bluuebunny/crossref_metadata_2025 huggingface dataset:
Ethylene to 2‐Butene in a Continuous Gas Phase Reaction using SILP‐Type Cationic Nickel Catalysts
Authors: Scholz Judith , Hager Veit , Wang Xinjiao , Kohler Florian T. U. , Sternberg Michelle , Haumann Marco , Szesni Normen , Meyer Karsten , Wasserscheid Peter
Published: November 2013

Owing to shifting market demands, it is important to convert ethylene to propylene. One attractive way to achieve this conversion is the dimerization of ethylene to 1‐butene, followed by isomerization to 2‐butene and subsequent metathesis of 2‐butene/ethylene olefin. Our contribution focuses on combining the first two steps. Herein, we report a highly selective tandem dimerization/isomerization of ethylene to 2‐butene catalyzed by homogeneously dissolved cationic nickel complexes. These catalysts can be efficiently immobilized by using the supported ionic liquid phase technology. Such supported ionic liquid phase materials have been tested under continuous gas phase conditions and demonstrated attractive catalytic performance with respect to both catalyst stability and productivity after the optimization of support, ionic liquid, ligand, and process parameters. The limited thermal stability of the nickel complexes and olefin condensation at too low temperatures require a careful thermal management of the fixed‐bed reactor.
The Partial Hydrogenation of 1,3‐Dienes Catalysed by Soluble Transition‐Metal Nanoparticles
Authors: Luza Leandro , Gual Aitor , Dupont Jairton
Published: November 2013

The partial hydrogenation of 1,3‐dienes is a structure sensitive reaction that is typically catalysed by classical heterogeneous (heterotopic) or homogeneous (homotopic) catalysts. Recently, soluble transition‐metal nanoparticles (M‐NPs), particularly palladium and gold‐based systems, have emerged as an efficient alternative. Here, we review the current state of the techniques for the partial hydrogenation of 1,3‐dienes by M‐NPs and conclude that, from the reactivity point of view, these materials possess heterotopic‐like and homotopic‐like characteristics. They are heterotopic‐like because the relative concentration of the monoalkene with respect to the diene does not affect the product selectivity and their catalytic performance is affected by their physical properties (such as size and shape). Furthermore, they are easily recoverable, with long catalytic lifetimes. Additionally, as homotopic systems, their reactivity can be tuned by using an appropriate organic stabiliser, which displays substrate‐selective levels that are not observed for classical heterotopic catalysts.
The Borosulfate Story Goes on—From Alkali and Oxonium Salts to Polyacids
Authors: Daub Michael , Kazmierczak Karolina , Höppe Henning A. , Hillebrecht Harald
Published: November 2013

The structural principles of borosulfates derived from the B/S ratio are confirmed and extended to new representatives of this class showing novel motifs. According to the composition, Na[B(S2O7)2] (P21/c; a=10.949(6), b=8.491(14), c=12.701(8) Å; β=110.227(1)°; Z=4) and K[B(S2O7)2] (Cc; a=11.3368(6), b=14.662(14), c=13.6650(8) Å; β=94.235(1)°; Z=8) contain isolated [B(S2O7)2]− ions, in which the central BO4 tetrahedron is coordinated by two disulfate units. The alkali cations have coordination numbers of 7 (Na) and 8 (K), respectively. The structure of Cs[B(S2O7)(SO4)] (P21/c; a=10.4525(6), b=11.3191(14), c=8.2760(8) Å; β=103.206(1); Z=4) combines, for the first time, sulfate and disulfate units into a chain structure. Cs has a coordination number of 12. The same structural units were found in H[B(S2O7)(SO4)] (P21/c; a=15.6974(6), b=11.4362(14), c=8.5557(8) Å; β=90.334(3)°; Z=8). This compound represents the first example of a polyacid. The hydrogen atoms were located and connect the chains to form layers through hydrogen‐bonding bridges. H3O[B(SO4)2] (P4/ncc; a=9.1377(6), c=7.3423(8) Å; Z=4) is the first oxonium compound of this type to be found. The BO4 tetrahedra are linked by SO4 tetrahedra to form linear chains similar to those in SiS2. The chains form a tetragonal rod packing structure with H3O+ between the rods. The structures of borosulfates can be classified following the concept described by Liebau for silicates, which was extended to borophosphates by Kniep et al. In contrast to these structures, borosulfates do not comprise B‐O‐B bonds but instead contain S‐O‐S connections. All compounds were obtained as colourless, moisture‐sensitive single crystals by reaction of B2O3 and the appropriate alkali salt in oleum.
Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes
Authors: Tropiano Manuel , Blackburn Octavia A. , Tilney James A. , Hill Leila R. , Placidi Matteo P. , Aarons Rebecca J. , Sykes Daniel , Jones Michael W. , Kenwright Alan M. , Snaith John S. , Sørensen Thomas Just , Faulkner Stephen
Published: November 2013

A study of the anion‐binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion‐binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery of the molecule, at a substantial distance from the binding pocket. Herein, we explore these remote substituent effects and explain the observed behaviour through discussion of the way in which remote substituents can influence and control the global structure of a molecule through their demands upon conformational space. Peripheral modifications to a binuclear lanthanide motif derived from α,α′‐bis(DO3 Ayl)‐m‐xylene are shown to result in dramatic changes to the binding constant for isophthalate. In this system, the parent compound displays considerable conformational flexibility, yet can be assumed to bind to isophthalate through a well‐defined conformer. Addition of steric bulk remote from the binding site restricts conformational mobility, giving rise to an increase in binding constant on entropic grounds as long as the ideal binding conformation is not excluded from the available range of conformers.
β‐Hydroxyamide‐Based Ligands and Their Use in the Enantioselective Borane Reduction of Prochiral Ketones
Authors: Azizoglu Murat , Erdogan Asli , Arslan Nevin , Turgut Yilmaz
Published: November 2013

