Characterisation of a proposed internet synthesis of N,N-dimethyltryptamine using liquid chromatography/electrospray ionisation tandem mass spectrometry.

PubMed

Martins, Cláudia P B; Freeman, Sally; Alder, John F; Brandt, Simon D

2009-08-14

The psychoactive properties of N,N-dimethyltryptamine (DMT) are known to induce altered states of consciousness in humans. These properties attract great interest from clinical, neuroscientific, clandestine and forensic communities. The Breath of Hope Synthesis was reported on an internet website as a convenient two-step methodology for the preparation of DMT. The analytical characterisation of the first stage was the subject of previous publications by the authors and involved the thermal decarboxylation of tryptophan and the formation of tryptamine. The present study reports on the characterisation of the second step of this procedure which was based on the methylation of tryptamine. This employed methyl iodide and benzyltriethylammonium chloride/sodium hydroxide as a phase transfer catalyst. The reaction product was characterised by liquid chromatography/electrospray ionisation tandem mass spectrometry and orthogonal acceleration time-of-flight mass spectrometry. Quantitative evaluation was carried out in positive multiple reaction monitoring mode (MRM), which included synthesis of the identified reaction products. MRM screening of the product did not lead to the detection of DMT. Instead, 11.1% tryptamine starting material, 21.0% N,N,N-trimethyltryptammonium iodide (TMT) and 47.4% 1-N-methyl-TMT were detected. A 0.5% trace of the monomethylated N-methyltryptamine was also detected. This study demonstrated the impact on product purity of doubtful synthetic methodologies discussed on the internet.

Proton-conducting ionic liquid-based Proton Exchange Membrane Fuel Cell membranes: The key role of ionomer-ionic liquid interaction

NASA Astrophysics Data System (ADS)

Martinez, Mathieu; Molmeret, Yannick; Cointeaux, Laure; Iojoiu, Cristina; Leprêtre, Jean-Claude; El Kissi, Nadia; Judeinstein, Patrick; Sanchez, Jean-Yves

The paper deals with the synthesis and characterisation of proton-conducting ionic liquids (PCILs) and their polymer electrolytes obtained by blending modified Nafion membranes with different concentrations of PCILs. The PCILs are obtained by the neutralization of triethylamine with different organic acids. The first part of the paper studies the influence of acidity and acid structure on PCIL thermal and electrochemical performance, while the second part examines membrane conductivity and reveals it to depend more on PCIL structure than on its intrinsic conductivity. At 130 °C, conductivities exceeding 10 mS cm -1 were obtained in fully anhydrous conditions.

Synthesis of Ge-nanoparticles in organic solution

NASA Astrophysics Data System (ADS)

Pugsley, Andrew James

Much interest is focused on the synthesis of semiconductor particles from organic solution, in order to provide luminescent tracers for biological assays. However, group IV semiconductors have been largely neglected be cause of the lack of suitable nanoparticle formation reactions by solution-phase chemistries. A potentially useful new route to solution-based synthesis of nanocrystalline-Si,Ge involves the reaction between Zintl phases (NaSi, Mg 2Ge) that formally contain anionic semiconducting group species (Si-, Ge4-) and liquid phase SiCU, GeCU, etc. Luminescent nanoparticles formed by these reactions in organic solvents (e.g. diglyme) have been decribed in work from the Kauzlarich group at UC Davis (California, USA). The aim of this project has been to characterise the structural chemistry and luminescent properties of the products of the reaction, as well as following the course of the reaction in situ via synchrotron measurements. The product of the reaction has been characterised by TEM and x-ray absorption spectroscopy as well as other techniques. In order to analyse the x-ray absorption spectroscopy data, a number of model compounds have been studied, including the precursor material which was previously uncharacterised by this technique. An in situ reaction cell has been designed and built and used at a number of synchrotron beamlines to follow the course of the reaction. It has been found that the presence of even low concentrations of water can greatly affect the formation reaction, this is described herein.

Development of Novel DNA Cleavage Systems Based on Copper Complexes. Synthesis and Characterisation of Cu(II) Complexes of Hydroxyflavones

PubMed Central

el Amrani, F. Ben-Allal; Perelló, L.; Torres, L.

2000-01-01

Copper(II) complexes of several hydroxyflavones were prepared and characterised through their physico-chemical properties. The nuclease activity of three synthesised complexes is reported. These copper(II) complexes present more nuclease activity than the ligands and the copper(II) ion. PMID:18475969

De novo design, synthesis and characterisation of MP3, a new catalytic four-helix bundle hemeprotein.

PubMed

Faiella, Marina; Maglio, Ornella; Nastri, Flavia; Lombardi, Angela; Lista, Liliana; Hagen, Wilfred R; Pavone, Vincenzo

2012-12-07

A new artificial metalloenzyme, MP3 (MiniPeroxidase 3), designed by combining the excellent structural properties of four-helix bundle protein scaffolds with the activity of natural peroxidases, was synthesised and characterised. This new hemeprotein model was developed by covalently linking the deuteroporphyrin to two peptide chains of different compositions to obtain an asymmetric helix-loop-helix/heme/helix-loop-helix sandwich arrangement, characterised by 1) a His residue on one chain that acts as an axial ligand to the iron ion; 2) a vacant distal site that is able to accommodate exogenous ligands or substrates; and 3) an Arg residue in the distal site that should assist in hydrogen peroxide activation to give an HRP-like catalytic process. MP3 was synthesised and characterised as its iron complex. CD measurements revealed the high helix-forming propensity of the peptide, confirming the appropriateness of the model procedure; UV/Vis, MCD and EPR experiments gave insights into the coordination geometry and the spin state of the metal. Kinetic experiments showed that Fe(III)-MP3 possesses peroxidase-like activity comparable to R38A-hHRP, highlighting the possibility of mimicking the functional features of natural enzymes. The synergistic application of de novo design methods, synthetic procedures, and spectroscopic characterisation, described herein, demonstrates a method by which to implement and optimise catalytic activity for an enzyme mimetic. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, crystal structure, and protonation behaviour in solution of the recently-discovered drug metabolite, N1,N10-diacetyltriethylenetetramine

NASA Astrophysics Data System (ADS)

Wichmann, Kathrin A.; Söhnel, Tilo; Cooper, Garth J. S.

2012-03-01

N1,N10-diacetyltriethylenetetramine (DAT) is a recently-discovered major in vivo metabolite of triethylenetetramine (TETA), a highly-selective CuII chelator currently under clinical development as a novel first-in-class therapeutic for the cardiovascular, renal and retinal complications of diabetes mellitus. Characterisation of DAT is an integral aspect of the pharmacological work-up required to support this clinical development programme and, to our knowledge, no previous synthesis for it has been published. Here we report the synthesis of DAT dihydrochloride (DAT·2 HCl); its crystal structure as determined by X-ray single-crystal (XRD) and powder diffraction (XRPD); and protonation constants and species distribution in aqueous solution, which represents the different protonation states of DAT at different pH values. The crystal structure of DAT·2 HCl reveals 3D-assemblies of alternating 2D-layers comprising di-protonated DAT strands and anionic species, which form an extensive hydrogen-bond network between amine groups, acetyl groups, and chloride anions. Potentiometric titrations show that HDAT+ is the physiologically relevant state of DAT in solution. These findings contribute to the understanding of TETA's pharmacology and to its development for the experimental therapeutics of the diabetic complications.

Purification, amino acid sequence and characterisation of kangaroo IGF-I.

PubMed

Yandell, C A; Francis, G L; Wheldrake, J F; Upton, Z

1998-01-01

Insulin-like growth factor-I (IGF-I) and IGF-II have been purified to homogeneity from kangaroo (Macropus fuliginosus) serum, thus this represents the first report of the purification, sequencing and characterisation of marsupial IGFs. N-Terminal protein sequencing reveals that there are six amino acid differences between kangaroo and human IGF-I. Kangaroo IGF-II has been partially sequenced and no differences were found between human and kangaroo IGF-II in the 53 residues identified. Thus the IGFs appear to be remarkably structurally conserved during mammalian radiation. In addition, in vitro characterisation of kangaroo IGF-I demonstrated that the functional properties of human, kangaroo and chicken IGF-I are very similar. In an assay measuring the ability of the proteins to stimulate protein synthesis in rat L6 myoblasts, all IGF-I proteins were found to be equally potent. The ability of all three proteins to compete for binding with radiolabelled human IGF-I to type-1 IGF receptors in L6 myoblasts and in Sminthopsis crassicaudata transformed lung fibroblasts, a marsupial cell line, was comparable. Furthermore, kangaroo and human IGF-I react equally in a human IGF-I RIA using a human reference standard, radiolabelled human IGF-I and a polyclonal antibody raised against recombinant human IGF-I. This study indicates that not only is the primary structure of eutherian and metatherian IGF-I conserved, but also the proteins appear to be functionally similar.

