oil (CO) replaced 50 and 100 % of fish oil (FO) in diets for farmed rainbow trout (initial weight 44 ± 3 g fish−1). The oilseed is particularly unique due to its high lipid content (40 %) and high amount of 18:3n‐3 (α‐linolenic acid, ALA) (30 %). Replacing 100 % of fish oil with camelina oil did not negatively affect growth of rainbow trout after a 12‐week feeding trial (FO = 168 ± 32 g fish−1; CO = 184 ± 35 g fish−1). Lipid and fatty acid profiles of muscle, viscera and skin were significantly affected by the addition of CO after 12 weeks of feeding. However, final 22:6n‐3 [docosahexaenoic acid (DHA)] and 20:5n‐3 [eicosapentaenoic acid (EPA)] amounts (563 mg) in a 75 g fillet (1 serving) were enough to satisfy daily DHA and EPA requirements (250 mg) set by the World Health Organization. Other health benefits include lower SFA and higher MUFA in filets fed CO versus FO. Compound‐specific stable isotope analysis (CSIA) confirmed that the δ13C isotopic signature of DHA in CO fed trout shifted significantly compared to DHA in FO fed trout. The shift in DHA δ13C indicates mixing of a terrestrial isotopic signature compared to the isotopic signature of DHA in fish oil‐fed tissue. These results suggest that ~27 % of DHA was synthesized from the terrestrial and isotopically lighter ALA in the CO diet rather than incorporation of DHA from fish meal in the CO diet. This was the first study to use CSIA in a feeding experiment to demonstrate synthesis of DHA in fish.
Characterization and Oxidative Stability of Human Milk Fat Substitutes Enzymatically Produced from Palm Stearin
Authors: Zou Xiaoqiang , Huang Jianhua , Jin Qingzhe , Guo Zheng , Liu Yuanfa , Cheong Lingzhi , Xu Xuebing , Wang Xingguo
Published: November 2013

Production of human milk fat substitutes (HMFSs) from three types of palm stearin with palmitic acid (PA) of 91.3, 70.3 and 62.6 %, respectively, was scaled up to a kilogram scale. The physiochemical properties of these products including fatty acid profiles, triacylglycerol compositions, tocopherol contents, oxidative stability and melting and crystallization profiles were compared with those of HMFSs from lard, butterfat and tripalmitin and fats from infant formulas. Based on their chemical compositions, HMFSs from palm stearin with PA contents of 70.3 and 62.6 % produced by enzymatic acidolysis were found to have the highest degree of similarity to human milk fat, which indicated that these HMFSs were the most suitable for use in infant formulas. However, HMFSs from palm stearin with PA content of 91.3 % had the highest tocopherol contents. By investigation of the primary and secondary oxidation products during accelerated oxidation, the oxidative stability of HMFSs was found to be positively correlated to the contents of tocopherols, and the volatile oxidation compounds with the highest relative contents in HMFSs were aldehydes analyzed by solid‐phase microextraction‐GC–MS. All HMFSs had final melting points lower than body temperature.
The anabolic catabolic transforming agent (ACTA) espindolol increases muscle mass and decreases fat mass in old rats
Authors: Pötsch Mareike S. , Tschirner Anika , Palus Sandra , von Haehling Stephan , Doehner Wolfram , Beadle John , Coats Andrew J. S. , Anker Stefan D. , Springer Jochen
Published: November 2013

Background

Sarcopenia, the age‐related, progressive loss of skeletal muscle mass, strength, and function, is a considerable socioeconomic burden by increasing risks of falls, fractures, and frailty. Moreover, sarcopenic patients are often obese and therapeutic options are very limited.

Methods

Here, we assessed the efficacy of espindolol on muscle mass in 19‐month‐old male Wistar Han rats (weight, 555 ± 18 g), including safety issues. Rats were randomized to treatment with 3 mg/kg/day espindolol (n = 8) or placebo (n = 14) for 31 days.