Hydroxyamide‐based ligands have occupied a considerable place in asymmetric synthesis. Here we report the synthesis of seven β‐hydroxyamide‐based ligands from the reaction of 2‐hydroxynicotinic acid with chiral amino alcohols and test their effect on the enantioselective reduction of aromatic prochiral ketones with borane in tetrahydofuran (THF). They produce the corresponding secondary alcohols with up to 76% enantiomeric excess (ee) and good to excellent yields (86‐99%). Chirality 26:21–26, 2013. © 2013 Wiley Periodicals, Inc.
Structural Design, Synthesis and Structure–Activity Relationships of Thiazolidinones with Enhanced Anti‐Trypanosoma cruzi Activity
Authors: Moreira Diogo Rodrigo Magalhães , Lima Leite Ana Cristina , Cardoso Marcos Verissimo Oliveira , Srivastava Rajendra Mohan , Hernandes Marcelo Zaldini , Rabello Marcelo Montenegro , da Cruz Luana Faria , Ferreira Rafaela Salgado , de Simone Carlos Alberto , Meira Cássio Santana , Guimaraes Elisalva Teixeira , da Silva Aline Caroline , dos Santos Thiago André Ramos , Pereira Valéria Rêgo Alves , Pereira Soares Milena Botelho
Published: November 2013

Pharmacological treatment of Chagas disease is based on benznidazole, which displays poor efficacy when administered during the chronic phase of infection. Therefore, the development of new therapeutic options is needed. This study reports on the structural design and synthesis of a new class of anti‐Trypanosoma cruzi thiazolidinones (4 a–p). (2‐[2‐Phenoxy‐1‐(4‐bromophenyl)ethylidene)hydrazono]‐5‐ethylthiazolidin‐4‐one (4 h) and (2‐[2‐phenoxy‐1‐(4‐phenylphenyl)ethylidene)hydrazono]‐5‐ethylthiazolidin‐4‐one (4 l) were the most potent compounds, resulting in reduced epimastigote proliferation and were toxic for trypomastigotes at concentrations below 10 μM, while they did not display host cell toxicity up to 200 μM. Thiazolidinone 4 h was able to reduce the in vitro parasite burden and the blood parasitemia in mice with similar potency to benznidazole. More importantly, T. cruzi infection reduction was achieved without exhibiting mouse toxicity. Regarding the molecular mechanism of action, these thiazolidinones did not inhibit cruzain activity, which is the major trypanosomal protease. However, investigating the cellular mechanism of action, thiazolidinones altered Golgi complex and endoplasmic reticulum (ER) morphology, produced atypical cytosolic vacuoles, as well as induced necrotic parasite death. This structural design employed for the new anti‐T. cruzi thiazolidinones (4 a–p) led to the identification of compounds with enhanced potency and selectivity compared to first‐generation thiazolidinones. These compounds did not inhibit cruzain activity, but exhibited strong antiparasitic activity by acting as parasiticidal agents and inducing a necrotic parasite cell death.
Usefulness of p16/Ki67 immunostaining in the triage of women referred to colposcopy
Authors: Ordi Jaume , Sagasta Amaia , Munmany Meritxell , Rodríguez‐Carunchio Leonardo , Torné Aureli , del Pino Marta
Published: November 2013

BACKGROUND

This study compared the performance of p16/Ki67 dual‐staining and human papillomavirus (HPV) testing in women referred to colposcopy and sought to determine the usefulness of a morphological evaluation of the double‐stained cells.

METHODS

This prospective study included 1123 women (mean age, 35.8 ± 10.9 years) referred to colposcopy from October 2009 to November 2012 due to positive HPV testing or abnormal cytology results (atypical squamous cells of unknown significance, or worse abnormalities). Liquid‐based cytology specimens (PreservCyt, Hologic) were used for HPV detection (Hybrid Capture 2 [HC2]; Qiagen) and p16/Ki67 dual‐staining (CINtec Plus; Roche‐mtm Laboratories). All women underwent histological study. After completion of the study, 18 patients were classified as having cervical cancer (CC), 378 had a high‐grade squamous intraepithelial lesion (HSIL), 304 had a low‐grade squamous intraepithelial lesion, and 423 were negative.

RESULTS

The sensitivity and specificity of p16/Ki67 dual‐staining for HSIL/CC were 90.9% (95% confidence interval [CI] = 87.9‐93.9) and 72.1 (95% CI = 68.7‐75.4), respectively. For HC2, the figures were, respectively, 96.0% (95% CI = 93.9‐98.0) and 41.4 (95% CI = 37.7‐45.0). The values were high both in women < 30 and ≥ 30 years old (86.9% and 63.3% versus 92.3% and 77.8%, respectively). The addition of a morphological evaluation of the dual‐stain–positive cells with establishment of HSIL features as the threshold for a positive reaction increased the specificity (93.5%) but decreased the sensitivity (84.1%).