New lethal disease involving type I and III collagen defect resembling geroderma osteodysplastica, De Barsy syndrome, and Ehlers-Danlos syndrome IV.

PubMed

Jukkola, A; Kauppila, S; Risteli, L; Vuopala, K; Risteli, J; Leisti, J; Pajunen, L

1998-06-01

We describe the clinical findings and biochemical features of a male child suffering from a so far undescribed lethal connective tissue disorder characterised by extreme hypermobility of the joints, lax skin, cataracts, severe growth retardation, and insufficient production of type I and type III procollagens. His features are compared with Ehlers-Danlos type IV, De Barsy syndrome, and geroderma osteodysplastica, as these disorders show some symptoms and signs shared with our patient. The child died because of failure of the connective tissue structures joining the skull and the spine, leading to progressive spinal stenosis. The aortic valve was translucent and insufficient. The clinical symptoms and signs, together with histological findings, suggested a collagen defect. Studies on both skin fibroblast cultures and the patient's serum showed reduced synthesis of collagen types I and III at the protein and RNA levels. The sizes of the mRNAs and newly synthesised proteins were normal, excluding gross structural abnormalities. These findings are not in accordance with any other collagen defect characterised so far.

Synthesis, structural characterisation and magnetic studies of polymetallic iron phosphonate cages.

PubMed

Khanra, Sumit; Helliwell, Madeleine; Tuna, Floriana; McInnes, Eric J L; Winpenny, Richard E P

2009-08-21

Four new polymetallic iron(III) phosphonate cages have been made and structurally characterised. These are an octanuclear cage [Fe(8)O(3)(OH)(2)(O(2)C(t)Bu)(11)(PhCH(2)PO(3))(3)(py)(3)], a decanuclear cage [Fe(10)O(2)(OH)(8)(O(2)C(t)Bu)(10)(PhCH(2)PO(3))(4)(pip)(2)], a heterometallic cage [Fe(6)Li(5)(mu(3)-O)(2)((t)BuPO(3))(6)(O(2)C(t)Bu)(8)(MeOH)(2)(Py)(4)] and a tridecanuclear cage [Et(3)NH](2)[Fe(13)(mu(3)-O)(3)(mu(2)-OH)(7)((t)BuPO(3))(7)(Me(3)CCO(2))(14)(H(2)O)] (pip = piperidine, py = pyridine). Magnetic studies of the first three compounds show anti-ferromagnetic exchange between the iron(III) centers leading to diamagnetic ground states for the homometallic cages. For the heterometallic cage, the six Fe(III) centers are arranged in two triangles, and each triangle has an S = 1/2 spin ground state.

Structural and Interfacial Properties of Hyperbranched-Linear Polymer Surfactant.

PubMed

Qiang, Taotao; Bu, Qiaoqiao; Huang, Zhaofeng; Wang, Xuechuan

2014-01-01

With oleic acid grafting modification, a series of hyperbranched-linear polymer surfactants (HLPS) were prepared by hydroxyl-terminated hyperbranched polymer (HBP), which was gained through a step synthesis method using trimethylolpropane and AB 2 monomer. The AB 2 monomers were obtained through the Michael addition reaction of methyl acrylate and diethanol amine. The structures of HLPS were characterised by Fourier transform infrared spectrophotometer and nuclear magnetic resonance (NMR), which indicated that HBP was successfully modified by oleic acid. Furthermore, the properties of surface tension and critical micelle concentration of HLPS solution showed that HLPS can significantly reduce the surface tension of water. The morphology of the HLPS solution was characterised by dynamic light scattering, which revealed that HLPS exhibited a nonmonotonic appearance in particle size at different scattering angles owing to the different replaced linear portions. The relationships of the surface pressure to monolayer area and time were measured using the Langmuir-Blodgett instrument, which showed that the surface tension of monolayer molecules increased with the increasing of hydrophobic groups. In addition, the interface conditions of different replaced HLPS solutions were simulated.

New coumarin carboxylates having trifluoromethyl, diethylamino and morpholino terminal groups: Synthesis and mesomorphic characterisations

NASA Astrophysics Data System (ADS)

Srinivasa, Hosapalya Thimmaiah; Harishkumar, Hosanagara Narayana; Palakshamurthy, Bandrehalli Siddagangappa

2017-03-01

New set of trifluromethyl, diethylamino and morpholino derived coumarin compounds were prepared by reacting various coumarin 3-carboxylic acids with various phenyl esters with peripheral alkyl, ester and polar cyano moieties in the presence of EDC.HCl/DMAP as esterification agent. The chemical structures of new coumarin derivatives were confirmed by standard spectroscopic techniques and mesomorphic behaviours were established by polarised optical microscopy (POM) and differential scanning calorimetry (DSC). Trifluoromethane and morpholino derivatives show SmA/Nematic phase, while diethylamino derivatives did not show liquid crystalline property.

Nanoparticles and self-organisation: the emergence of hierarchical properties from the nanoparticle soup (i.e., the small is getting bigger). Concluding remarks for Faraday Discussion: Nanoparticle Synthesis and Assembly.

PubMed

Schiffrin, David J

2015-01-01

Some four years ago, one of the participants in this Discussion (Prof. Nicholas Kotov) predicted that: "within five years we shall see multiple examples of electronic, sensor, optical and other devices utilizing self-assembled superstructures" (N. A. Kotov, J. Mater. Chem., 2011, 21, 16673-16674). Although this prediction came partially to fruition, we have witnessed an unprecedented interest in the properties of materials at the nanoscale. The point highlighted by Kotov, however, was the importance of self-assembly of structures from well characterised building blocks to yield hierarchical structures, hopefully with predictable properties, a concept that is an everyday pursuit of synthetic chemists. This Discussion has brought together researchers from a wide range of disciplines, i.e., colloid science, modelling, nanoparticle synthesis and organisation, magnetic and optical materials, and new imaging methods, within the excellent traditional Faraday Discussion format, to discuss advances in areas relevant to the main theme of the meeting.

Eco-friendly and green synthesis of BiVO4 nanoparticle using microwave irradiation as photocatalayst for the degradation of Alizarin Red S

NASA Astrophysics Data System (ADS)

Abraham, S. Daniel; David, S. Theodore; Bennie, R. Biju; Joel, C.; Kumar, D. Sanjay

2016-06-01

Bismuth vanadate (BiVO4) nanocrystals have been successfully synthesised using microwave-assisted combustion synthesis (MCS), and characterised using Fourier transform infrared (FT-IR) and Raman spectra, surface area analysis (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), Energy Dispersive X-ray analysis (EDX), diffused reflectance spectroscopy (DRS) and Photoluminescence (PL) spectroscopy. The XRD results confirmed the formation of monoclinic bismuth vanadate. The formations of BiO & VO43-vibrations were ascertained from FT-IR data. The morphology of hallow internal structural micro entities were confirmed by SEM. The optical properties were determined by DRS and PL spectra. Hence, the influence of the preparation methods on the structure, morphology and optical activities of bismuth vanadate was investigated systematically. Photocatalytic degradation (PCD) of Alizarin Red S (ARS), an effective disrupting chemical in aqueous medium was investigated using BiVO4 nanoparticles. The kinetics of PCD was found to follow pseudo first-order.

Electrochemical synthesis, characterisation and phytogenic properties of silver nanoparticles

NASA Astrophysics Data System (ADS)

Singaravelan, R.; Bangaru Sudarsan Alwar, S.

2015-12-01

This work exemplifies a simple and rapid method for the synthesis of silver nanodendrite with a novel electrochemical technique. The antibacterial activity of these silver nanoparticles (Ag NPs) against pathogenic bacteria was investigated along with the routine study of optical and spectral characterisation. The optical properties of the silver nanoparticles were characterised by diffuse reflectance spectroscopy. The optical band gap energy of the electrodeposited Ag NPs was determined from the diffuse reflectance using Kubelka-Munk formula. X-ray diffraction (XRD) studies were carried out to determine the crystalline nature of the silver nanoparticles which confirmed the formation of silver nanocrystals. The XRD pattern revealed that the electrodeposited Ag NPs were in the cubic geometry with dendrite preponderance. The average particle size and the peak broadening were deliberated using Debye-Scherrer equation and lattice strain due to the peak broadening was studied using Williamson-Hall method. Surface morphology of the Ag NPs was characterised by high-resolution scanning electron microscope and the results showed the high degree of aggregation in the particles. The antibacterial activity of the Ag NPs was evaluated and showed unprecedented level antibacterial activity against multidrug resistant strains such as Staphylococcus aureus, Bacillus subtilis, Klebsiella pneumonia and Escherichia coli in combination with Streptomycin.

