bluuebunny/crossref_metadata_2025 huggingface dataset:
High‐temperature steam‐treatment of PBI, PEKK, and a PEKK‐PBI Blend: A solid‐state NMR and IR spectroscopic study
Authors: Guenther Johannes , Wong Minhao , Sue Hung‐Jue , Bremner Tim , Blümel Janet
Published: October 2012

Blends of polyaryletherketones (PAEK) with polybenzimidazole (PBI) are of commercial interest due to their improved upper service temperatures and wear properties when compared with the PAEK analogs examined to date. The retention of properties of the PBI component generally thought to be disadvantageous in more thermally or chemically aggressive environments is not well understood, nor are the specifics of interactions between the PBI and PAEK components in a melt or dry blend systems. In this initial investigation, focus is placed on the behavior and mechanism of polyetherketoneketone (PEKK)/PBI systems in contact with steam or condensed phase water. The goal is to understand the chemistry of the reaction, if any, upon exposure to steam as well as to examine the reversibility of moisture uptake of this material when exposed to liquid water or saturated steam. In this contribution, the pure polymer components and the PEKK‐PBI (60 : 40 wt %) blend are steam‐treated at 149°C (300°F) and 316°C (600°F). IR and solid‐state NMR spectroscopy are used to study chemical or morphological transformations of the polymers. All changes detectable by 13C cross‐polarization with magic angle spinning (CP/MAS) upon steam‐treatment are reversible, and not of a chemical nature, indicating that under the conditions of exposure used here no detectable chemical degradation occurs during steam exposure and with moisture uptake. The temporary water uptake of the samples, as studied by 1H wideline NMR and 13C T1 time measurements, leads to a change in the ratio of rigid versus mobile domains of the materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Steady‐state and time‐resolved fluorescence of tetramethylrhodamine attached to DNA: correlation with DNA sequences
Authors: Chen Tingting , Fu Leixiaomeng , Zu Lily
Published: October 2012

Time‐resolved fluorescence as well as steady‐state absorption and fluorescence were detected in order to study the interactions between tetramethylrhodamine (TAMRA) and DNA when TAMRA was covalently labeled on single‐ and double‐stranded oligonucleotides. Fluorescence intensity quenching and lifetime changes were characterized and correlated with different DNA sequences. The results demonstrated that the photoinduced electron transfer interaction between guanosine residues and TAMRA introduced a short lifetime fluorescence component when guanosine residues were at the TAMRA‐attached terminal of the DNA sequences. The discrepancy of two‐state and three‐state models in previous studies was due to the DNA sequence selection and sensitivity of techniques used to detect the short lifetime component. The results will help the design of fluorescence‐based experiments related to a dye labeled probe. Copyright © 2012 John Wiley & Sons, Ltd.
Simultaneous determination of sunitinib and its two metabolites in plasma of Chinese patients with metastatic renal cell carcinoma by liquid chromatography–tandem mass spectrometry
Authors: Qiu Feng , Bian Weihua , Li Jun , Ge Zhicheng
Published: October 2012

A simple and rapid liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method was developed and validated for the simultaneous determination of sunitinib and its two metabolites in plasma of Chinese patients with metastatic renal cell carcinoma (mRCC). After simple one‐step protein precipitation with methanol–acetonitrile (1:1, v/v), all three analytes were separated on an Agilent Zorbax SB‐C18 column using a gradient mobile phase consisting of water (0.1% formic acid)–acetonitrile (0.1% formic acid) at a flow rate of 0.50 mL/min. The detection was performed in multiple reaction monitoring mode, using the transitions of m/z 399.0 → 326.2, m/z 371.0 → 283.1, m/z 343.0 → 283.1 and m/z 386.3 → 122.2 for sunitinib, M1, M2 and buspirone, respectively. The method was linear over the range of 0.10–100 ng/mL for all three analytes using only 50 μL of plasma and the lower limit of quantifications for the three analytes were all 0.10 ng/mL. The intra‐day and inter‐day precisions were all less than 15% and the accuracies were within the range of ±15%; recoveries were between 85.0 and 115%. The validated method was successfully applied to an explorative pharmacokinetic study of sunitinib in Chinese patients with mRCC following multi‐dose oral administration. Copyright © 2012 John Wiley & Sons, Ltd.
Boron‐Doped Tri(9,10‐anthrylene)s: Synthesis, Structural Characterization, and Optoelectronic Properties
Authors: Hoffend Claas , Schödel Frauke , Bolte Michael , Lerner Hans‐Wolfram , Wagner Matthias
Published: October 2012