CONCLUSIONS

Use of the molecular markers p16 and Ki67 has higher specificity than HC2 tests for HSIL or CC, which may support p16/Ki67 dual‐staining use in the triage of patients referred for abnormal screening results. Morphological evaluation of p16/Ki67‐positive cells may have some benefits in women younger than 30 years or with low‐grade squamous intraepithelial lesion. Cancer (Cancer Cytopathol) 20141;22:227–235. © 2013 American Cancer Society.
Influence of descriptive terminology on management of atypical thyroid fine‐needle aspirates
Authors: Vivero Marina , Renshaw Andrew A. , Krane Jeffrey F.
Published: November 2013

BACKGROUND

The Bethesda System category of atypia of undetermined significance/follicular lesion of undetermined significance (AUS/FLUS) is used to classify a variety of mild abnormalities in thyroid FNAs. Modifying terminology is often added to FNA reports, but it is unknown whether specific phrases affect clinical management. To answer this question, the authors correlated treatment of patients who had initial AUS/FLUS diagnoses from Baptist Hospital (Miami, Fla) (BH) and Brigham and Women's Hospital (Boston, Mass) (BWH) with the language used in pathology reports.

METHODS

In total, 146 FNAs from BH, including 115 women and 31 men with a median age of 53 years (range, 21‐79 years), and 300 FNAs from BWH, including 241 women and 59 men with a median age of 66 years (range, 10‐85 years), were included. FNA reports were evaluated for predetermined descriptive phrases and were correlated with subsequent management.

RESULTS

More patients with available follow‐up underwent excision at BH than at BWH (86% vs 8%; P < .001), and fewer underwent a repeat biopsy (14% vs 92%; P < .001). Qualifiers associated with differing malignancy risk affected patient management (P < .05) at BH, but not at BWH. Reports indicating a scant or limited specimen increased rebiopsy rates at BH (100% vs 4.8%; P < .05), but not at BWH (93% vs 91%; P = .67), as did explicit recommendation for rebiopsy at BH (35% vs 14%; P = .03). No other phrases affected patient management (P > .05).

CONCLUSIONS

In practice settings that follow The Bethesda System management guidelines, descriptive report terminology does not modify patient treatment. In less standardized settings, terminology associated with differing risk of malignancy on subsequent excision, pathologist recommendations, and phrases indicative of limited sampling significantly alter patient management. Cancer (Cancer Cytopathol) 2014;122:175–181. © 2013 American Cancer Society.
One‐Step Hydrothermal Synthesis of a Porous Cu2O Film and Its Photoelectrochemical Properties
Authors: Ji Ran , Sun Wendong , Chu Ying
Published: November 2013

A cuprous oxide (Cu2O) film with a novel porous structure is successfully synthesized on Cu foil by using a simple hydrothermal method. A redox reaction occurs between Cu and Cu2+ in aqueous solution to form the Cu2O film. The porous structures are formed as a result of the Ostwald ripening mechanism. In addition, photoluminescence measurements indicate that the porous Cu2O film may reduce the recombination of photogenerated electrons and holes. The UV/Vis absorption property of the porous Cu2O film is better than that of the granular Cu2O film, and its high photocurrent is expected to make the porous Cu2O film more suitable for solar energy applications.
Managing Corporate Sustainability and CSR: A Conceptual Framework Combining Values, Strategies and Instruments Contributing to Sustainable Development
Authors: Baumgartner Rupert J.
Published: November 2013

Sustainable development can be a source of success, innovation, and profitability for companies. To use this source and to deal with the challenge of sustainability, corporations need a framework they can rely on in order to identify opportunities and threats and to develop, implement, control, and improve corporate sustainability strategies to be both more sustainable (for themselves and the society) and more successful in economic terms. Based on an extensive literature review of strategic management, CSR, and corporate sustainability, a conceptual framework is developed which offers an integrated view on the relevance of sustainability aspects for an individual company and enables the integration of these sustainability aspects on different management levels. Contextual factors are used to identify the relevance of sustainable development and the significant sustainability aspects. Based on this initial step, the relevance of sustainability issues for the different management levels, as well as opportunities and threats related to sustainable development, can be identified. The framework distinguishes three different management levels: normative management, strategic management, and operational management. Questions of vision and mission of a company and of the fit between sustainability engagement and organizational culture are in focus of the normative management level. Developing an effective corporate sustainability strategy is part of the strategic level. The implementation of the sustainability strategy in the different corporate functions is part of the operational level. This framework for corporate sustainability management is supported by instruments which are clustered in different areas like performance measurement, assessment and evaluation, operational management or strategic management. Copyright © 2013 John Wiley & Sons, Ltd and ERP Environment
Design, Synthesis, and Evaluation of Nonaqueous Silylamines for Efficient CO2 Capture
Authors: Switzer Jackson R. , Ethier Amy L. , Hart Emily C. , Flack Kyle M. , Rumple Amber C. , Donaldson Jordan C. , Bembry Ashley T. , Scott Owen M. , Biddinger Elizabeth J. , Talreja Manish , Song Myoung‐Geun , Pollet Pamela , Eckert Charles A. , Liotta Charles L.
Published: November 2013

A series of silylated amines have been synthesized for use as reversible ionic liquids in the application of post‐combustion carbon capture. We describe a molecular design process aimed at influencing industrially relevant carbon capture properties, such as viscosity, temperature of reversal, and enthalpy of regeneration, while maximizing the overall CO2‐capture capacity. A strong structure–property relationship among the silylamines is demonstrated in which minor structural modifications lead to significant changes in the bulk properties of the reversible ionic liquid formed from reaction with CO2.
Is population structure in theEuropean white stork determined by flyway permeability rather than translocation history?
Authors: Shephard Jill M. , Ogden Rob , Tryjanowski Piotr , Olsson Ola , Galbusera Peter
Published: November 2013