Simple chemical synthesis of novel ZnO nanostructures: Role of counter ions

NASA Astrophysics Data System (ADS)

Pudukudy, Manoj; Yaakob, Zahira

2014-04-01

This article reports the synthesis, characterisation and photocatalytic activity of novel ZnO nanostructures prepared via the thermal decomposition of hydrozincite. Hydrozincites were obtained by the conventional precipitation route using different zinc salts such as acetate, nitrate, chloride and sulphate. The effect of counter ions (CH3COO-, Cl-, NO3-, and SO42-) on the structural, textural, morphological and optical properties was investigated. Various characterisations depicted the active role of counter ions in the properties of ZnO. Hexagonal wurtzite structure of ZnO with fine crystalline size was obvious from the XRD results, irrespective of the counter ions. Electron microscopic images indicated the role of counter ions in the surface and internal morphology of ZnO nanomaterials. Special coral like agglomerated morphology of elongated particles with high porosity was observed for the ZnO prepared from acetate precursor. Spherical, elongated and irregular shaped bigger lumps of ZnO nanoparticles with various novel morphologies were resulted for the sulphate, nitrate and chloride precursors respectively. Highly ordered porous micro disc like morphology was noted for the ZnO samples prepared from the sulphate and nitrate salts. Photoluminescence spectra showed the characteristic blue and green emission bands, depicting the presence of large crystal defects and high oxygen vacancies in the samples. Photocatalytic activity of the as-prepared ZnO catalysts was examined by the degradation of methylene blue under UV light irradiation. Degradation results indicated their substantial activity with respect to the counter ions. ZnO prepared from the acetate precursor showed highest photoactivity due to its high surface area, special morphology and high oxygen vacancies.

Biosynthesis of silver and platinum nanoparticles using orange peel extract: characterisation and applications.

PubMed

Castro, Laura; Blázquez, María Luisa; González, Felisa; Muñoz, Jesús Ángel; Ballester, Antonio

2015-10-01

This study focuses on the green synthesis of noble metal nanoparticles (silver (Ag) and platinum (Pt)) and how the size and shape of the nanoparticles produced can be controlled through changes in the initial pH value of the precursor solution. The nanoparticles were characterised by ultra-violet-visible spectroscopy, transmission electron microscopy and X-ray diffraction. This simple and environmentally friendly method allows the synthesis of diverse nanostructures in the absence of a surfactant or polymer to direct nanoparticle growth, and without externally adding seed crystallites. The antibacterial effects of Ag nanoparticles and catalytic properties of Pt nanoparticles were explored for future promising biotechnological approaches in different fields.

Synthesis, characterisation and anion exchange properties of copper, magnesium, zinc and nickel hydroxy nitrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biswick, Timothy; Jones, William; Pacula, Aleksandra

2006-01-15

Anion exchange reactions of four structurally related hydroxy salts, Cu{sub 2}(OH){sub 3}NO{sub 3}, Mg{sub 2}(OH){sub 3}NO{sub 3}, Ni{sub 2}(OH){sub 3}NO{sub 3} and Zn{sub 3}(OH){sub 4}(NO{sub 3}){sub 2} are compared and trends rationalised in terms of the strength of the covalent bond between the nitrate group and the matrix cation. Powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and elemental analysis are used to characterise the materials. Replacement of the nitrate anions in the zinc and copper salts with benzoate anions is possible although exchange of the zinc salt is accompanied by modification of the layer structure frommore » one where zinc is exclusively six-fold coordinated to a structure where there is both six- and four-fold zinc coordination. Magnesium and nickel hydroxy nitrates, on the other hand, hydrolyse to their respective metal hydroxides. -- Graphical abstract: PXRD patterns of exchange products of (a) Zn{sub 3}(OH){sub 4}(NO{sub 3}){sub 2} (b) Zn{sub 5}(OH){sub 8}(NO{sub 3}){sub 2}.2H{sub 2}O and (c) Cu{sub 2}(OH){sub 3}NO{sub 3} with benzoate anions.« less

Mechanism of plant-mediated synthesis of silver nanoparticles - A review on biomolecules involved, characterisation and antibacterial activity.

PubMed

Rajeshkumar, S; Bharath, L V

2017-08-01

Engineering a reliable and eco-accommodating methodology for the synthesis of metal nanoparticles is a crucial step in the field of nanotechnology. Plant-mediated synthesis of metal nanoparticles has been developed as a substitute to defeat the limitations of conventional synthesis approaches such as physical and chemical methods. Biomolecules, such as proteins, amino acids, enzymes, flavonoids, and terpenoids from several plant extracts have been used as a stabilising and reducing agents for the synthesis of AgNPs. Regardless of an extensive range of biomolecules assistance in the synthesis procedure, researchers are facing a significant challenge to synthesise stable and geometrically controlled AgNPs. In the past decade, several efforts were made to develop Plant-mediated synthesis methods to produce stable, cost effective and eco-friendly AgNPs. More than hundred different plants extract sources for synthesising AgNPs were described in the last decade by several researchers. Most of the reviews were focused on various plant sources for synthesis, various characterization techniques for characteristic analysis, and antibacterial activity against bacterial. There are many reviews are available for the plant-mediated synthesis of AgNPs as well as antibacterial activity of AgNPs but this is the first review article mainly focused on biomolecules of plants and its various parts and operating conditions involved in the synthesis. Apart from, this review includes the characterisation of AgNPs and antibacterial activity of such nanoparticles with size, shape and method used for this study. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and Structural characterization of β-ketoiminate-stabilized gallium hydrides for chemical vapor deposition applications.

PubMed

Marchand, Peter; Pugh, David; Parkin, Ivan P; Carmalt, Claire J

2014-08-11

Bis-β-ketoimine ligands of the form [(CH2 )n {N(H)C(Me)CHC(Me)O}2 ] (L(n) H2 , n=2, 3 and 4) were employed in the formation of a range of gallium complexes [Ga(L(n) )X] (X=Cl, Me, H), which were characterised by NMR spectroscopy, mass spectrometry and single-crystal X-ray diffraction analysis. The β-ketoimine ligands have also been used for the stabilisation of rare gallium hydride species [Ga(L(n) )H] (n=2 (7); n=3 (8)), which have been structurally characterised for the first time, confirming the formation of five-coordinate, monomeric species. The stability of these hydrides has been probed through thermal analysis, revealing stability at temperatures in excess of 200 °C. The efficacy of all the gallium β-ketoiminate complexes as molecular precursors for the deposition of gallium oxide thin films by chemical vapour deposition (CVD) has been investigated through thermogravimetric analysis and deposition studies, with the best results being found for a bimetallic gallium methyl complex [L(3) {GaMe2 }2 ] (5) and the hydride [Ga(L(3) )H] (8). The resulting films (F5 and F8, respectively) were amorphous as-deposited and thus were characterised primarily by XPS, EDXA and SEM techniques, which showed the formation of stoichiometric (F5) and oxygen-deficient (F8) Ga2 O3 thin films. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterisation of the hollandite solid solution Ba1.2-xCsxFe2.4-xTi5.6+xO16 for partitioning and conditioning of radiocaesium

NASA Astrophysics Data System (ADS)

Bailey, Daniel J.; Stennett, Martin C.; Mason, Amber R.; Hyatt, Neil C.

2018-05-01

The geological disposal of high level radioactive waste requires careful budgeting of the heat load produced by radiogenic decay. Removal of high-heat generating radionuclides, such as 137Cs, reduces the heat load in the repository allowing the remaining high level waste to be packed closer together therefore reducing demand for repository space and the cost of the disposal of the remaining wastes. Hollandites have been proposed as a possible host matrix for the long-term disposal of Cs separated from HLW raffinate. The incorporation of Cs into the hollandite phase is aided by substitution of cations on the B-site of the hollandite structure, including iron. A range of Cs containing iron hollandites were synthesised via an alkoxide-nitrate route and the structural environment of Fe in the resultant material characterised by Mössbauer and X-ray Absorption Near Edge Spectroscopy. The results of spectroscopic analysis found that Fe was present as octahedrally co-ordinated Fe (III) in all cases and acts as an effective charge compensator over a wide solid solution range.

Synthesis and structural characterization of transition metal doped MgO: Mg0.95Mn0.01TM0.04O (TM = Co, Ni, Cu)

NASA Astrophysics Data System (ADS)

Islam, Ishtihadah; Khandy, Shakeel Ahmad; Hafiz, Aurangzeb Khurram

2018-05-01

In the present work, preparation and characterization of transition metal doped MgO: Zn0.94Mn0.01TM0.05O (TM = Co, Ni and Cu) nano-particles have been reported. Transition metal doped samples of MgO were synthesized by Sol gel auto combustion method. Structural characterisation from XRD and SEM show the formation of single-phase primary particles, nearly of spherical shaped nano-crystallites. The crystallite size was found to be 78.2, 67.02, 78.11 and 64 nm for pure, Co, Cu and Ni doped MgMnO nano-particles, respectively. Hence, the average crystallite size increases monotonously from Co to Cu doping.