The reaction of 9,10‐dibromo‐9,10‐dihydro‐9,10‐diboraanthracene (9,10‐dibromo‐DBA, 3) with two equivalents of 9‐lithio‐2,6‐ or 9‐lithio‐2,7‐di‐tert‐butylanthracene gave the corresponding 9,10‐dianthryl‐DBAs featuring two (4) or four (5) inward‐pointing tert‐butyl groups. Compound 4 exists as two atropisomers, 4 and 4′, due to hindered rotation about the exocyclic BC bonds. X‐ray crystallography of 5 suggests that the overall interactions between facing tert‐butyl groups are attractive rather than repulsive. Even in solution, 4/4′ and 5 are stable toward air and moisture for several hours. Treatment of 3 with 10‐lithio‐9‐R‐2,7‐di‐tert‐butylanthracenes carrying phenyl (R=Ph), dimesitylboryl (R=Mes2B), or N,N‐di(p‐tolyl)amino (R=Tol2N) groups gave the corresponding 9,10‐dianthryl‐DBA derivatives 9–11 in moderate to good yields. In these molecules, all four solubilizing tert‐butyl groups are outward pointing. The solid‐state structures of 4, 5, 9, and 10 reveal twisted conformations about the exocyclic BC bonds with dihedral angles of 70–90°. A significant electron‐withdrawing character was proven for the Mes2B moiety, but no appreciable +M effect was evident for Tol2N. Compounds 5, 9, and 11 show two reversible DBA‐centered reduction waves in the cyclic voltammogram. In the case of 10, a third reversible redox transition can be assigned to the Mes2B–anthryl substituents. The UV/Vis absorption spectrum of 5 is characterized by a very broad band at λmax=510 nm, attributable to a twisted intramolecular charge‐transfer interaction from the anthryl donors to the DBA acceptor. The corresponding emission band shows pronounced positive solvatochromism (λem=567 nm, C6H12; 680 nm, CH2Cl2) in line with a highly polar excited state. The charge‐transfer bands of 10 and 11, as well as the emission bands of 9 and 10, are redshifted relative to those of 5. The Tol2N derivative 11 is essentially nonfluorescent in solution, but emits bright wine‐red light in the solid state.
Syntheses and Applications of Monofluorinated Cyclopropanes
Authors: David Emilie , Milanole Gaëlle , Ivashkin Pavel , Couve‐Bonnaire Samuel , Jubault Philippe , Pannecoucke Xavier
Published: October 2012

The combination of a fluorine atom and a cyclopropane ring, which both possess unique structural and chemical features, can generate new relevant building blocks for the discovery of efficient fluorinated biologically active agents. In this review, we report the different strategies to access monofluorocyclopropanes and highlight some of their attractive biological applications.
Fetuin‐A in the developing brain
Authors: Elsas Johannes , Sellhaus Bernd , Herrmann Marietta , Kinkeldey Anne , Weis Joachim , Jahnen‐Dechent Willi , Häusler Martin
Published: October 2012

The serum protein fetuin‐A is essential for mineral homeostasis and shows immunomodulatory functions, for example by binding to TGF superfamily proteins. It proved neuroprotective in a rat stroke model and reduced lethality after systemic lipopolysaccharide challenge in mice. Serum fetuin‐A concentrations are highest during intrauterine life. Different species show intrauterine cerebral fetuin‐A immunoreactivity, suggesting a contribution to brain development. We therefore aimed at specifying fetuin‐A immunoreactivity in brains of newborn rats (age P0–P28) and human neonates (20–40 weeks of gestation). In humans and rats, fetuin‐A was found in cortex, white matter, subplate, hippocampus, subventricular zone, and ependymal cells which supports a global role for brain function. In rats, overall fetuin‐A immunoreactivity decreased with age. At P0 fetuin‐A immunoreactivity affected most brain structures. Thereafter, it became increasingly restricted to distinct cells of the hippocampus, cingular gyrus, periventricular stem cell layer, and ependyma. In ependymal cells the staining pattern complied with active transependymal transport from cerebrospinal fluid. Double immunofluorescence studies revealed colocalization with NeuN (mature neurons), beta III tubulin (immature neurons), GFAP (astrocytes), and CD68 (activated microglia). This points to a role of fetuin‐A in different brain functional systems. In human neonatal autopsy cases, frequently affected from severe neurological and non‐neurological diseases, fetuin‐A immunoreactivity was heterogeneous and much less associated with age than in healthy tissues studied earlier, suggesting an impact of exogeneous noxious factors on fetuin‐A regulation. Further research on the role of fetuin‐A in the neonatal brain during physiological and pathological conditions is recommended. © 2012 Wiley Periodicals, Inc. Develop Neurobiol 73: 354–369, 2013
Transcriptional evolution underlying vertebrate sexual development
Authors: Valenzuela Nicole , Neuwald Jennifer L. , Literman Robert
Published: October 2012

Explaining the diversity of vertebrate sex‐determining mechanisms ranging from genotypic (GSD) to temperature‐dependent (TSD) remains a developmental and evolutionary conundrum. Using a phylogenetic framework, we explore the transcriptional evolution during gonadogenesis of several genes involved in sexual development, combining novel data from Chrysemys picta turtles (TSD) and published data from other TSD and GSD vertebrates. Our novel C. picta dataset underscores Sf1 and Wt1 as potential activators of the thermosensitive period and uncovered the first evidence of Dax1 involvement in male development in a TSD vertebrate. Contrasting transcriptional profiles revealed male‐biased Wt1 expression in fish while monomorphic expression is found in tetrapods but absent in turtles. Sf1 expression appears highly labile with transitions among testicular, ovarian, and non‐sex‐specific gonadal formation patterns among and within lineages. Dax1's dual role in ovarian and testicular formation is found in fish and mammals but is dosage‐sensitive exclusively in eutherian mammals due to its X‐linkage in this group. Contrastingly, Sox9 male‐biased and Aromatase female‐biased expression appear ancestral and virtually conserved throughout vertebrates despite significant heterochronic changes in expression as other elements likely replaced their function in early gonadogenesis. Finally, research avenues are highlighted to further study the evolution of the regulatory network of sexual development. © 2012 Wiley Periodicals, Inc. Developmental Dynamics 242:307–319, 2013. © 2012 Wiley Periodicals, Inc.
Wild edible fruits as a potential source of phytochemicals with capacity to inhibit lipid peroxidation
Authors: Morales Patricia , Ferreira Isabel C.F.R. , Carvalho Ana Maria , Fernández‐Ruiz Virginia , Sánchez‐Mata Mª Cortes , Cámara Montaña , Morales Ramón , Tardío Javier
Published: October 2012