European white stork are long considered to diverge to eastern and western migration pools as a result of independent overwintering flyways. In relatively recent times, the western and northern distribution has been subject to dramatic population declines and country‐specific extirpations. A number of independent reintroduction programs were started in the mid 1950s to bring storks back to historical ranges. Founder individuals were sourced opportunistically from the Eastern and Western European distributions and Algeria, leading to significant artificial mixing between eastern and western flyways. Here we use mitochondrial and microsatelliteDNAto test the contention that prior to translocation, eastern and western flyways were genetically distinct. The data show a surprising lack of structure at any spatial or temporal scale suggesting that even though birds were moved between flyways, there is evidence of natural mixing prior to the onset of translocation activities. Overall a high retention of genetic diversity, highNef, and an apparent absence of recent genetic bottleneck associated with early 20th century declines suggest that the species is well equipped to respond to future environmental pressures.
Community Resilience, Transitional Corridors and Macro‐Scalar Lock‐in Effects
Authors: Wilson Geoff A.
Published: November 2013

This article analyses interlinkages between community resilience, transitional corridors and macro‐scalar lock‐in effects, with specific emphasis on exogenous drivers. Transition theory is used as an approach to analyse resilience pathways. The article suggests that transitional corridors shape decision‐making opportunities, which are ultimately mediated by the individual/household within a community and turned into action with tangible effects on resilience/vulnerability ‘on the ground’. The importance of macro‐structural ‘lock‐ins’ for understanding constraints and opportunities for raising community resilience is highlighted, including in particular political and policy‐based decision‐making pathways, macro‐structural lock‐ins, ideological lock‐in effects and macro‐economic lock‐ins. The article concludes by arguing that transitional corridors are key processes for understanding community resilience, and that more empirical work is needed to unravel interlinkages between how the ‘boundaries’ of these corridors specifically affect community resilience and how communities can help shape or influence these transitional corridors to build more resilient futures. Copyright © 2013 John Wiley & Sons, Ltd and ERP Environment.
Graphene Oxide Modified Ag2O Nanocomposites with Enhanced Photocatalytic Activity under Visible‐Light Irradiation
Authors: Ji Zhenyuan , Shen Xiaoping , Yang Jinglei , Xu Yuling , Zhu Guoxing , Chen Kangmin
Published: November 2013

Owing to its unique two‐dimensional structure and extraordinary physicochemical properties, graphene oxide (GO) is considered an ideal support for developing highly efficient photocatalysts. In this study, a novel Ag2O/GO nanocomposite, as a visible‐light‐induced photocatalyst, has been fabricated by a simple solution route. The electrostatic interactions between positively charged Ag+ and negatively charged GO sheets are responsible for the formation of the Ag2O/GO nanocomposite. The anchoring of the Ag2O nanoparticles on the GO nanosheets was confirmed by X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The photocatalytic degradation of Methylene Blue (MB) under visible‐light irradiation was studied to evaluate the photocatalytic activity of the Ag2O/GO nanocomposites. Due to the enhanced adsorption capacity, the smaller size of the Ag2O nanoparticles, and the improved separation of electron–hole pairs after the incorporation with GO sheets, the Ag2O/GO nanocomposites showed enhanced photocatalytic activity compared with bare Ag2O nanoparticles. In addition, the kinetics of the photocatalytic degradation reaction and a plausible photocatalytic mechanism are presented. The results pave the way to the design of highly efficient visible‐light‐responsive photocatalysts for the removal of organic pollutants for water purification.
Recurrent and second primary squamous cell carcinoma of the head and neck: When and how to reirradiate
Authors: Strojan Primož , Corry June , Eisbruch Avraham , Vermorken Jan B. , Mendenhall William M. , Lee Anne W. M. , Haigentz Missak , Beitler Jonathan J. , de Bree Remco , Takes Robert P. , Paleri Vinidh , Kelly Charles G. , Genden Eric M. , Bradford Carol R. , Harrison Louis B. , Rinaldo Alessandra , Ferlito Alfio
Published: November 2013

Background

Local and/or regional recurrence and metachronous primary tumor arising in a previously irradiated area are rather frequent events in patients with head and neck squamous cell carcinoma (HNSCC). Re‐treatment is associated with an increased risk of serious toxicity and impaired quality of life (QOL) with an uncertain survival advantage.

Methods

We analyzed the literature on the efficacy and toxicity of photon/electron‐based external beam reirradiation for previously irradiated patients with HNSCC of non‐nasopharyngeal origin. Studies were grouped according to the radiotherapy technique used for reirradiation. Patient selection criteria, target volume identification method, tumor dose, fractionation schedule, systemic therapy administration, and toxicities were reviewed.

Results

In addition to disease‐related factors, current comorbidities and preexisting organ dysfunction must be considered when selecting patients for reirradiation. As morbidity from re‐treatment may be considerable and differ depending on which mode of re‐treatment is used, it is important to give patients information on potential morbidity outcomes so that an informed choice can be made within a shared decision‐making context. With improved dose distribution and adequate imaging support, including positron emission tomography‐CT, modern radiotherapy techniques may improve local control and reduce toxicity of reirradiation. A reirradiation dose of ≥60 Gy and a volume encompassing the gross tumor with up to a 5‐mm margin are recommended. Concomitant administration of systemic therapeutics and reirradiation is likely to be of similar benefit as observed in large randomized studies of upfront therapy.