Engineering education as a complex system

NASA Astrophysics Data System (ADS)

Gattie, David K.; Kellam, Nadia N.; Schramski, John R.; Walther, Joachim

2011-12-01

This paper presents a theoretical basis for cultivating engineering education as a complex system that will prepare students to think critically and make decisions with regard to poorly understood, ill-structured issues. Integral to this theoretical basis is a solution space construct developed and presented as a benchmark for evaluating problem-solving orientations that emerge within students' thinking as they progress through an engineering curriculum. It is proposed that the traditional engineering education model, while analytically rigorous, is characterised by properties that, although necessary, are insufficient for preparing students to address complex issues of the twenty-first century. A Synthesis and Design Studio model for engineering education is proposed, which maintains the necessary rigor of analysis within a uniquely complex yet sufficiently structured learning environment.

Nanosize Fe x O y @SBA-3: A Comparative Study Between Conventional and Microwave Assisted Synthesis.

PubMed

Barik, Sunita; Badamali, Sushanta K; Sahoo, Sagarika; Behera, Nandakishor; Dapurkar, Sudhir E

2018-01-01

The present study is focussed on development of highly dispersed nanosize iron oxide (FexOy) particles within the uniform mesopore channels of SBA-3. Herein we report a comparative study between conventional incipient wetness and microwave assisted synthesis routes adopted to devise nanoparticles. The developed materials are characterised by following X-ray diffraction, high resolution transmission electron microscopy, proton induced X-ray emission, diffuse reflectance UV-visible spectroscopy, thermogravimetry and Fourier transform infrared spectroscopy. Mesoporous siliceous SBA-3 was prepared at room temperature to obtain samples with good crystallinity and ordered pore structure. Pore channels of SBA-3 were used as nanoreactor for developing iron oxide nanoparticles. Iron oxide nanoparticles developed under microwave activation showed uniform distribution within the SBA-3 structure along with retaining the orderness of the pore architecture. On the contrary, iron oxides developed under incipient wetness method followed by conventional heating resulted in agglomeration of nanoparticles along with significant loss in SBA-3 pore structure. Proton induced X-ray emission studies revealed the extremely high purity of the samples and almost thrice higher amount of iron oxide particles are encapsulated within the host by microwave assisted preparation as compared to incipient/conventional heating method.

Synthesis, PtS-type structure, and anomalous mechanics of the Cd(CN)2 precursor Cd(NH3)2[Cd(CN)4].

PubMed

Coates, Chloe S; Makepeace, Joshua W; Seel, Andrew G; Baise, Mia; Slater, Ben; Goodwin, Andrew L

2018-05-15

We report the nonaqueous synthesis of Cd(CN)2 by oxidation of cadmium metal with Hg(CN)2 in liquid ammonia. The reaction proceeds via an intermediate of composition Cd(NH3)2[Cd(CN)4], which converts to Cd(CN)2 on prolonged heating. Powder X-ray diffraction measurements allow us to determine the crystal structure of the previously-unreported Cd(NH3)2[Cd(CN)4], which we find to adopt a twofold interpenetrating PtS topology. We discuss the effect of partial oxidation on the Cd/Hg composition of this intermediate, as well as its implications for the reconstructive nature of the deammination process. Variable-temperature X-ray diffraction measurements allow us to characterise the anisotropic negative thermal expansion (NTE) behaviour of Cd(NH3)2[Cd(CN)4] together with the effect of Cd/Hg substitution; ab initio density functional theory (DFT) calculations reveal a similarly anomalous mechanical response in the form of both negative linear compressibility (NLC) and negative Poisson's ratios.

Development of a colourimetric assay for glycosynthases.

PubMed

Hayes, Marc R; Bochinsky, Kevin A; Seibt, Lisa S; Elling, Lothar; Pietruszka, Jörg

2017-09-10

The synthesis of glycosidic structures by catalysis via glycosynthases has gained much interest due to the potential high product yields and specificity of the enzymes. Nevertheless, the characterisation and implementation of new glycosynthases is greatly hampered by the lack of high-throughput methods for reaction analysis and screening of potential glycosynthase variants. Fluoride detection, via silyl ether chemosensors, has recently shown high potential for the identification of glycosynthase mutants in a high-throughput manner, though limited by the low maximal detection concentration. In the present paper, we describe a new version of a glycosynthase activity assay using a silyl ether of p-nitrophenol, allowing fast reliable detection of fluoride even at concentrations of 4mM and higher. This improvement of detection allows not only screening and identification but also kinetic characterisation of glycosynthases and synthetic reactions in a fast microtiter plate format. The applicability of the assay was successfully demonstrated by the biochemical characterisation of the mesophilic β-glucosynthase of Abg-E358S (Rhizobium radiobacter) and psychrotolerant β-glucosynthase BglU-E377A (Micrococcus antarcticus). The limitation of hyperthermophilic glycosidases as potential glycosynthases, when using glycosyl fluoride donors, was also illustrated by the example of the putative β-galactosidase GalPf from Pyrococcus furiosus. Copyright © 2017 Elsevier B.V. All rights reserved.

The truth about false unicorn (Chamaelirium luteum): total synthesis of 23R,24S-chiograsterol B defines the structure and stereochemistry of the major saponins from this medicinal herb.

PubMed

Matovic, Nicholas J; Stuthe, Julia M U; Challinor, Victoria L; Bernhardt, Paul V; Lehmann, Reginald P; Kitching, William; De Voss, James J

2011-06-27

Chamaelirium luteum is used in traditional medicine systems and commercial botanical dietary supplements for the treatment of female reproductive health problems. Despite the wide use of this herb, only very limited phytochemical characterisation is available. Our investigation of C. luteum roots led to the isolation of two new steroidal saponins 1 and 2 that contain an unusual aglycone 3. The absolute configurations of these molecules were unable to be determined spectroscopically and thus the total synthesis of 3 was undertaken and achieved in 16 steps and 1.6 % overall yield from pregnenolone. The key step in the synthesis was the stereoselective installation of the side chain at C-17 and C-20, which employed anion-accelerated oxy-Cope methodology. The relative configuration of aglycone 3 was determined by X-ray crystallography of an advanced synthetic intermediate. The absolute configuration was based upon that of the pregnenolone-derived steroidal skeleton and determined to be 23R,24S. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bright-field electron tomography of individual inorganic fullerene-like structures

NASA Astrophysics Data System (ADS)

Bar Sadan, Maya; Wolf, Sharon G.; Houben, Lothar

2010-03-01

Nanotubes and fullerene-like nanoparticles of various inorganic layered compounds have been studied extensively in recent years. Their characterisation on the atomic scale has proven essential for progress in synthesis as well as for the theoretical modelling of their physical properties. We show that with electron tomography it is possible to achieve a reliable reconstruction of the 3D structure of nested WS2 or MoS2 fullerene-like and nanotube structures with sub-nanometre resolution using electron microscopes that are not aberration-corrected. Model-based simulations were used to identify imaging parameters, under which structural features such as the shell structure can be retained in the tomogram reconstructed from bright-field micrographs. The isolation of a particle out of an agglomerate for the analysis of a single structure and its interconnection with other particles is facilitated through the tomograms. The internal structure of the layers within the particle alongside the shape and content of its internal void are reconstructed. The tomographic reconstruction yields insights regarding the growth process as well as structural defects, such as non-continuous layers, which relate to the lubrication properties.Nanotubes and fullerene-like nanoparticles of various inorganic layered compounds have been studied extensively in recent years. Their characterisation on the atomic scale has proven essential for progress in synthesis as well as for the theoretical modelling of their physical properties. We show that with electron tomography it is possible to achieve a reliable reconstruction of the 3D structure of nested WS2 or MoS2 fullerene-like and nanotube structures with sub-nanometre resolution using electron microscopes that are not aberration-corrected. Model-based simulations were used to identify imaging parameters, under which structural features such as the shell structure can be retained in the tomogram reconstructed from bright-field micrographs. The isolation of a particle out of an agglomerate for the analysis of a single structure and its interconnection with other particles is facilitated through the tomograms. The internal structure of the layers within the particle alongside the shape and content of its internal void are reconstructed. The tomographic reconstruction yields insights regarding the growth process as well as structural defects, such as non-continuous layers, which relate to the lubrication properties. Electronic supplementary information (ESI) available: Figs. S1 and S2 and movies S1-S6. See DOI: 10.1039/b9nr00251k

Synthesis and characterisation of the uranium pyrochlore betafite [(Ca,U)₂(Ti,Nb,Ta)₂O₇].