The edible fruits of four wild small trees or shrubs (Arbutus unedo, Crataegus monogyna, Prunus spinosa, and Rubus ulmifolius) traditionally consumed in the Iberian Peninsula were studied to evaluate their potential for human nutrition, considering their content in bioactive compounds. Lipophilic phytochemicals, such as fatty acids and tocopherols, as well as some hydrophilic antioxidants, such as vitamin C and organic acids, were analyzed. In addition, the antioxidant activity, measured as lipid peroxidation inhibition (β‐carotene/linoleate and TBARS assays), was evaluated in each fruit. As far as we know, this is the first report relating to bioactive compounds in wild fruits with relation to the lipid peroxidation inhibition. Data revealed that these wild edible fruits are good sources of bioactive compounds as organic acids, vitamin C, tocopherols, and polyunsaturated fatty acids. They could be considered as functional foods or potential sources of bioactive compounds with antioxidant synergism effect, to be included as antioxidant food ingredients or in dietary supplements, mainly Rubus ulmifolius, due to its high content in tocopherols. This study provides useful and relevant information that justify tocopherols influence in the prevention of lipid peroxidation, due to the strong correlation observed (r>0.95) between these lipophilic bioactive compounds and the antioxidant activity.
Conformationally Constrained Oxides of 1,3‐Dithiane: Synthesis and NMR Spectroscopic Investigations
Authors: Ulshöfer Roland , Wedel Tobias , Süveges Bastian , Podlech Joachim
Published: October 2012

Conformationally constrained derivatives of 1,3‐dithianes (5‐tert‐butyl‐ and 4,6‐dimethyl‐1,3‐dithiane and dithiadecalin) have been oxidised with various oxidants to yield axial and equatorial sulfoxides, disulfoxides and sulfones. Axial sulfoxides were prepared by nucleophilic hydroxide addition to the corresponding 2‐alkylidene derivatives with subsequent retro‐aldol‐type elimination. The reaction outcome is related to the relative energies of the derivatives, as demontstrated by DFT calculations. The NMR spectroscopic data of the compounds obtained were analysed to identify 4J couplings. It was found that only 4J W couplings can be observed regardless of whether there is an axial or an equatorial sulfoxide, sulfide or sulfone group present in between the respective C–H moieties. A previously postulated γ‐gauche effect of axial sulfoxides (but not of equatorial sulfoxides or sulfones) leading to the shielding of carbon atoms is not unambiguously supported by the NMR spectroscopic data of conformationally fixed derivatives.
Asymmetric Synthesis of the C14–C26 Building Block of Eribulin Mesylate
Authors: Murthy Akondi Srirama , Mahipal Bodugum , Chandrasekhar Srivari
Published: October 2012

An alternative route for the synthesis of the C14–C26 building block of the anticancer drug eribulin mesylate is described. The key steps involved in the synthesis are a Julia–Kocienski olefination between aldehyde 4 and sulfone 5 and a tandem Sharpless asymmetric dihydroxylation/SN2 cyclisation reaction on mesyl compound 3.
Overexpression of insulin‐like growth factor 1 receptor and frequent mutational inactivation of SDHA in wild‐type SDHB‐negative gastrointestinal stromal tumors
Authors: Belinsky Martin G. , Rink Lori , Flieder Douglas B. , Jahromi Mona S. , Schiffman Joshua D. , Godwin Andrew K. , von Mehren Margaret
Published: October 2012

Approximately 15% of gastrointestinal stromal tumors (GISTs) in adults and 85% in children lack mutations in KIT and PDGFRA and are known as wild‐type GISTs. Wild‐type GISTs from adults and children express high levels of insulin‐like growth factor 1 receptor (IGF1R) and exhibit stable genomes compared to mutant GISTs. Pediatric wild‐type GISTs, GISTs from the multitumor Carney–Stratakis syndrome, and the Carney triad share other clinicopathological properties (e.g., early‐onset, multifocal GISTs with epitheliod cell morphology), suggesting a common etiology. Carney–Stratakis is an inherited association of GIST and paragangliomas caused by germline mutations in succinate dehydrogenase (SDH) genes. The connection between defective cellular respiration and GIST pathology has been strengthened by the utilization of SDHB immunohistochemistry to identify SDH deficiency in pediatric GISTs, syndromic GISTs, and some adult wild‐type GISTs. SDHB and IGF1R expression was examined in 12 wild‐type and 12 mutant GIST cases. Wild‐type GISTs were screened for coding‐region alterations in SDH genes and for chromosomal aberrations using genome‐wide single‐nucleotide polymorphism and MIP arrays. SDHB‐deficiency, identified in 11/12 wild‐type GIST cases, was tightly associated with overexpression of IGF1R protein and transcript. Biallelic inactivation of the SDHA gene was a surprisingly frequent event, identified in 5 of 11 SDHB‐negative cases, generally due to germline point mutations accompanied by somatic SDHA allelic losses. As a novel finding, inactivation of the SDHC gene from a combination of a heterozygous coding‐region mutation and hypermethylation of the wild‐type allele was found in one SDHB‐negative case. © 2012 Wiley Periodicals, Inc.
Tumour burden at diagnosis as the main clinical predictor of cell resistance in patients with early stage, favourable Hodgkin lymphoma treated with VBM chemotherapy plus radiotherapy
Authors: Gobbi Paolo G. , Bergonzi Manuela , Bassi Emilio , Merli Francesco , Coriani Chiara , Federico Massimo
Published: October 2012