Results

Placebo‐treated rats progressively lost body weight (−15.5 ± 7.2 g), lean mass (−1.5 ± 4.2 g), and fat mass (−15.6 ± 2.7 g), while espindolol treatment increased body weight (+8.0 ± 6.1 g, p < 0.05), particularly lean mass (+43.4 ± 3.5 g, p < 0.001), and reduced fat mass further (−38.6 ± 3.4 g, p < 0.001). Anabolic/catabolic signaling was assessed in gastrocnemius muscle. Espindolol decreased proteasome and caspase‐3 proteolytic activities by approximately 50 % (all p < 0.05). Western blotting showed a reduced expression of key catabolic regulators, including NFκB, MuRF1, and LC‐3 (all p < 0.01). The 50‐ and 26‐kDa forms of myostatin were downregulated fivefold and 20‐fold, respectively (both p < 0.001). Moreover, 4E‐BP‐1 was reduced fivefold (p < 0.01), while phospho‐PI3K was upregulated fivefold (p < 0.001), although Akt expression and phosphorylation were lower compared to placebo (all p < 0.05). No regulation of p38 and expression of ERK1/2 were observed, while phosphorylation of p38 was reduced (−54 %, p < 0.001) and ERK1/2 was increased (115 and 83 %, respectively, both p < 0.01). Espindolol did not affect cardiac function (echocardiography) or clinical plasma parameters.

Conclusion

Espindolol reversed the effects of aging/sarcopenia, particularly loss of muscle mass and increased fat mass. Thus, espindolol is an attractive candidate drug for the treatment of sarcopenia patients.

Electronic supplementary material

The online version of this article (doi:10.1007/s13539‐013‐0125‐7) contains supplementary material.
Phage protein‐targeted cancer nanomedicines
Authors: Petrenko V.A. , Jayanna P.K.
Published: November 2013

Nanoencapsulation of anticancer drugs improves their therapeutic indices by virtue of the enhanced permeation and retention effect which achieves passive targeting of nanoparticles in tumors. This effect can be significantly enhanced by active targeting of nanovehicles to tumors. Numerous ligands have been proposed and used in various studies with peptides being considered attractive alternatives to antibodies. This is further reinforced by the availability of peptide phage display libraries which offer an unlimited reservoir of target‐specific probes. In particular landscape phages with multivalent display of target‐specific peptides which enable the phage particle itself to become a nanoplatform creates a paradigm for high throughput selection of nanoprobes setting the stage for personalized cancer management. Despite its promise, this conjugate of combinatorial chemistry and nanotechnology has not made a significant clinical impact in cancer management due to a lack of using robust processes that facilitate scale‐up and manufacturing. To this end we proposed the use of phage fusion protein as the navigating modules of novel targeted nanomedicine platforms which are described in this review.
p38‐Mediated phosphorylation of Eps15 endocytic adaptor protein
Authors: Zhou Yue , Tanaka Tomohiro , Sugiyama Naoyuki , Yokoyama Satoru , Kawasaki Yuki , Sakuma Tsutomu , Ishihama Yasushi , Saiki Ikuo , Sakurai Hiroaki
Published: November 2013

Epidermal growth factor receptor pathway substrate 15 (Eps15) has been suggested to be involved in the endocytosis of cell surface receptors, including epidermal growth factor receptor (EGFR). Eps15 is phosphorylated at Tyr‐849 upon stimulation with EGF during endocytic processes. In the present study, we found that stimulation of HeLa cells with EGF or TNF‐α induced transient phosphorylation of Eps15 at Ser‐796. Inhibition of p38 completely blocked phosphorylation and recombinant p38α directly phosphorylated the residue. These results demonstrate a novel stress kinase‐mediated signaling pathway to Eps15 endocytic adapter protein.
The U–Pb SHRIMP age of zircons from diorites of the Tomino–Bereznyaki ore field (South Urals, Russia): evolution of porphyry Cu–epithermal Au–Ag system
Authors: Grabezhev A.I. , Bea F. , Montero M.P. , Fershtater G.B.
Published: November 2013