PubMed

McMaster, Scott A; Ram, Rahul; Charalambous, Fiona; Pownceby, Mark I; Tardio, James; Bhargava, Suresh K

2014-09-15

Betafite of composition [(Ca,U)2(Ti,Nb,Ta)2O7] was prepared via a solid state synthesis route. The synthesis was shown to be sensitive to initial reactant ratios, the atmosphere used (oxidising, neutral, reducing) and time. The optimum conditions for the synthesis of betafite were found to be heating the reactants required at 1150°C for 48 h under an inert gas atmosphere. XRD characterisation revealed that the synthesised betafite contained minor impurities. EPMA analysis of a sectioned surface showed very small regions of Ca-free betafite on grain boundaries as well as minor rutile impurities. Some heterogeneity between the Nb:Ta ratio was observed by quantitative EPMA but was generally within the nomenclature requirements stated for betafite. SEM analysis revealed the synthesised betafite was comprised mostly of hexaoctohedral crystals of ∼ 3 μm in diameter. XPS analysis of the sample showed that the uranium in the synthesised betafite was predominately present in the U(5+) oxidation state. A minor amount of U(6+) was also detected which was possibly due to surface oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.

Structural studies of the crystallisation of microporous materials

NASA Astrophysics Data System (ADS)

Davies, Andrew Treharne

A range of powerful synchrotron radiation characterisation techniques have been used to study fundamental aspects of the fonnation of microporous solids, specifically alumi nosilicates, heteroatom substituted aluminophosphates and titanosilicates. This work has been performed with the aim of investigating in situ the structural changes occurring during crystallisation and post synthetic treatment. In situ EDXRD was used to follow the crystallisation of these materials under a wide range of synthesis conditions using a hydrothermal cell and a solid-state detector array. A quantitative analysis of the crystallisation kinetics was performed for the large pore aluminosilicate, zeolite A, using a simple mathematical model to calculate the activation energy of formation. The results obtained were found to closely agree with both the experimental results and theoretical models of others. A qualitative study of the effect of altering the synthesis conditions was also investigated for this material. Similar kinetic studies were then performed for a range of microporous aluminophosphates and their cobalt substituted derivatives in order to follow the effects of varying synthesis conditions such as the synthesis temperature, organic template type, and cobalt concentration. Distinct trends were noted in the formation times, stability and nature of the resulting crystalline phases as conditions were varied. The relationship between the cobalt and organic template molecules during crystallisation was considered in some detail with reference to other experimental data and theoretical models. The alumi nophosphate studies were subsequently extended to a range of other heteroatom substituted aluminophosphates, using in situ EDXRD, complimented by EXAFS, which allowed investigation of the local environments around the heteroatoms within the microporous structure. EDXRD and EXAFS studies have been performed on the microporous titanosilicate, ETS-10, while the thermal stability of this material has also been investigated in situ using synchrotron X-ray diffraction in conjunction with a high temperature environmental cell.

Synthesis, characterization, crystal structure and DNA-binding studies of transition metal hydrazone complexes

NASA Astrophysics Data System (ADS)

Kanchanadevi, S.; Parveen, S.; Mahalingam, V.

2018-04-01

Three new complexes containing salicylaldazine (HL) ligand were synthesised by reacting suitable precursor complex [MCl2(PPh3)2] with the ligand (where M = Cu(II) or Ni(II) or Co(II)). The new complexes were characterised by various spectral studies such as IR, UV-Vis,1H NMR,EPR,fluorescence and elemental analyses. The binding modes of the complexes with HS-DNA have been studied by UV-Vis absorption titration. Binding of the complexes with bovine serum albumin (BSA) protein has been investigated using UV-visible, fluorescence and synchronous fluorescence spectroscopic methods. Redox behaviour of the complexes has been investigated by cyclic voltammetry.

Studies on the magnetic ground state of a spin Mobius strip

DOE PAGES

Newton, Graham N.; Hoshino, Norihisa; Matsumoto, Takuto; ...

2016-08-22

In this paper, we report the synthesis, structure and detailed characterisation of three n-membered oxovanadium rings, Na n[(V=O) nNa n(H 2O) n(α, β, or γ-CD) 2]•m H 2O (n=6, 7, or 8), prepared by the reactions of (V=O)SO 4•x H 2O with α, β, or γ-cyclodextrins (CDs) and NaOH in water. Their alternating heterometallic vanadium/sodium cyclic core structures were sandwiched between two CD moieties such that O-Na-O groups separated the neighbouring vanadyl ions. Antiferromagnetic interactions between the S=1/2 vanadyl ions led to S=0 ground states for the even-membered rings, but to two quasi-degenerate S=1/2 states for the spin-frustrated heptanuclear cluster.

Novel Red-Orange Phosphors Na2BaMg(PO4)2:Pr3+: Synthesis, Crystal Structure and Photoluminescence Performance

NASA Astrophysics Data System (ADS)

Pan, Lu; Yang, Xiaozhan; Xiong, Chaoyue; Deng, Dashen; Qin, Chunlin; Feng, Wenlin

2018-01-01

A series of new red-orange emission phosphors Na2BaMg(PO4)2:Pr3+ were synthesised by a high-temperature solid-state reaction. The crystal structure and photoluminescence properties of these samples were characterised by X-ray diffraction and spectroscopic measurements. This compound holds P3̅m1 space group of the trigonal system with the lattice parameters of hexagonal cell a=0.5304(3) nm and c=0.6989(3) nm. The phosphor emits the strongest peak at 606 nm when excited by 449 nm. The average Commission Internationale de l'Eclairage chromaticity coordinates calculated for the phosphors are (0.52, 0.46). The results demonstrate the potential application of these phosphors in solid-state lighting and other fields.

Synthesis and characterisation of new types of side chain cholesteryl polymers.

PubMed

Wang, Bin; Du, Haiyan; Zhang, Junhua

2011-01-01

A series of cholesterol derivatives have been synthesised via the alkylation reaction of the 3-hydroxyl group with the aliphatic bromide compounds with different chain lengths, namely 3β-alkyloxy-cholesterol. The double bond between the C5 and C6 positions in these cholesterol derivatives was oxidised into epoxy, followed by an epoxy-ring-opening reaction with the treatment with acrylic acid, resulting in a series of 3β-alkyloxy-5α-hydroxy-6β-acryloyloxycholesterol, C(n)OCh (n=1, 2, 4, 6, 8, 10, 12), The acrylate group is connected to the C6 position, which is confirmed by the single crystal structure analysis. The corresponding polymers, PC(n)OCh, were prepared via free radical polymerisation. The structure of monomers and the resulting polymers were characterised with nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The thermal properties of PC(n)OCh were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). To determine the secondary structure of polymers, circular dichroism (CD) spectra were performed. It was found that not all monomers produce high-molecular-weight polymers because of steric hindrance. However, all polymers have a helical structure, which can be enhanced by increasing the alkoxy chain length. In addition, increasing the alkoxy chain length decreases the glass transition temperature and increases the decomposition temperature of the polymers. Copyright © 2010 Elsevier Inc. All rights reserved.

Toxicological methods for tracing drug abuse: chromatographic, spectroscopic and biological characterisation of ecstasy derivatives.

PubMed

Belhadj-Tahar, Hafid; Payoux, Pierre; Tafani, Mathieu; Coulais, Yvon; Calet, Serge; Bousseksou, Azzedine

2010-03-01

Analysis often reveals variability in the composition of ecstasy pills from pure 3,4-methylenedioxymethamphetamine (MDMA) to mixtures of MDMA derivatives, amphetamine, and other unidentified substances. For a comprehensive toxicological analysis one needs to know all steps to MDMA synthesis which may originate impurities. The aim of this study was to synthesise and determine the chemical-physical and in vitro biological properties of a series of MDMA derivatives.3,4-methylendioxyphenyl-2-nitropropene (MDNP) was obtained by condensation of piperonal with an excess of nitroethane in the presence of ammonium acetate. MDNP was then reduced to methylenedioxyamphetamine (MDA) by LiAlH3. All compounds were analysed using HPLC and spectroscopic technique [Raman, nuclear magnetic resonance (NMR), or infrared (IR)] at all the steps of synthesis. In addition, we assessed the biological potentials of these compounds by measuring in vitro their (i) blood cell/whole blood partition coefficient, (ii) binding to plasmatic proteins (Fbp), and (iii) membrane adsorption. Chemical structure was determined with antibody fluorescence polarisation immunoassay (FPIA). This study showed the presence of solid impurities, particularly of a neurotoxic compound of Al3+ in the final products. FPIA identified the aminoethane group close to the substituted benzene ring, but did not detect the two major precursors of MDMA: MDNP and piperonal. Raman spectroscopy is an attractive alternative technique to characterise ecstasy pills and it can identify stereoisomeric forms such as cis-MDNP and trans-MDNP, which exhibit signals at 1650 cm-1 and 1300 cm-1, respectively.

Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine.