We verified whether early resistance to treatment can be predicted in a subset of patients with very favourable, early stage Hodgkin lymphoma, treated with VBM (vinblastine, bleomycin and methotrexate) chemotherapy and involved‐field radiotherapy, an effective combination with very low early and late toxicity. The relative tumour burden (rTB) was volumetrically measured from the staging computed tomography and analysed together with the parameters of pre‐therapy evaluation in 61 patients enrolled into the protocol MH‐1b of the Gruppo Italiano Studio Linfomi between 1996 and 2003. Early failure, codified by either less than complete remission (i.e. partial/null response or progression) or early relapse (within 12 months from the end of therapy), was considered as clinical expression of resistance to treatment. Logistic regression and failure‐free survival were the statistical tools for the analysis. The rTB demonstrated to be the best predictor of early failure, outperforming every other pre‐treatment parameter, International Prognostic Score included. With a mean rTB value of 44.964 ± 34.788 cm3/m2 in the 53 patients successfully treated and of 130.185 ± 63.993 cm3/m2 in the eight with early treatment failure, the risk of resistance showed fivefold and 10‐fold increases at rTB of 52.002 and 74.497 cm3/m2, respectively. Only two patients relapsed more than 12 months after the end of therapy; both had a high initial rTB. The rTB is the best predictor of resistance also in the subset of patients with very favourable, early stage disease. Safe rTB limits are proposed for successful administration of VBM chemotherapy plus involved‐field radiotherapy. Copyright © 2012 John Wiley & Sons, Ltd.
Bortezomib as salvage treatment for heavily pretreated relapsed lymphoma patients: a multicenter retrospective study
Authors: Zinzani Pier Luigi , Pellegrini Cinzia , Merla Emanuela , Ballerini Filippo , Fabbri Alberto , Guarini Attilio , Pavone Vincenzo , Quintini Gerlando , Puccini Benedetta , Vigliotti Maria Luigia , Stefoni Vittorio , Derenzini Enrico , Broccoli Alessandro , Gandolfi Letizia , Quirini Federica , Casadei Beatrice , Argnani Lisa , Baccarani Michele
Published: October 2012

Current treatments for non‐Hodgkin lymphomas are not optimally effective. Among new agents, bortezomib seems to play a pivotal role in the regulation of several cell pathways involved in the development of lymphomas. After results were obtained with clinical trials, we aimed to observe treatment with bortezomib in everyday clinical practice. We performed a multicenter retrospective analysis to assess the efficacy of bortezomib in heavily pretreated (median number of previous therapies 4, range 2–6) lymphoma patients in an off‐label setting. Bortezomib therapy was scheduled for 4–6 cycles (1.3 mg/m2 biweekly). Data from 50 patients were collected: 22% had a complete remission, 26% obtained a partial response and the remaining 52% was non‐responder. According to histotype, we observed an overall response rate (ORR) of 51.6% in mantle cell lymphomas, an ORR of 60% among follicular lymphoma patients, and an ORR of 50% in the indolent nonfollicular lymphomas. None of diffuse large B‐cell lymphoma patients obtained a response. Extra‐hematological toxicity was really mild, and peripheral neuropathy occurred in only 5 patients; hematological toxicity was grades 3–4 thrombocytopenia in nine patients and grades 3–4 neutropenia in only three patients. In conclusion, treatment with bortezomib as single agent resulted safe and effective in a subset of heavily pretreated lymphoma patients with usually poor outcome. New future hypotheses of investigation are indicated. Copyright © 2012 John Wiley & Sons, Ltd.
Removal of user fees for caesareans and under‐fives in northern Sudan: a review of policy implementation and effectiveness
Authors: Witter Sophie , Khalid Mousa Khalda , Abdel‐Rahman Manar E. , Hussein Al‐Amin Rania , Saed Mohammed
Published: October 2012

In 2008, the Government of Sudan launched a policy of free curative care for under‐fives and caesareans. This paper presents the findings of a review of this policy, on the basis of research conducted in five focal states of northern Sudan in 2010. Policy implementation was assessed using four research tools: key informant interviews, exit interviews, a facility survey, and analysis of facility finances and the cost of the package of care.

The findings point to important weaknesses in implementation, such as unclear specification of the exact target group and package of care and inadequate funding. Despite this, service utilisation appears to have responded, at least in the short term. The findings also highlight the urgent need for improved access to basic health care and financial protection against health care costs in northern Sudan (for those with and without national health insurance membership).

This review contributes to the growing literature on the selective removal of user fees for priority services. It indicates the range of challenges to effective implementation (strategic, financial and organisational). Some of these are particular to Sudan, but many are shared, and indicate important lessons for improving access to and quality of care for women and children in Africa.

Copyright © 2012 John Wiley & Sons, Ltd.
PTHrP regulates the modeling of cortical bone surfaces at fibrous insertion sites during growth
Authors: Wang Meina , VanHouten Joshua N , Nasiri Ali R , Johnson Randy L , Broadus Arthur E
Published: October 2012