Conclusion

Reirradiation, administered either with or without concurrent systemic therapy, is feasible and tolerable in properly selected patients with recurrent or a new primary tumor in a previously irradiated area of the head and neck, offering a meaningful survival (in the range of 10% to 30% at 2 years). Whenever feasible, salvage surgery is the method of choice for curative intent; patients at high‐risk for local recurrence should be advised that postoperative reirradiation is expected to increase locoregional control at the expense of higher toxicity and without survival advantage compared to salvage surgery without reirradiation. © 2014 Wiley Periodicals, Inc. Head Neck 37: 134–150, 2015
The snakes and ladders of National Health Service management in England
Authors: Powell Martin
Published: November 2013

This article explores managerial careers in the National Health Service (NHS) through the lens of talent management, particularly focusing on how managers view barriers (snakes) and facilitators (ladders) to career progression. There is a significant literature on enablers and barriers to career progression, but much of this focuses on specific groups such as black and minority ethnic and female workers, and there is relatively little material on the general workforce of the NHS. The research design is a mixed method quantitative (questionnaire) and qualitative (interview and focus group) approach consisting of a quasi‐probability element that focuses on a maximum variety sample and a purposive element that seeks policy views at central and strategic health authority level, and examines talent management in high‐performing NHS organisations. Ladders are identified as follows: volunteering, secondment, networking, mentoring, academic qualifications, development, good role models/managers and appraisal/personal development plan. Snakes are identified as managing expectations; identity and cognitive diversity; location; sector; NHS toxic and favouritism culture; poor talent spotting; credentialism; exclusive approach to talent; and sustainability. It concludes that while previous conceptual and empirical work is fairly clear on any ladders, it is less clear on snakes. Copyright © 2013 John Wiley & Sons, Ltd.
Hepatic fibrogenesis and transforming growth factor/Smad signaling activation in rats chronically exposed to low doses of lead
Authors: Perez Aguilar Rossana C. , Honoré Stella M. , Genta Susana B. , Sánchez Sara S.
Published: November 2013

Lead is an important heavy metal pollutant in the environment. The nervous system, kidney and liver are the most susceptible organs to lead deposition, showing that this pollutant has no single target system. To examine the cellular and molecular mechanisms involved in their pathobiology of chronic lead at low‐dose exposure in the liver, male Wistar rats were exposed to 0.06% lead acetate in drinking water every day for 4 months. At the end of the study, hepatic metal accumulation, morphology and function were examined. Immunochemical staining and Western blot analysis were performed to detect extracellular matrix proteins, α‐smooth muscle actin and transforming growth factor (TGF)β1/Smad pathway expression. Results showed increased laminin, collagen IV and fibronectin, located at the perisinusoidal space. Phenotypic transformation of hepatic stellate cells into myofibroblast‐like cells was evidenced at the ultrastructural level and a significant expression of α‐smooth muscle actin in Disse's space was observed. These findings were associated with a marked increase in TGFβ1/Smad2/3 signaling. Our data suggest that, chronically, exposure to low levels of lead could trigger the onset of a hepatic fibrogenic process through upregulated TGFβ1/Smad signaling. Copyright © 2013 John Wiley & Sons, Ltd.
Median nerve T2 assessment in the wrist joints: Preliminary study in patients with carpal tunnel syndrome and healthy volunteers
Authors: Cha Jang Gyu , Han Jong Kyu , Im Soo Bin , Kang Sung Jin
Published: November 2013

Purpose

To perform a prospective quantitative analysis of median nerve T2 values and cross‐sectional area (CSA) in patients with carpal tunnel syndrome (CTS) as compared to asymptomatic volunteers.

Materials and Methods

Twelve CTS patients with positive nerve conduction results and 12 healthy volunteers (controls) were enrolled and underwent axial T2 mapping of the wrist joints. Median nerve T2 values and CSAs at the distal radioulnar joint, pisiform, and hook of hamate levels were compared between the groups.

Results

The T2 values at the proximal and distal carpal tunnel were higher in the CTS patients than in the controls (P < 0.05). The T2 values at the distal radioulnar joint did not differ between the groups (P = 0.99). The CSAs of the median nerve at all levels of the carpal tunnel were significantly larger in the CTS patients than in the controls (P < 0.05).

Conclusion

In conclusion, our study demonstrated that median nerve T2 assessment is feasible and that T2 assessment may offer functional information about the median nerve in the carpal tunnel and has the potential to be a promising complementary method for evaluation of CTS patients. A future study with larger sample sizes is necessary to investigate the potential effect of median nerve T2 assessment to a reliable tool in the diagnosis of CTS.J. Magn. Reson. Imaging 2014;40:789–795 © 2013 Wiley Periodicals, Inc.
On the impact of physiological noise in spinal cord functional MRI
Authors: Fratini Michela , Moraschi Marta , Maraviglia Bruno , Giove Federico
Published: November 2013

Functional magnetic resonance imaging (fMRI) techniques are widely exploited for the study of brain activation. In recent years, similar approaches have been attempted for the study of spinal cord function; however, obtaining good functional images of spinal cord still represents a technical and scientific challenge. Some of the main limiting factors can be classified under the broad category of “physiological noise,” and are related to 1) the cerebrospinal fluid (CSF) flux in the subarachnoid space surrounding the spinal cord; 2) the cord motion itself; and 3) the small area of the cord, which makes it critical to have a high image resolution. In addition, the different magnetic susceptibility properties of tissues surrounding the spinal cord reduce the local homogeneity of the static magnetic field, causing image distortion, reduction of the effective resolution, and signal loss, all effects that are modulated by motion. For these reasons, a number of methods have been developed for the purpose of denoising spinal cord fMRI time series. In this work, after a short introduction on the relevant features of the spinal cord anatomy, we review the main sources of physiological noise in spinal cord fMRI and discuss the main approaches useful for its mitigation. J. Magn. Reson. Imaging 2014;40:770–777. © 2013 Wiley Periodicals, Inc.
Acetone cation chemistry under varying electron density conditions: from unimolecular decomposition to dissociative recombination processes
Authors: Parnis J. Mark , King Kaitlynn A. , Thompson Matthew G. K.
Published: November 2013