PubMed

Bennett, Martin A; Bhargava, Suresh K; Bond, Alan M; Burgar, Iko M; Guo, Si-Xuan; Kar, Gopa; Privér, Steven H; Wagler, Jörg; Willis, Anthony C; Torriero, Angel A J

2010-10-14

Four new complexes, [PdX(κ(2)-2-C(6)R(4)PPh(2))(PPh(2)Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh(2)Fc) have been prepared and fully characterised. The X-ray structures of complexes trans-1, cis-2 and cis-4, and that of a decomposition product of 4, [Pd(κ(2)-2-C(6)F(4)PPh(2))(μ-I)(μ-2-C(6)F(4)PPh(2))PdI(PPh(2)Fc)] (5), have been determined. These complexes show a distorted square planar geometry about the metal atom, the bite angles of the chelate ligands being about 69°, as expected. The cis/trans ratio of 1-4 in solution is strongly dependent on solvent. The new complexes and the uncoordinated PPh(2)Fc ligand were electrochemically characterised by cyclic and rotating disk voltammetry, UV-visible spectroelectrochemistry, and bulk electrolysis in dichloromethane and acetonitrile. In both cases, oxidation occurs at both the ferrocene and phosphine centres, but the complexes oxidise at more positive potentials than uncoordinated PPh(2)Fc; subsequently, the metal-phosphorus bond is cleaved, leading to free PPh(2)Fc(+), which undergoes further chemical and electrochemical reactions.

Green synthesis, characterisation and bioactivity of plant-mediated silver nanoparticles using Decalepis hamiltonii root extract.

PubMed

Rashmi, Venkatasubbaiah; Sanjay, Konasur R

2017-04-01

Consistent search of plants for green synthesis of silver nanoparticles (SNPs) is an important arena in Nanomedicine. This study focuses on synthesis of SNPs using bioreduction of silver nitrate (AgNO 3 ) by aqueous root extract of Decalepis hamiltonii . The biosynthesis of SNPs was monitored by UV-vis analysis at absorbance maxima 432 nm. The fluorescence emission spectra of SNPs illustrated the broad emission peak 450-483 nm at different excitation wavelengths. The surface characteristics were studied by scanning electron microscope and atomic force microscopy, showed spherical shape of SNPs and dynamic light scattering analysis confirmed the average particle size 32.5 nm and the presence of metallic silver was confirmed by energy dispersive X-ray. Face centred cubic structure with crystal size 33.3 nm was revealed by powder X-ray diffraction. Fourier transform infrared spectroscopy indicated the biomolecules involved in the reduction mainly polyols and phenols present in root extracts were found to be responsible for the synthesis of SNPs. The stability and charge on SNPs were revealed by zeta potential analysis. In addition, on therapeutic forum, the synthesised SNPs elicit antioxidant and antimicrobial activity against Bacillus cereus , Bacillus licheniformis , Escherichia coli , Pseudomonas aeruginosa and Staphylococcus aureus .

Bright-field electron tomography of individual inorganic fullerene-like structures.

PubMed

Bar Sadan, Maya; Wolf, Sharon G; Houben, Lothar

2010-03-01

Nanotubes and fullerene-like nanoparticles of various inorganic layered compounds have been studied extensively in recent years. Their characterisation on the atomic scale has proven essential for progress in synthesis as well as for the theoretical modelling of their physical properties. We show that with electron tomography it is possible to achieve a reliable reconstruction of the 3D structure of nested WS(2) or MoS(2) fullerene-like and nanotube structures with sub-nanometre resolution using electron microscopes that are not aberration-corrected. Model-based simulations were used to identify imaging parameters, under which structural features such as the shell structure can be retained in the tomogram reconstructed from bright-field micrographs. The isolation of a particle out of an agglomerate for the analysis of a single structure and its interconnection with other particles is facilitated through the tomograms. The internal structure of the layers within the particle alongside the shape and content of its internal void are reconstructed. The tomographic reconstruction yields insights regarding the growth process as well as structural defects, such as non-continuous layers, which relate to the lubrication properties.

Designed topology and site-selective metal composition in tetranuclear [MM'...M'M] linear complexes.

PubMed

Barrios, Leoní A; Aguilà, David; Roubeau, Olivier; Gamez, Patrick; Ribas-Ariño, Jordi; Teat, Simon J; Aromí, Guillem

2009-10-26

The ligand 1,3-bis[3-oxo-3-(2-hydroxyphenyl)propionyl]benzene (H(4)L), designed to align transition metals into tetranuclear linear molecules, reacts with M(II) salts (M=Ni, Co, Cu) to yield complexes with the expected [MMMM] topology. The novel complexes [Co(4)L(2)(py)(6)] (2; py=pyridine) and [Na(py)(2)][Cu(4)L(2)(py)(4)](ClO(4)) (3) have been crystallographically characterised. The metal sites in complexes 2 and 3, together with previously characterised [Ni(4)L(2)(py)(6)] (1), favour different coordination geometries. These have been exploited for the deliberate synthesis of the heterometallic complex [Cu(2)Ni(2)L(2)(py)(6)] (4). Complexes 1, 2, 3 and 4 exhibit antiferromagnetic interactions between pairs of metals within each cluster, leading to S=0 spin ground states, except for the latter cluster, which features two quasi-independent S=1/2 moieties within the molecule. Complex 4 gathers the structural and physical conditions, thus allowing it to be considered as prototype of a two-qbit quantum gate.

Dendrimers

NASA Astrophysics Data System (ADS)

Bryant, L. Henry; Bulte, Jeff W. M.

Dendrimers have received an enormous amount of attention in the last ten years and several recent review articles have appeared in the literature that address their potential applications [1-3]. Stoddart et al [1] have stated that: "We are now approaching a time when the study of dendriniers bec omes inextricably linked with many other fields, leaving the comprehensive reviewer of the subject a near-impossible task to fulfil". On that note, this review provides a brief introduction to the chemical principles of dendrimers by highlighting main synthetic strategies and methods for characterisation. p]Dendrimers containing heteroatoms will not be reviewed per se since these have recently been reviewed [4]. The major thrust of this review is the potential applications of dendrimers in such areas as boron neutron capture therapy, as contrast agents in magnetic resonance imaging, as vaccines, as cellular transfection agents and as bioconjugate dendrimers, i.e., in-vitro immunoassays for antigens. The outline used in this review proved to be effective in classifying most published papers about dendrimers, but it must be kept in mind that some articles not only transcended two different classifications, such as synthesis and characterisation, but several classifications such as synthesis, characterisation and at least one potential application covered in this review.

Hydroxyapatite, fluor-hydroxyapatite and fluorapatite produced via the sol-gel method. Optimisation, characterisation and rheology.

PubMed

Tredwin, Christopher J; Young, Anne M; Georgiou, George; Shin, Song-Hee; Kim, Hae-Won; Knowles, Jonathan C

2013-02-01

Currently, most titanium implant coatings are made using hydroxyapatite and a plasma spraying technique. There are however limitations associated with plasma spraying processes including poor adherence, high porosity and cost. An alternative method utilising the sol-gel technique offers many potential advantages but is currently lacking research data for this application. It was the objective of this study to characterise and optimise the production of Hydroxyapatite (HA), fluorhydroxyapatite (FHA) and fluorapatite (FA) using a sol-gel technique and assess the rheological properties of these materials. HA, FHA and FA were synthesised by a sol-gel method. Calcium nitrate and triethylphosphite were used as precursors under an ethanol-water based solution. Different amounts of ammonium fluoride (NH4F) were incorporated for the preparation of the sol-gel derived FHA and FA. Optimisation of the chemistry and subsequent characterisation of the sol-gel derived materials was carried out using X-ray Diffraction (XRD) and Differential Thermal Analysis (DTA). Rheology of the sol-gels was investigated using a viscometer and contact angle measurement. A protocol was established that allowed synthesis of HA, FHA and FA that were at least 99% phase pure. The more fluoride incorporated into the apatite structure; the lower the crystallisation temperature, the smaller the unit cell size (changes in the a-axis), the higher the viscosity and contact angle of the sol-gel derived apatite. A technique has been developed for the production of HA, FHA and FA by the sol-gel technique. Increasing fluoride substitution in the apatite structure alters the potential coating properties. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

The synthesis, characterisation and in vivo study of a bioceramic for potential tissue regeneration applications

PubMed Central

Poinern, Gérrard Eddy Jai; Brundavanam, Ravi Krishna; Thi Le, Xuan; Nicholls, Philip K.; Cake, Martin A.; Fawcett, Derek

2014-01-01

Hydroxyapatite (HAP) is a biocompatible ceramic that is currently used in a number of current biomedical applications. Recently, nanometre scale forms of HAP have attracted considerable interest due to their close similarity to the inorganic mineral component of the bone matrix found in humans. In this study ultrafine nanometre scale HAP powders were prepared via a wet precipitation method under the influence of ultrasonic irradiation. The resulting powders were compacted and sintered to form a series of ceramic pellets with a sponge-like structure with varying density and porosity. The crystalline structure, size and morphology of the powders and the porous ceramic pellets were investigated using advanced characterization techniques. The pellets demonstrated good biocompatibility, including mixed cell colonisation and matrix deposition, in vivo following surgical implantation into sheep M. latissimus dorsi. PMID:25168046

Structural, morphological, and optical study of titania-based nanopowders suitable for photocatalytic applications

NASA Astrophysics Data System (ADS)

Šćepanović, M.; Grujić-Brojčin, M.; Abramović, B.; Golubović, A.