The sites that receive ligament and tendon insertions (entheses) on the cortical surfaces of long bones are poorly understood, particularly regarding modeling and regulation. Entheses are classified as either fibrocartilaginous or fibrous based on their structures. Fibrous entheses typically insert into the metaphysis or diaphysis of a long bone, bear a periosteal component, and are modeled during long-bone growth. This modeling forms a root system by which the insertions attach to the cortical surface. In the case of the medial collateral ligament, modeling drives actual migration of the ligament along the cortical surface in order to accommodate linear growth, whereas in other sites modeling may excavate a deep cortical root system (eg, the teres major insertion) or a shallow root system with a large footprint (eg, the latissimus dorsi insertion). We report here that conditionally deleting parathyroid hormone-related protein (PTHrP) in fibrous entheses via Scleraxis-Cre targeting causes modeling to fail in these three iterations of osteoclast-driven enthesis excavation or migration. These iterations appear to represent formes frustes of a common modeling strategy, presumably differing from each other as a consequence of differences in biomechanical control. In sites in which PTHrP is not induced, either physiologically or because of conditional deletion, modeling does not take place and fibrocartilage is induced. These findings represent the initial genetic evidence that PTHrP regulates periosteal/intramembranous bone cell activity on cortical bone surfaces and indicate that PTHrP serves as a load-induced modeling tool in fibrous insertion sites during linear growth. © 2013 American Society for Bone and Mineral Research.
Proximal femoral density distribution and structure in relation to age and hip fracture risk in women
Authors: Carballido-Gamio Julio , Harnish Roy , Saeed Isra , Streeper Timothy , Sigurdsson Sigurdur , Amin Shreyasee , Atkinson Elizabeth J , Therneau Terry M , Siggeirsdottir Kristin , Cheng Xiaoguang , Melton L Joseph , Keyak Joyce , Gudnason Vilmundur , Khosla Sundeep , Harris Tamara B , Lang Thomas F
Published: October 2012

Hip fracture risk rises exponentially with age, but there is little knowledge about how fracture-related alterations in hip structure differ from those of aging. We employed computed tomography (CT) imaging to visualize the three-dimensional (3D) spatial distribution of bone mineral density (BMD) in the hip in relation to age and incident hip fracture. We used intersubject image registration to integrate 3D hip CT images into a statistical atlas comprising women aged 21 to 97 years (n = 349) and a group of women with (n = 74) and without (n = 148) incident hip fracture 4 to 7 years after their imaging session. Voxel-based morphometry was used to generate Student's t test statistical maps from the atlas, which indicated regions that were significantly associated with age or with incident hip fracture. Scaling factors derived from intersubject image registration were employed as measures of bone size. BMD comparisons of young, middle-aged, and older American women showed preservation of load-bearing cortical and trabecular structures with aging, whereas extensive bone loss was observed in other trabecular and cortical regions. In contrast, comparisons of older Icelandic fracture women with age-matched controls showed that hip fracture was associated with a global cortical bone deficit, including both the superior cortical margin and the load-bearing inferior cortex. Bone size comparisons showed larger dimensions in older compared to younger American women and in older Icelandic fracture women compared to controls. The results indicate that older Icelandic women who sustain incident hip fracture have a structural phenotype that cannot be described as an accelerated pattern of normal age-related loss. The fracture-related cortical deficit noted in this study may provide a biomarker of increased hip fracture risk that may be translatable to dual-energy X-ray absorptiometry (DXA) and other clinical images. © 2013 American Society for Bone and Mineral Research.
Comparison of two simulation methods to compute solvation free energies and partition coefficients
Authors: Yang Li , Ahmed Alauddin , Sandler Stanley I.
Published: October 2012

The thermodynamic integration (TI) and expanded ensemble (EE) methods are used here to calculate the hydration free energy in water, the solvation free energy in 1‐octanol, and the octanol‐water partition coefficient for a six compounds of varying functionality using the optimized potentials for liquid simulations (OPLS) all‐atom (AA) force field parameters and atomic charges. Both methods use the molecular dynamics algorithm as a primary component of the simulation protocol, and both have found wide applications in fields such as the calculation of activity coefficients, phase behavior, and partition coefficients. Both methods result in solvation free energies and 1‐octanol/water partition coefficients with average absolute deviations (AAD) from experimental data to within 4 kJ/mol and 0.5 log units, respectively. Here, we find that in simulations the OPLS‐AA force field parameters (with fixed charges) can reproduce solvation free energies of solutes in 1‐octanol with AAD of about half that for the solute hydration free energies using a extended simple point charge (SPC/E) model of water. The computational efficiency of the two simulation methods are compared based on the time (in nanoseconds) required to obtain similar standard deviations in the solvation free energies and 1‐octanol/water partition coefficients. By this analysis, the EE method is found to be a factor of nine more efficient than the TI algorithm. For both methods, solvation free energy calculations in 1‐octanol consume roughly an order of magnitude more CPU hours than the hydration free energy calculations. © 2012 Wiley Periodicals, Inc.
Thermal Properties Improvement of Bismaleimide Resin by a New Phosphorus‐containing Polycyclic Bismaleimide
Authors: Tsai Pai‐Feng , Kuo Wen‐Lung , Shau Min‐Da
Published: October 2012

A new phosphorus‐containing polycyclic bismaleimide resin (BMPI) was prepared by the reaction of bis(3‐maleimidophenyl) methylphosphine oxide (BAMP) with benzene‐1,2,4,5‐tetracarboxylic dianhydride (BTD) and maleic anhydride (MA). BMPI was confirmed by infrared (IR), 1H‐ and 13C‐NMR spectroscopies. Its thermal properties were carried out by a differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) that revealed that the polymers have excellent thermal properties in the high temperature region and a high char yield of up to 53∼65%. Furthermore, three conventional bismaleimide resins were prepared from different phosphorus‐free bismaleimides for comparison, e.g. 4,4′‐bismaleimidodiphenylmethane (BDM), 4,4′‐bismaleimidodiphenylether (BDE), 4,4′‐bismaleimidodiphenylsulfone (BDS).
Immunolocalization of keratin‐associated beta‐proteins in developing epidermis of lizard suggests that adhesive setae contain glycine–cysteine‐rich proteins
Authors: Alibardi Lorenzo
Published: October 2012