The Tomino–Bereznyaki ore field lies in the western part of the East Urals volcanic megazone (20–30 km southwest of Chelyabinsk). The commercial Tomino porphyry (Mo, Au)–Cu deposit is localized in the east of the field, within a small mesoabyssal intrusion of quartz–diorite composition. The epithermal Au–Ag Bereznyaki deposit is confined to subvolcanic dioritic porphyrites in the west of the field. The western and eastern parts of the ore field have a tectonic boundary. Granitoids belong to a single volcanoplutonic complex of K–Na-quartz–diorite composition. The U–Pb concordant age of zircons from the ore-bearing dioritic porphyrite of the Tomino and Bereznyaki deposits is 428 ± 3 Ma (MSWD = 0.9) and 427 ± 6 Ma (MSWD = 1.1), respectively. A Silurian absolute age has been established for the Urals porphyry Cu ore-magmatic system for the first time. The diorites and acid metasomatites of both deposits contain a unique three-mica assemblage (Mu, Pa, and Mu0.36Pa0.64). The metasomatized diorites are of similar isotope-petrogeochemical compositions; they have close total REE contents (24–52 ppm) and REE patterns. Their Zr–Hf, Nb–Ta, and La–Ce diagrams show similar trends. The obtained data indicate the close time of formation of the porphyry and epithermal deposits and their probable genetic unity. The vertical evolution of the porphyry Cu column from meso- and hypabyssal to subvolcanic level includes the isotope (Sr, S, and O) crust–mantle interaction. The deposits formed at different depths expose on the modern surface as a result of the block tectonic processes in the ore field.
Ultramafic–mafic igneous complexes of the Precambrian East Siberian metallogenic province (southern framing of the Siberian craton): age, composition, origin, and ore potential
Authors: Polyakov G.V. , Tolstykh N.D. , Mekhonoshin A.S. , Izokh A.E. , Podlipskii M.Yu. , Orsoev D.A. , Kolotilina T.B.
Published: November 2013

Based on new data on the age, mineralogy, and geochemistry of ultramafic–mafic complexes in the Precambrian structures of the southern periphery of the Siberian Platform, the East Siberian metallogenic (PGE–Cu–Ni) province is recognized. It includes the Yenisei Ridge, Precambrian Kan uplift, Alkhadyr terrane with the adjacent structures of the Biryusa block, and northern Baikal region (Yoko-Dovyren and other massifs of the Baikal–Patom basin). We have established that the U–Pb and Ar–Ar ages of ore-bearing complexes of dunite–peridotite– pyroxenite–gabbro association correspond to the Late Riphean (728–710 Ma). The mineralogical and geochemical similarity of ore-bearing complexes in different areas testifies to their genetic entity. All parental melts were similar in composition to picrites. The calculation results and the PGE enrichment of rocks and ores show high degrees of melting of the mantle source, which agrees with the plume model of formation of the ore-magmatic system. The recognized province is similar in the type of magmatism and time of its occurrence to the Franklin LIP in northern Canada. It is one of the highly promising ore districts of East Siberia.
GPS-measurements of recent crustal deformation in the junction zone of the rift segments in the central Baikal rift system
Authors: Lukhnev A.V. , San’kov V.A. , Miroshnichenko A.I. , Ashurkov S.V. , Byzov L.M. , San’kov A.V. , Bashkuev Yu.B. , Dembelov M.G. , Calais E.
Published: November 2013

Based on multiyear measurements of present-day motions in the central area of the Baikal rift system, new data on the kinematics of horizontal motions, relative horizontal deformation rates, and rotation velocities in the area of junction of the South Baikal, North Baikal, and Barguzin rift basins have been obtained. This area is an intricate structure with two transfer zones: Ol’khon–Svyatoi Nos and Ust’-Barguzin. It is shown that crustal blocks are moving southeastward, normally to the structures of transfer zones and at an acute angle to the Baikal Rift strike, which corresponds to the right-lateral strike-slip extensional faulting along the major structure. The average horizontal velocities increase from 3.0 mm yr–1 in the northern South Baikal basin to 6.5 mm yr–1 in the Barguzin basin. The elongation axes prevailing in the study region are mainly of NW–SE direction. The areas of intense deformations are confined to structures with high seismic activity in the South Baikal and, partly, Barguzin basins. This confirms the existence of a present-day zone of the Earth’s crust destruction in the Baikal rift system, which is the most likely source of strong earthquakes in the future. Two zones with rotations in opposite directions are recognized in the rotation velocity field. Clockwise rotation is typical of structures of N–NE strike (Maloe More basin, southern North Baikal basin, Barguzin Ridge rise). Counterclockwise rotation is determined for NE-striking structures (northern South Baikal basin, southern Barguzin basin). In general, the obtained data show an intricate pattern of present-day horizontal dislocations and deformations in the area of junction of NE- and N–NE-striking rift structures. This suggests left- and right-lateral strike-slip faults, respectively, within them.
Typomorphic characteristics of the Ural diamonds (from FTIR spectroscopy data)
Authors: Fedorova E.N. , Logvinova A.M. , Luk’yanova L.I. , Sobolev N.V.
Published: November 2013