2017-01-01

Systematic investigation of the relationship between structural, morphological, optical and photocatalytic properties of the titania-based nanopowders is presented. A series of pure and doped titania catalysts with various (anatase and brookite) phase compositions have been prepared by sol-gel or hydrothermal route. The crystal structure and composition of the synthesized samples have been extensively characterised by XRD and Raman scattering measurements. The nanopowder morphology has been studied using microscopic methods (SEM, AFM, and STM), whereas the porous structure has been revealed by the analysis of nitrogen sorption data. The optical and electronic properties have been studied by spectroscopic ellipsometry. All investigated properties have been correlated to photocatalytic activity, tested in degradation of the pharmaceutically active substances (such as metoprolol and alprazolam) induced by UVA or visible radiation. Based on this correlation, the physical properties which contribute most to the increase in photocatalytic activity of synthesized nanopowders have been determined, in order to optimize the synthesis conditions which could lead to the maximal efficiency in degradation of particular pollutant.

Synthesis optimisation and characterisation of the organic-inorganic layered materials ZnS(m-xylylenediamine){sub 1/2} and ZnS(p-xylylenediamine){sub 1/2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luberda-Durnaś, K.; Guillén, A. González; Łasocha, W., E-mail: lasocha@chemia.uj.edu.pl

2016-06-15

Hybrid organic-inorganic layered materials of the type ZnS(amine){sub 1/2}, where amine=m-xylylenediamine (MXDA) or p-xylylenediamine (PXDA), were synthesised using a simple solvothermal method. Since the samples crystallised in the form of very fine powder, X-ray powder diffraction techniques were used for structural characterisation. The crystal structure studies, involving direct methods, show that both compounds crystallised in the orthorhombic crystal system, but in different space groups: ZnS(MXDA){sub 1/2} in non-centrosymmetric Ccm2{sub 1}, ZnS(PXDA){sub 1/2} in centrosymmetric Pcab. The obtained materials are built according to similar orders: semiconducting monolayers with the formula ZnS, parallel to the (010) plane, are separated by diamines. Themore » organic and inorganic fragments are connected by covalent bonds between metal atoms of the layers and nitrogen atoms of the amino groups. The optical properties of the hybrid materials differ from those of their bulk counterpart. In both compounds a blue-shift of about 0.8 or 0.9 eV was observed with reference to the bulk phase of ZnS. - Highlights: • New hybrid compounds: ZnS(MXDA){sub 1/2} and ZnS(PXDA){sub 1/2} were obtained. • Hybrids were studied using XRD, TG/DSC, XRK, SEM, UV–vis spectroscopy. • Structures of both materials were solved by powder diffraction methods.« less

Biosynthesis, characterisation and antimicrobial activity of silver nanoparticles using Hibiscus rosa-sinensis petals extracts.

PubMed

Nayak, Debasis; Ashe, Sarbani; Rauta, Pradipta Ranjan; Nayak, Bismita

2015-10-01

Green synthesis of metallic nanoparticles has lured the world from the chemical and physical approaches owing to its rapid, non-hazardous and economic aspect of production mechanism. In this study, silver nanoparticles (AgNPs) were synthesised using petal extracts of Hibiscus rosa-sinensis. The AgNPs displayed characteristic surface plasmon resonance peak at around 421 nm having a mean particle size of 76.25±0.17 nm and carried a charge of -41±0.2 mV. The X-ray diffraction patterns displayed typical peaks of face centred cubic crystalline silver. The surface morphology was characterised by scanning electron microscopy and atomic force microscopy. Fourier transform infrared spectroscopy studies confirmed the surface modifications of the functional groups for the synthesis of AgNPs. Furthermore, the synthesised AgNPs displayed proficient antimicrobial activity against pathogenic strains of Vibrio cholerae, Escherichia coli, Klebsiella pneumoniae and Staphylococcus aureus.

N-benzoylimido complexes of palladium. Synthesis, structural characterisation and structure-reactivity relationship.

PubMed

Besenyei, Gábor; Párkányi, László; Szalontai, Gábor; Holly, Sándor; Pápai, Imre; Keresztury, Gábor; Nagy, Andrea

2004-07-07

Benzoyl azides, ArC(O)N3, 2, (Ar = phenyl or substituted phenyl), react with [Pd2Cl2(dppm)2], 1, [dppm = bis(diphenylphosphino)methane] with the formation of novel [Pd2Cl2(mu-NC(O)Ar)(dppm)2], 3, benzoylnitrene complexes that were structurally characterised by multinuclear magnetic resonance and IR spectroscopy and, in several instances, by single crystal X-ray diffraction. As shown by crystallographic studies, the C2P4Pd2 rings adopt extended twist-boat conformations with methylene groups bending towards the bridging benzoylimido moieties. X-ray diffraction studies have revealed the chiral nature of the imido complexes, the chiral element being the propeller-like C2P4Pd2 ring. Structural data accumulated on complexes 3 such as short C-N distances (1.32 A), elongated C=O bonds (1.30 A) as well as the outstandingly high barrier to internal rotation around the N-C(O) linkage (88.3 kJ mol(-1)) are in line with extensive ppi-ppi interaction between the bridging nitrogen and the carbonyl carbon atoms. Theoretical calculations indicate an electron shift from the dimer towards the apical nitrogen atom, which, in turn, facilitates the donation of electrons towards the carbonyl moiety. To elucidate the structure-reactivity relationship of benzoyl azides towards 1, crystallographic and solution IR spectroscopic studies were carried out on a series of para-substituted benzoyl azides. The reaction obeys the Hammett equation. The large positive value of the reaction constant indicates that the azides act as electrophiles in the reaction studied. The enhanced reactivity of 2-nitrobenzoyl azide has been attributed to a decreased conjugation of the phenyl and carbonyl moieties in this reagent.

fac-Re(CO)3 complexes of 2,6-bis(4-substituted-1,2,3-triazol-1-ylmethyl)pyridine "click" ligands: synthesis, characterisation and photophysical properties.

PubMed

Anderson, Christopher B; Elliott, Anastasia B S; Lewis, James E M; McAdam, C John; Gordon, Keith C; Crowley, James D

2012-12-28

The syntheses of the 4-n-propyl and 4-phenyl substituted fac-Re(CO)(3) complexes of the tridentate "click" ligand (2,6-bis(4-substituted-1,2,3-triazol-1-ylmethyl)pyridine) are described. The complexes were obtained by refluxing methanol solutions of [Re(CO)(5)Cl], AgPF(6) and either the 4-propyl or 4-phenyl substituted ligand for 16 h. The ligands and the two rhenium(I) complexes were characterised by elemental analysis, HR-ESMS, ATR-IR, (1)H and (13)C NMR spectroscopy and the molecular structures of both complexes were confirmed by X-ray crystallography. The electronic structure of the fac-Re(CO)(3) "click" complexes was probed using UV-Vis, Raman and emission spectroscopy, cyclic voltammetry and DFT calculations. Altering the electronic nature of the ligand's substituent, from aromatic to alkyl, had little effect on the absorption/emission maxima and electrochemical properties of the complexes indicating that the 1,2,3-triazole unit may insulate the metal centre from the electronic modification at the ligands' periphery. Both Re(I) complexes were found to be weakly emitting with short excited state lifetimes. The electrochemistry of the complexes is defined by quasi-reversible Re oxidation and irreversible triazole-based ligand reduction processes.

Identification and functional characterisation of genes encoding the omega-3 polyunsaturated fatty acid biosynthetic pathway from the coccolithophore Emiliania huxleyi.

PubMed

Sayanova, Olga; Haslam, Richard P; Calerón, Monica Venegas; López, Noemi Ruiz; Worthy, Charlotte; Rooks, Paul; Allen, Michael J; Napier, Johnathan A

2011-05-01

The Prymnesiophyceae coccolithophore Emiliania huxleyi is one of the most abundant alga in our oceans and therefore plays a central role in marine foodwebs. E. huxleyi is notable for the synthesis and accumulation of the omega-3 long chain polyunsaturated fatty acid docosahexaenoic acid (DHA; 22:6Δ(4,7,10,13,16,19), n-3) which is accumulated in fish oils and known to have health-beneficial properties to humans, preventing cardiovascular disease and related pathologies. Here we describe the identification and functional characterisation of the five E. huxleyi genes which direct the synthesis of docosahexaenoic acid in this alga. Surprisingly, E. huxleyi does not use the conventional Δ6-pathway, instead using the alternative Δ8-desaturation route which has previously only been observed in a few unrelated microorganisms. Given that E. huxleyi accumulates significant levels of the Δ6-desaturated fatty acid stearidonic acid (18:4Δ(6,9,12,15), n-3), we infer that the biosynthesis of DHA is likely to be metabolically compartmentalised from the synthesis of stearidonic acid. Copyright © 2011 Elsevier Ltd. All rights reserved.