The localization of specific keratin‐associated beta‐proteins (formerly referred to as beta‐keratins) in the embryonic epidermis of lizards is not known. Two specific keratin‐associated beta‐proteins of the epidermis, one representing the glycine‐rich subfamily (HgG5) and the other the glycine‐cysteine medium‐rich subfamily (HgGC10), have been immunolocalized at the ultrastructural level in the lizard Anolis lineatopus. The periderm and granulated subperiderm are most immunonegative for these proteins. HgG5 is low to absent in theOberhäutchen layer while is present in the forming beta‐layer, and disappears in mesos‐ and alpha‐layers. Instead, HgGC10 is present in the Oberhäutchen, beta‐, and also in the following alpha‐layers, and specifically accumulates in the developing adhesive setae but not in the surrounding cells of the clear layer. Therefore, setae and their terminal spatulae that adhere to surfaces allowing these lizards to walk vertically contain cysteine–glycine rich proteins. The study suggests that, like in adult and regenerating epidermis, the HgGC10 protein is not only accumulated in cells of the beta‐layer but also in those forming the alpha‐layer. This small protein therefore is implicated in resistance, flexibility, and stretching of the epidermal layers. It is also hypothesized that the charges of these proteins may influence adhesion of the setae of pad lamellae. Conversely, glycine‐rich beta‐proteins like HgG5 give rise to the dense, hydrophobic, and chromophobic corneous material of the resistant beta‐layer. This result suggests that the differential accumulation of keratin‐associated beta‐proteins over the alpha‐keratin network determines differences in properties of the stratified layers of the epidermis of lizards. J. Morphol. 2013. © 2012 Wiley Periodicals, Inc.
“Pollical palmar interosseous muscle” (musculus adductor pollicis accessorius): Attachments, innervation, variations, phylogeny, and implications for human evolution and medicine
Authors: Bello‐Hellegouarch Gaelle , Aziz M. Ashraf , Ferrero Eva M. , Kern Michael , Francis Nadia , Diogo Rui
Published: October 2012

Most atlases and textbooks dealing with human anatomy do not refer to the “pollical palmar interosseous” (PPI) muscle of Henle. In order to undertake a fresh and detailed study of this muscle and to thus better understand human comparative anatomy and evolution, we: 1) analyze the frequency of the PPI in a large sample of human hands; 2) describe the attachments, innervation and varieties of the PPI in these hands; 3) compare the data obtained with the information available in the literature; and 4) discuss the phylogenetic origin of the PPI and the implications of our observations and comparisons for medicine and for the understanding of human evolutionary history. Within the 72 hands dissected by us, the PPI is present in 67 hands (93%), commonly having a single muscular branch, originating from the medial side of the base of metacarpal I only, inserting onto the medial side of the base of the pollical proximal phalanx and/or surrounding structures (e.g., ulnar sesamoid bone, wing tendon of extensor apparatus), and passing at least partially, and usually mainly, medial to the princeps pollicis artery. A careful study of the human PPI, as well as a detailed comparison with other mammals, strongly suggest that the muscle is evolutionarily derived from the adductor pollicis, and namely from its oblique head. Therefore, we propose that PPI should be designated by the name musculus adductor pollicis accessorius, which indicates that the muscle is most likely a de novo structure derived from the adductor pollicis. J. Morphol., 2013. © 2012 Wiley Periodicals, Inc.
Autophosphorylation activation and inhibition by curcumin of the epidermal growth factor receptor reconstituted in liposomes
Authors: Doumiati Samah , Haupt Karsten , Rossi Claire
Published: October 2012

The epidermal growth factor receptor (EGFR) is a 170‐kDa transmembrane protein with intrinsic protein kinase activity. It is involved in the regulation of essential cellular processes such as proliferation, differentiation, survival, and migration. An increase in EGFR activity has been correlated to malignant evolution of the cells. We have used proteoliposomes as a platform to study the mechanism of activation and inhibition of EGFR. We have been able to reconstitute functional EGFR in liposomes through detergent removal by Bio‐Beads and have measured the receptor dimerization and its autophosphorylation resulting from its inherent tyrosine kinase activity. In particular, we have studied the activation of autophosphorylation by the natural ligand epidermal growth factor and its inhibition by curcumin, a polyphenol from Curcuma longa. This artificial membrane model provides a convenient tool to both qualitatively and quantitatively elucidate the mechanism of activation and inhibition of EGFR. It allows studying the isolated receptor under well‐defined conditions, which enables one to use a number of biochemical and physico‐chemical techniques that are difficult to put into practice with living cells. We believe that this platform can be used as a systematic screening tool for membrane receptor modulators, which are potential drug candidates. Copyright © 2012 John Wiley & Sons, Ltd.
An overview of lectins purification strategies
Authors: Nascimento Kelany S. , Cunha Ana I. , Nascimento Kyria S. , Cavada Benildo S. , Azevedo Ana M. , Aires‐Barros Maria Raquel
Published: October 2012

Lectins hold great promise not only as reagents for diagnostics and drug discovery but also as a novel class of biopharmaceutical products. In fact, new research directions in the last years have led to major developments in the uses of plant lectins as therapeutic agents against numerous diseases in an ageing society. It is even expected that lectins may occupy an important place in the biopharmaceutical industry next to monoclonal antibodies. All these new trends are placing a tremendous emphasis on the development of new approaches for faster lectins development, selection, and optimization, including alternatives methods of purification. This article reviews the isolation and purification methods used for lectins purification. Origins and applications of lectins are described, highlighting the special features of this class of proteins, such as the carbohydrated‐binding domains and their importance in the development of affinity methodologies to increase and facilitate lectins purification. Published strategies for the purification of lectins from different sources are analyzed in relation to the purification methods used, their sequence, and the number of times they are used in a purification procedure. The purity of lectins is analyzed in relation to the average overall yield and purification factors obtained for each purification scheme for these proteins and the purification steps necessary. New directions are described for improving lectins separation and purification. Copyright © 2012 John Wiley & Sons, Ltd.
Purification of urease from jack bean (Canavalia ensiformis) with copper (II) chelated poly(hydroxyethyl methacrylate‐N‐methacryloyl‐(l)‐histidine methyl ester) cryogels
Authors: Tekiner Pınar , Perçin Işık , Ergün Bahar , Yavuz Handan , Aksöz Erol
Published: October 2012