The chemistry of ionized acetone:Ar mixtures under varied ionizing electron density conditions has been studied using matrix‐isolation techniques. Gaseous acetone diluted in excess argon gas was subjected to electron bombardment with 300 eV electrons at currents between 20 and 200 μA. Linear wire ‘pin’ and metal ‘plate’ electron collector geometries were employed, allowing a wide range of electron density conditions to be explored. The products of subsequent reaction processes were matrix isolated and analyzed by Fourier transform infrared absorption spectroscopy. Products included methane, ketene, 1‐propen‐2‐ol (the enol isomer of acetone), CO, HCO, ethane, ethane, acetylene and CCCO. Product absolute and relative yields varied with acetone number density, the choice of anode geometry and the rate of electron bombardment. The overall chemistry observed is rationalized in terms of mechanistic steps involving unimolecular cation decomposition, ion–molecule reactions, radical–radical reactions and dissociative recombination processes. Copyright © 2013 John Wiley & Sons, Ltd.
A comparison of screen temperature as measured by two Met Office observing systems
Authors: Clark M. R. , Lee D. S. , Legg T. P.
Published: November 2013

During 2009, the Met Office implemented a new surface observing system, the Meteorological Monitoring System (MMS). We report the results of a comparison of screen temperature as measured by MMS, and the Semi‐Automatic Meteorological Observing System (SAMOS), the most widely used of the systems which MMS replaces. In each system, temperature was measured at 1‐min resolution using 100 Ω platinum resistance thermometers. Comparison of MMS and SAMOS temperatures in separate Stevenson screens revealed acceptably small mean temperature differences (0.05 °C); however, MMS temperatures tended to be 0.3–0.5 °C higher than SAMOS temperatures during conditions of strong solar radiation, with extreme differences of up to 0.8 °C. Such differences were largely absent when MMS and SAMOS temperatures were measured from within the same screen, suggesting that differences in the immediate environment of each screen may have been responsible. However, even within the same screen, a diurnal cycle in the (SAMOS–MMS) temperature differences of amplitude (peak‐to‐peak) ∼0.04–0.06 °C was observed, which was likely due to the effects of low‐angle solar radiation. Additional testing using a third, independent temperature unit revealed a slight temperature dependency in the SAMOS measurements; extrapolation of the results suggests differences of 0.2–0.3 °C between SAMOS and MMS temperatures at ambient temperatures >30 °C (MMS warmer). Overall, however, the differences between SAMOS and MMS temperatures were small, being well within World Meteorological Organization (WMO) accuracy limits for mean and extreme temperatures. The results therefore demonstrate that any step change in climatological temperature records associated with the introduction of MMS may be considered negligible.
Metabolomic analysis of the polyphenols in germinating mung beans (Vigna radiata) seeds and sprouts
Authors: Tang Dongyan , Dong Yinmao , Guo Na , Li Li , Ren Hankun
Published: November 2013

BACKGROUND

The mung bean (Vigna radiata) is a key food crop in much of Asia and contains plentiful biological activities to prevent human disease. Mung bean sprouts have more plentiful metabolites and activities after germination.

RESULTS

The metabolite profile of polyphenols in the germination process was described using the methods of ultra‐high‐performance liquid chromatography coupled with time‐of‐flight mass spectrometry and partial least squares discriminant analysis. Sprouts from different periods were clearly discriminated from each other. Eight flavonoids – vitexin, isovitexin, rutin, kaempferol 3‐O‐rutinoside, isoquercitrin, genistein, daidzein and isorhamnetin – and two phenolic acids – shikimic acid and caffeic acid – were thought to be chemical markers of the sprouts. The method of high‐performance liquid chromatography with diode array detection was established to quantitatively analyze the eight chemical markers of flavonoids, and provides good linearity, repeatability, intra‐ and inter‐day precision, accuracy and recovery. The main metabolic and transformation pathways of the polyphenols in the germination process were discussed.

CONCLUSION

The proposed method is sensitive, rapid and robust. Understanding the complete profile of polyphenol metabolites in the germination process may be useful for better utilizing mung beans sprouts as the raw materials of functional food, health products and cosmetics. © 2013 Society of Chemical Industry
Tracheostomy as Treatment for Adult Obstructive Sleep Apnea
Authors: Camacho Macario , Certal Victor , Brietzke Scott E. , Holty Jon‐Erik C. , Guilleminault Christian , Capasso Robson
Published: November 2013

Objectives/Hypothesis

To systematically review outcomes for polysomnography, sleepiness, and mortality in patients who undergo tracheostomy for the treatment of adult obstructive sleep apnea (OSA).

Data Sources

MEDLINE, Scopus, and the Cochrane Library were searched from inception to March 2013, followed by extensive hand searching for the identification of relevant English language studies that met predefined criteria.

Review Methods

Adult studies of tracheostomies or tracheotomies as treatment for OSA with outcomes for apnea index (AI), apnea–hypopnea index (AHI), oxygen desaturation index (ODI), effect on daytime sleepiness or mortality were identified, abstracted and pooled (as appropriate). Preferred Reporting Items for Systematic Reviews and Meta‐Analyses (PRISMA) guidelines were followed.