Natural diamonds from the Ural alluvial deposits have been studied by FTIR spectroscopy. It is shown that these diamonds are similar in some typomorphic features, such as nitrogen content and aggregation state, to the diamonds of the Coromandel (Brazil) and Verkhnee Molodo (Lena region, Yakutia) placers and to the diamonds from kimberlites of the Arkhangel’sk Region but differ significantly in lower contents of hydrogen and higher contents of platelets. The high contents of hydrogen (5–20 cm–1) determined in some diamonds are due to the specific formation of their internal structure and to the presence of inclusions. The nonuniform distribution of nitrogen A- and B-centers throughout the crystal testifies to the zonal structure of diamonds. The temperature conditions of formation of the Ural diamonds have been estimated.
Native gold in complex Ti–Zr placers of the southern West Siberian Plain
Authors: Nesterenko G.V. , Kolpakov V.V. , Boboshko L.P.
Published: November 2013

Typomorphic features of native gold and its contents in complex Ti–Zr placers in the southern West Siberian Plain are reported. Three of the placers are of littoral-marine genesis, and two formed under conditions of an alluvial piedmont plain. Native gold from the studied Ti–Zr placers occurs mainly as flattened thin (–0.1 mm) particles which underwent mechanical action. It is marked by wide fineness variation and the abundance of a very fine (990–1000‰) variety. Most likely, this is chemically transformed clastogenic metal. The gold content of the productive bed (5–30 mg/m3 native gold and 8–140 ppb bulk gold) is consistent with the dispersion of heavy ore and accessory minerals during mechanical migration in water flows simultaneously with their concentration on geochemical barriers. The native-gold content of complex Ti–Zr placers shows a higher negative correlation with the primary source–placer distance than those of Ti and Zr minerals and a positive correlation with the degree of hydrodynamic reworking (gravity concentration) of transit terrigenous material. On the southern framing of the West Siberian Plain, some regions of northern Kazakhstan are promising for gold of complex Ti–Zr placers as well as fine- and thin-gold placers, gold-bearing weathering crusts, and primary gold deposits.
Coastal-zone shallow-aquifer characterization study using geoelectrical and geochemical methods in Zirconium Complex, Atomic Energy, Pazhayakayal, Thoothukudi, India
Authors: Ravindran A. Antony
Published: November 2013

Groundwater is a very important component of water resources in coastal aquifers in Thoothukudi. It has been established that the groundwaters in the coastal zone of the Zirconium Complex, Pazhayakayal, Thoothukudi district, Tamilnadu, India, are subjected to wave and tidal impact. The groundwater quality was studied by hydrogeological methods, 2D electrical resistivity imaging (ERI) techniques (six profiles), 11 Wenner vertical electrical sounding (VES), and well log analysis. Also, nine geochemical water samples were taken from the study area. The 2D ERI and VES surveys were carried out using WGMD-4 Ltd., Chennai, resistivity meter, multicore cable, and multielectrodes with Wenner array. The collected resistivity data were interpreted using the Res2DINV software. The research shows that the groundwaters are the result of the paleoriver flow along the Tamirabarani Channel in the western area and of the seawater intrusion in the eastern area. The fresh water is characterized by resistivity of about 10–100 Ohm⋅m in the study area. The resistivity of 10–50 Ohm⋅m indicates that the subsurface section is made up of sand, clay, and caliche. Resistivity values of more than 200 Ohm⋅m are specific to sand dunes. The very low resistivity (<5 Ohm⋅m) layer might be due to the seawater intrusion in the study area. Six water samples from the well drilled in the coastal area were analyzed, which made it possible to determine the concentrations of major and trace elements in the groundwaters. These data were used to establish the seawater intrusion and coastal environment characteristics in the study area.