Jack bean (Canavalia ensiformis) is the source of interesting proteins that contribute to modern biochemistry, and urease is the primary of these proteins. Owing to its role and occurrence in nature, urease has become a part of extensive studies. In this study, jack bean urease (JBU) was purified by immobilized metal affinity chromatography using Cu2+ chelated poly(hydroxyethyl methacrylate‐N‐methacryloyl‐(l)‐histidine methyl ester) [PHEMAH‐Cu2+]–based cryogels. PHEMAH‐Cu2+ cryogel was synthesized and characterized for swelling degree, morphology (by SEM), N‐methacryloyl‐(l)‐histidine methyl ester and Cu2+ incorporation (by elemental analysis and atomic absorption spectrophotometry). The binding of JBU to PHEMAH‐Cu2+ cryogel was optimized by examining the effect of pH, flow rate and JBU concentration on binding. The maximal binding of JBU was 23.2 mg/dry gram of adsorbent. The maximal binding of JBU extracted from jack bean meal was 67.8 mg/dry gram of adsorbent. The elution of JBU from cryogel column was accomplished by 1.0 M NaCl in 20 mM phosphate buffer (pH 8.0). Molecular weight and purity of JBU from jack bean meal was estimated by sodium dodecyl sulfate–polyacrylamide gel electrophoresis. It was observed that JBU could be repeatedly bound and eluted from (PHEMAH)‐Cu2+ cryogel with less than 10% loss in column capacity. Copyright © 2012 John Wiley & Sons, Ltd.
Identification of colorants on XVIII century scientific hand‐coloured print volumes
Authors: Zannini Paolo , Baraldi Pietro , Aceto Maurizio , Agostino Angelo , Fenoglio Gaia , Bersani Danilo , Canobbio Eleonora , Schiavon Elisabetta , Zanichelli Giusi , De Pasquale Andrea
Published: October 2012

Two series of printed volumes, respectively, created in Parma and in Vienna at the end of XVIII century, were analysed in order to characterise the palettes used in the hand‐coloured miniatures and to determine whether decoration had been carried out simultaneously to, or shortly after, the time of printing. The application of complementary non‐invasive analytical techniques allowed to yield a thorough knowledge of the colorants present and to determine that artists used a mixing of ancient, traditional materials such as cinnabar, minium or indigo, and materials of recent introduction in late XVIII century such as gamboge, Prussian blue or blue verditer. There was no evidence of colorants created successively to the age of printing, so that it can be concluded that decoration could have been done at the time of printing. Interesting is the use of metal pigments in the Vienna volumes, either in powder form and in foil form as a basis to obtain iridescence effects, a clue to evaluate the great skillfulness of the artist. Among the colorants identified, particularly relevant is the identification of gamboge, a colorant almost exclusively used among Far Eastern Asian painters according to the literature; this fact suggests that information on the use of pictorial materials can be strongly updated by diagnostic analyses. Copyright © 2012 John Wiley & Sons, Ltd.
A new‐type dynamic SERS method for ultrasensitive detection
Authors: Qian Kai , Yang Liangbao , Li Zhiyuan , Liu Jinhuai
Published: October 2012

In this study, we proposed a simple and ultrasensitive approach called dynamic surface‐enhanced Raman spectroscopy, which has been experimentally and theoretically demonstrated. The signal for rhodamine 6G is at least four orders of magnitude higher than that for the traditional method. A series of experiments have been exploited so as to verify the universality of our strategies. The results highlight a rapid and effective method in addictive narcotics residue apparatus, pesticide residue, crime scene or other public security field. Copyright © 2012 John Wiley & Sons, Ltd.
Deep UV resonance Raman spectroscopic study of CnF2n+2 molecules: the excitation of C–C σ bond
Authors: Jin Shaoqing , Guo Meiling , Fan Fengtao , Yang Jingxiu , Zhang Ying , Huang Baokun , Feng Zhaochi , Li Can
Published: October 2012

The σ–σ* transition of C–C bond in CnF2n+2 molecules was studied by deep UV resonance Raman spectroscopy. With the C–C σ bond selectively excited by the deep UV laser at 177.3 nm, the resonance Raman spectra of CnF2n+2 molecules were obtained on our home‐assembled deep UV Raman spectrograph. The Raman bands at 1299, 1380 and 2586 cm−1 due to the C–C skeletal stretching modes are evidently enhanced owing to the resonance Raman effect. Based on the resonance Raman spectra and theoretical calculation results, it is proposed that the electronic geometry of CnF2n+2 molecules at the σσ* excited state is displaced along the directions perpendicular and parallel to the C–C skeleton, and the excited C–C bond is not dissociative due to the delocalization of the excited electron in σ* orbital. Copyright © 2012 John Wiley & Sons, Ltd.
Adsorption of dicarboxylic acids onto nano‐structured silver surfaces – surface‐enhanced Raman scattering studies of pH‐dependent adsorption geometries
Authors: Schulte J. P. , Grass S. , Treuel L.
Published: October 2012

Understanding and shaping adsorption orientations of molecular compounds on nano‐structured metallic surfaces is an important issue across many areas of contemporary research including the design of nano‐structured surfaces and catalytic processes. Here, we used surface‐enhanced Raman spectroscopy to study these orientations on nano‐structured silver surfaces using dicarboxylic acids (maleic acid and fumaric acid) as model substances.