Results

The systematic search identified 18 relevant studies that were primarily case series, using retrospective review. Posttracheostomy AI improved from 73.0 ± 27.1 to 0.2 ± 1.2/h and an AI mean difference of −83.47 (95% CI, −106.07 to −60.87; P < 0.0001). Mean AHI decreased from 92.0 ± 34.8 to 17.3 ± 20.5/h and an AHI mean difference −79.82 (95% CI, −63.74 to −95.90; P < 0.0001) compared with preoperative status was observed. Postsurgically, there was a development of central apneas; however, the central AI demonstrated near normalization to a mean of 2.1 ± 3.5/h after 14 weeks. ODI decreased from 78.2 ± 25.8/h to 20.8 ± 25.5/h. Four studies demonstrated a statistically significant improvement in subjective sleepiness posttracheostomy. Postoperative statistically significant reductions in overall and in cardiovascular mortality compared with untreated historical cohorts was reported.

Conclusion

Tracheostomies significantly decrease apnea index, oxygen desaturation index, sleepiness, and mortality in OSA subjects.

Level of Evidence

NA. Laryngoscope, 124:803–811, 2014
Extracellular and intracellular melanin in inflammatory middle ear disease
Authors: Fritz Mark A. , Roehm Pamela C. , Bannan Michael A. , Lalwani Anil K.
Published: November 2013

Objectives/Hypothesis

Melanin is a pigmented polymer with a known role in dermal solar protection. In vertebrates, melanogenesis has been reported in leukocyte populations, suggesting a potential role in innate immunity. In this study, we report the novel finding of melanin associated with chronic inflammation and speculate on its potential role in the middle ear and mastoid.

Study Design

Retrospective review of case series.

Methods

Medical records of six patients who demonstrated melanin in the ear were reviewed.

Results

Six patients from 1 to 63 years of age were identified with extracellular melanin and melanin‐laden histiocytes within the middle ear and/or mastoid air cells at time of surgery. Concurrent intraoperative findings included cholesteatoma (n = 3), chronic suppurative otitis media (n = 2), and coalescent mastoiditis (n = 1). Histologically, extracellular melanin and melanin‐laden histiocytes were identified by Fontana‐Masson stain; absence of melanocytes was confirmed by the absence of Melan‐A staining. One patient had a positive stain for CD163 (a marker for macrophages).

Conclusion

This case series is the first demonstration of melanin within middle ear mucosa without melanocytes in immediate proximity or metastatic melanocytic lesions. Melanin's presence in the setting of inflammation suggests that there may be a heretofore unreported link between the pigmentary and immune systems in the middle ear.

Level of Evidence

4. Laryngoscope, 124:E241–E244, 2014
Internal mammary perforator vessels as recipient site for microsurgical breast reconstruction: A comparative histomorphometric analysis and incidence of degenerative vascular changes
Authors: Mendonça Munhoz Alexandre , Ishida luis h. , Montag Eduardo , Saito Fábio L. , Mendes Marcio , Alves Hélio , Gemperli Rolf
Published: November 2013

Background

In microsurgical breast reconstruction, an adequate selection of recipient vessels is crucial for a successful outcome. Although the internal mammary (IM) vessels offer an attractive option, the internal mammary perforator (IMP) vessels are becoming a reliable alternative. The purpose of this study is to investigate the external diameters, lumen area, and atherosclerotic lesions changes of the IMP, IM, and deep inferior epigastric (DIE) vessels through quantitative and qualitative histomorphometric analysis.

Methods

Ninety‐six vessels of bilateral IM, IMP, and DIE vessels from 16 fresh female cadavers were evaluated. Mean age was 54.06 ± 5.7 years. External diameters, lumen area, and degenerative changes of the tunica intimae and media were analyzed by qualitative histomorphometric analysis.

Results

Seventy‐one vessels (20 IM, 31 IMP, and 20 DIE vessels) were included in the final histological analysis. A statistically lower external diameters and lumen area were presented by the IMP. The DIE vessels showed a lower incidence (10%) of moderate and severe intimal layer degenerative changes (P = 0.0589). The IMP and DIE vessels showed a lower incidence (9.4 and 25%, respectively) of major media layer degenerative changes (P = 0.0001). No major arterial degenerative lesions were observed in the IMP arteries.

Conclusion

Although the IMP external diameters and lumen area were lower than the IM, the results of this study indicated that the tunica media layer in the IMP is less damaged than the other recipient vessels. The results of the comparative histological study permitted to describe additional advantages and disadvantages of using IMP as a recipient vessel for free flap breast reconstruction. © 2013 Wiley Periodicals, Inc. Microsurgery 34:217–223, 2014.
13C and 15N CP/MAS, 1H–15N SCT CP/MAS and FTIR spectroscopy as tools for qualitative detection of the presence of zwitterionic and non‐ionic forms of ansa‐macrolide 3‐formylrifamycin SV and its derivatives in solid state
Authors: Przybylski Piotr , Pyta Krystian , Klich Katarzyna , Schilf Wojciech , Kamieński Bohdan
Published: November 2013