Results revealed a clear pH dependence of the observed adsorption geometries of dicarboxylic acids correlating well with the dissociation states of the two acidic groups. Our data demonstrate the potential of the technique and contribute to an improved understanding of adsorption orientations of molecules at the interface between nano‐structured metal surfaces and a liquid phase. Copyright © 2012 John Wiley & Sons, Ltd.
Development of an extraction method for the determination of avermectins in soil using supercritical CO2 modified with ethanol and liquid chromatography‐tandem mass spectrometry
Authors: Park Jong‐Hyouk , Choi Jeong‐Heui , Abd El‐Aty A. M. , Park Joon‐Seong , Kim Bo Mi , Na Tae‐Woong , Park Ki Hun , Yang Angel , Rahman Md. Musfiqur , Shim Jae‐Han
Published: October 2012

The aim of the present study was to develop a multiresidue analytical method for determination of avermectins (abamectin, ivermectin, moxidectin, and doramectin) in soil samples using supercritical fluid extraction and LC‐MS/MS. The optimal extraction conditions for supercritical fluid extraction were 80°C for temperature, 300 kg/cm2 for pressure, 40 min as an extraction time, and 30% of a modifier ratio. The linearity of the calibration curves was excellent and yielded the correlation coefficients (r2 = 0.998–0.999, at a range of 1.5–500 ng/g). Soil samples were fortified with known quantities of the analytes at three different concentration levels (5, 10, and 50 ng/g) and the recoveries were in the range of 82.5–96.2% with relative standard deviation values ranging between 2.1 and 7.9%. The limits of detections and limits of quantitations were 1.5 and 5 ng/g, respectively. The developed method was successfully applied to analyze avermectin residues in soil samples collected from 13 sites in the Honam area, Republic of Korea. In sum, a combination of supercritical fluid extraction and LC‐MS/MS has been proven to be highly efficient as an environmentally friendly technique for the simultaneous determination of avermectins in soil samples.
Transfer Reactions in Phenyl Carbamate Ethyl Acrylate Polymerizations
Authors: Bennet Francesca , Rölle Thomas , Fäcke Thomas , Weiser Marc‐Stephan , Bruder Friedrich‐Karl , Barner‐Kowollik Christopher , Junkers Tanja
Published: October 2012

The transfer reactions occurring during polymerization of 2‐(phenylcarbamoyloxy)ethyl acrylate (PhCEA) were studied by a detailed product mapping with electrospray ionization mass spectrometry (ESI‐MS). Unlike postulated before, PhCEA exhibits the same characteristic transfer reactions as other acrylic monomers at elevated temperatures, resulting in vinyl‐terminated and saturated products. Transfer to monomer via abstraction of a hydrogen atom from the ester side chain as suggested before is not observed. When polymerized in a poly(ethylene glycol) (PEG) matrix to increase viscosity, transfer into matrix products are observed in minor amounts, demonstrating that PEG can be employed as a solvent to further increase the overall rate of polymerization without interference from side reactions.
Polynorbornenes With Pendant Europium (III) Coordination Compounds
Authors: Knall Astrid‐Caroline , Schinagl Christina , Pein Andreas , Noormofidi Nadja , Saf Robert , Slugovc Christian
Published: October 2012

Europium‐containing monomers with different bidentate and tridentate N‐donor ligands carrying norbornoyl side chains and theonyl trifluoroacetylacetonate (TTA) as coligand are obtained and incorporated in random copolymers and amphiphilic block copolymers using ring‐opening metathesis polymerization (ROMP). The characteristic bright red long‐lived europium luminescence is retained in the polymers. The polymers are characterized (using 1H NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, fluorescence spectroscopy, and dynamic light scattering) and tested as water vapor sensor materials. A sensitivity increase over time and changes in the luminescence spectra of the polymer samples indicate dissociation of Eu(TTA)3 from the polymer chains.
Isothiocyanate concentrations and interconversion of sulforaphane to erucin in human subjects after consumption of commercial frozen broccoli compared to fresh broccoli
Authors: Saha Shikha , Hollands Wendy , Teucher Birgit , Needs Paul W. , Narbad Arjan , Ortori Catharine A. , Barrett David A. , Rossiter John T. , Mithen Richard F. , Kroon Paul A.
Published: October 2012

Scope

Sulforaphane (a potent anticarcinogenic isothiocyanate derived from glucoraphanin) is widely considered responsible for the protective effects of broccoli consumption. Broccoli is typically purchased fresh or frozen and cooked before consumption. We compared the bioavailability and metabolism of sulforaphane from portions of lightly cooked fresh or frozen broccoli, and investigated the bioconversion of sulforaphane to erucin.

Methods and results

Eighteen healthy volunteers consumed broccoli soups produced from fresh or frozen broccoli florets that had been lightly cooked and sulforaphane thio‐conjugates quantified in plasma and urine. Sulforaphane bioavailability was about tenfold higher for the soups made from fresh compared to frozen broccoli, and the reduction was shown to be due to destruction of myrosinase activity by the commercial blanching‐freezing process. Sulforaphane appeared in plasma and urine in its free form and as several thio‐conjugates forms. Erucin N‐acetyl‐cysteine conjugate was a significant urinary metabolite, and it was shown that human gut microflora can produce sulforaphane, erucin, and their nitriles from glucoraphanin.

Conclusion

The short period of blanching used to produce commercial frozen broccoli destroys myrosinase and substantially reduces sulforaphane bioavailability. Sulforaphane was converted to erucin and excreted in urine, and it was shown that human colonic flora were capable of this conversion.