13C, 15N CP/MAS, including 1H–13C and 1H–15N short contact time CP/MAS experiments, and FTIR methods were applied for detailed structural characterization of ansa‐macrolides as 3‐formylrifamycin SV (1) and its derivatives (2–6) in crystal and in powder forms. Although HPLC chromatograms for 2/CH3OH and 2/CH3CCl3 were the same for rifampicin crystals dissolved in respective solvents, the UV–vis data recorded for them were different in 300–375 nm region. Detailed solid state 13C and 15N CP/MAS NMR and FTIR studies revealed that rifampicin (2), in contrast to 3‐formylrifamycin SV (1) and its amino derivatives (3–6), can occur in pure non‐ionic or zwitterionic forms in crystal and in pure these forms or a mixture of them in a powder. Multinuclear CP/MAS and FTIR studies demonstrated also that 3–6 derivatives were present exclusively in pure zwitterionic forms, both in powder and in crystal. On the basis of the solid state NMR and FTIR studies, two conformers of 3‐formylrifamycin SV were detected in powder form due to the different orientations of carbonyl group of amide moiety. The PM6 molecular modeling at the semi‐empirical level of theory, allowed visualization the most energetically favorable non‐ionic and zwitterionic forms of 1–6 antibiotics, strongly stabilized via intramolecular H‐bonds. FTIR studies indicated that the originally adopted forms of these type antibiotics in crystal or in powder are stable in standard laboratory conditions in time. The results presented point to the fact that because of a possible presence of two forms of rifampicin (compound 2), quantification of the content of this antibiotic in relevant pharmaceuticals needs caution. Copyright © 2013 John Wiley & Sons, Ltd.
Patient demographics and health plan paid costs in chronic inflammatory demyelinating polyneuropathy
Authors: Guptill Jeffrey T. , Bromberg Mark B. , Zhu Li , Sharma Bal K. , Thompson Amy R. , Krueger Andrew , Sanders Donald B.
Published: November 2013

Introduction: We determined health plan paid costs and healthcare resource usage of patients with chronic inflammatory demyelinating polyneuropathy (CIDP). Methods: CIDP patients from 9 U.S. commercial health plans with claims in 2011 were identified from the Accordant Health Services claims database. We examined demographics, prevalence of comorbidities, prescribed drugs, place of service, and mean annual health plan paid costs per patient. Results: From 6.5 million covered lives, 73 (56% men; mean age 47) met study entry criteria. The most prescribed therapies were intravenous immunoglobulin (IVIg) (26% of patients), gabapentin (26%), and prednisone (16%). The annual health plan paid cost was $56,953. Pharmacy cost was the major cost driver (57% of the total), and IVIg totaled 90% of the pharmacy costs. Conclusions: Healthcare costs for CIDP patients are substantial, with a large burden in pharmacy usage. Studies are needed to determine optimal long‐term treatment strategies for CIDP, particularly related to IVIg. Muscle Nerve 50: 47–51, 2014
Ti/C‐3Ni/Al as a Replacement Time Delay Composition
Authors: Miklaszewski Eric J. , Poret Jay C. , Shaw Anthony P. , Son Steven F. , Groven Lori J.
Published: November 2013

Replacement reactive systems for the tungsten delay composition (W/BaCrO4/KClO4/diatomaceous earth) are needed due to recent concerns over the toxicity of hexavalent chromium and perchlorates. Systems based on condensed phase reactions, that are typically used in combustion synthesis (e.g., Ti/C or Ni/Al) are of interest as replacements due to their wide range of combustion velocities and potentially low environmental impact. In this work, the combustion characteristics of the Ti/C‐3Ni/Al reactive system were examined in microchannels with inner diameters ranging from 3.0–6.0 mm (i.e., similar to that of a common delay housing). It was found that this reactive system could be tailored to overcome the heat losses associated with small diameter microchannels by changing the relative amounts of Ti/C and 3Ni/Al. At 40 wt.‐% Ti/C content, the failure diameter was found to be between 3.0 and 4.0 mm, while at 30 wt.‐% Ti/C the failure diameter was between 4.8 and 6.0 mm. Measured combustion temperatures in metal microchannels were approximately 1700 K while those of unconfined pellets were around 100 K greater. Increasing Ti/C content resulted in faster combustion velocities while decreasing microchannel diameter resulted in slower combustion velocities. At these small sizes the effects of adding a thermal barrier (specifically Grafoil™) to minimize radial heat losses to the microchannel were shown to be minimal with respect to combustion velocity. The Ti/C‐3Ni/Al system was shown to be a suitable delay fuze composition with tunable combustion velocities ranging from 2.1–38.1 mm s−1 in aluminum microchannels with diameters ranging from 4.0–6.0 mm.
Solution properties of γ‐crystallins: Hydration of fish and mammal γ‐crystallins
Authors: Zhao Huaying , Chen Yingwei , Rezabkova Lenka , Wu Zhengrong , Wistow Graeme , Schuck Peter
Published: November 2013

Lens γ crystallins are found at the highest protein concentration of any tissue, ranging from 300 mg/mL in some mammals to over 1000 mg/mL in fish. Such high concentrations are necessary for the refraction of light, but impose extreme requirements for protein stability and solubility. γ‐crystallins, small stable monomeric proteins, are particularly associated with the lowest hydration regions of the lens. Here, we examine the solvation of selected γ‐crystallins from mammals (human γD and mouse γS) and fish (zebrafish γM2b and γM7). The thermodynamic water binding coefficient B1 could be probed by sucrose expulsion, and the hydrodynamic hydration shell of tightly bound water was probed by translational diffusion and structure‐based hydrodynamic boundary element modeling. While the amount of tightly bound water of human γD was consistent with that of average proteins, the water binding of mouse γS was found to be relatively low. γM2b and γM7 crystallins were found to exhibit extremely low degrees hydration, consistent with their role in the fish lens. γM crystallins have a very high methionine content, in some species up to 15%. Structure‐based modeling of hydration in γM7 crystallin suggests low hydration is associated with the large number of surface methionine residues, likely in adaptation to the extremely high concentration and low hydration environment in fish lenses. Overall, the degree of hydration appears to balance stability and tissue density requirements required to produce and maintain the optical properties of the lens in different vertebrate species.