Insight into the core-shell structures of Cu-In-S microspheres

NASA Astrophysics Data System (ADS)

Wochnik, Angela S.; Frank, Anna; Heinzl, Christoph; Häusler, Jonas; Schneider, Julian; Hoffmann, Ramona; Matich, Sonja; Scheu, Christina

2013-12-01

In this study we report about the inner and outer structure of CuInS2 microspheres which might be used e.g. in pastes for simple, low-cost solar cell preparation, as well as in electrodes for light-driven water splitting. The microspheres are synthesized via a mild, template-free solvothermal synthesis route and characterised by electron and focused ion beam microscopy, X-ray diffraction, inductively coupled plasma atomic emission and energy dispersive X-ray spectroscopy. The investigations of cross sections prepared by focused ion beam showed that the spheres consist of compact cores and flaky surface structures. Depending on the reaction time, the core possesses a stoichiometric or Cu-rich chemical composition surrounded by an In-rich shell. The flaky surface always comprises a stoichiometric composition in tetragonal chalcopyrite crystal structure, whereas the other areas additionally show minor contributions of CuS, and CuInS2 in hexagonal wurtzite structure. The presence of different phases can be beneficial for future applications since they offer different absorption behaviour in the visible range.

Asymmetric flavone-based liquid crystals: synthesis and properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timmons, Daren J.; Jordan, Abraham J.; Kirchon, Angelo A.

2017-02-01

A series of flavones (n-F) substituted at the 4', and 6 positions was prepared, characterised by NMR (1H,13C), HRMS, and studied for liquid crystal properties. The 4'-alkoxy,6-methoxyflavones (4-F–16-F) exhibit varying ranges of nematic and smectic A phases as evidenced by polarised optical microscopy and differential scanning calorimetry (DSC). As the tail length is increased, the smectic phase becomes more prevalent. Smectic phases for (8-F–16-F) were further analysed by powder X-ray diffraction (XRD), and the rate of structural transformations was explored by combined DSC/XRD studies. Flavonol 6-F–OH was also prepared but no mesogenic behaviour was observed. The molecular structures of 6-Fmore » and 6-F–OH were determined by single-crystal XRD and help to explain the differences in material properties. Additionally, fluorescence and electrochemical studies were conducted on solutions of n-F.« less

Synthesis, structure, and magnetic properties of two 1-D helical coordination polymeric Cu(II) complexes

NASA Astrophysics Data System (ADS)

Bian, He-Dong; Yang, Xiao-E.; Yu, Qing; Chen, Zi-Lu; Liang, Hong; Yan, Shi-Ping; Liao, Dai-Zheng

2008-01-01

Two helical coordination polymeric copper(II) complexes bearing amino acid Schiff bases HL or HL', which are condensed from 2-hydroxy-1-naphthaldehyde with 2-aminobenzoic acid or L-valine, respectively, have been prepared and characterised by X-ray crystallography. In [CuL] n ( 1) the copper(II) atoms are bridged by syn- anti carboxylate groups giving infinite 1-D right-handed helical chains which are further connected by weak C-H⋯Cu interactions to build a 2-D network. While in [CuL'] n ( 2) the carboxylate group acts as a rare monatomic bridge to connect the adjacent copper(II) atoms leading to the formation of a left-handed helical chain. Magnetic susceptibility measurements indicate that 1 exhibits weak ferromagnetic interactions whereas an antiferromagnetic coupling is established for 2. The magnetic behavior can be satisfactorily explained on the basis of the structural data.

A blueprint for the synthesis and characterisation of thin graphene oxide with controlled lateral dimensions for biomedicine

NASA Astrophysics Data System (ADS)

Filipe Rodrigues, Artur; Newman, Leon; Lozano, Neus; Mukherjee, Sourav P.; Fadeel, Bengt; Bussy, Cyrill; Kostarelos, Kostas

2018-07-01

Graphene-based materials (GBMs) have ignited a revolution in material science and technology, with electronic, optical and mechanical properties that are of relevant interest for a wide range of applications. To support the development of these enabling technologies, a global research effort has been invested to assess their hazard and biocompatibility. Different production methods have however generated a diverse collection of GBMs with different physicochemical properties, leading to a variety of biological outcomes that are still not fully understood. To better understand the biological interactions of GBMs with biological systems and allow the design of safer materials, a thorough physicochemical characterisation is therefore highly recommended. The aim of the present work was to produce a blueprint for the synthesis and characterisation of non-pyrogenic graphene oxide (GO) flakes with three different controlled lateral dimensions, which could be further used for either hazard assessment or biomedical proof-of-concept studies. A battery of techniques used to characterise the physicochemical properties of the GO samples included atomic force microscopy, transmission electron microscopy, Fourier-transformed infra-red spectroscopy, x-ray photoelectron spectroscopy and Raman spectroscopy. The combination of these different techniques confirmed that only the lateral dimension varied among the GO materials produced, without significant change in any other of their fundamental physicochemical properties, such as the thickness or surface chemistry. The proposed systematic approach in GO batch production for biology will hopefully contribute to a better understanding of the material properties that govern their interactions with biological systems and offer a blueprint towards standardisation of biologically relevant 2D materials.

Toolboxes for a standardised and systematic study of glycans

PubMed Central

2014-01-01

Background Recent progress in method development for characterising the branched structures of complex carbohydrates has now enabled higher throughput technology. Automation of structure analysis then calls for software development since adding meaning to large data collections in reasonable time requires corresponding bioinformatics methods and tools. Current glycobioinformatics resources do cover information on the structure and function of glycans, their interaction with proteins or their enzymatic synthesis. However, this information is partial, scattered and often difficult to find to for non-glycobiologists. Methods Following our diagnosis of the causes of the slow development of glycobioinformatics, we review the "objective" difficulties encountered in defining adequate formats for representing complex entities and developing efficient analysis software. Results Various solutions already implemented and strategies defined to bridge glycobiology with different fields and integrate the heterogeneous glyco-related information are presented. Conclusions Despite the initial stage of our integrative efforts, this paper highlights the rapid expansion of glycomics, the validity of existing resources and the bright future of glycobioinformatics. PMID:24564482

Morphological, structural and thermal studies of gallium nitride ferrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Indrakanti, Rajani; Rao, V. Brahmaji; Kiran, C. Udaya

2016-05-06

We report the synthesis and Characterization of III-V doped Nano ferrite Ga{sub (2x+2)}N Fe{sub 2(49-x)}O{sub 3} for x=1 and x=5 by Sol-Gel method. The Morphological, structural and Thermal characterisation studies are done by using Transmission Electron Microscopy, Energy Dispersive X-ray Analysis, Selected Area Electron Diffraction, Thermo-Gravimetric Analysis and Differential Thermal Analysis. Using the Sci-Finder software we could not trace any reports related to GaNFe{sub 2}O{sub 3} in the literature. It has been observed from our studies that the particles are in the Cylindrical and the Globular structure. The particle diameter values from the Histograms are in good agreement with themore » XRD values that were communicated by us earlier. The SAED and the EDAX studies reveal the confirmation of the composition and also that the synthesized Ferrite exhibits crystalline nature. The TG-DTA results show that the compound indicates constant sample weight.« less

Crystallisation and crystal forms of carbohydrate derivatives

NASA Astrophysics Data System (ADS)

Lennon, Lorna

This thesis is focused on the synthesis and solid state analysis of carbohydrate derivatives, including many novel compounds. Although the synthetic chemistry surrounding carbohydrates is well established in the literature, the crystal chemistry of carbohydrates is less well studied. Therefore this research aims to improve understanding of the solid state properties of carbohydrate derivatives through gaining more information on their supramolecular bonding. Chapter One focuses on an introduction to the solid state of organic compounds, with a background to crystallisation, including issues that can arise during crystal growth. Chapter Two is based on glucopyranuronate derivatives which are understudied in terms of their solid state forms. This chapter reports on the formation of novel glucuronamides and utilising the functionality of the amide bond for crystallisation. TEMPO oxidation was completed to form glucopyranuronates by oxidation of the primary alcohol groups of glucosides to the carboxylic acid derivatives, to increase functionality for enhanced crystal growth. Chapter Three reports on the synthesis of glucopyranoside derivatives by O-glycosylation reactions and displays crystal structures, including a number of previously unsolved acetate protected and deprotected crystal structures. More complex glycoside derivatives were also researched in an aim to study the resultant supramolecular motifs. Chapter Four contains the synthesis of aryl cellobioside derivatives including the novel crystal structures that were solved for the acetate protected and deprotected compounds. Research was carried out to determine if 1-deoxycellodextrins could act as putative isostructures for cellulose. Our research displays the presence of isostructural references with 1-deoxycellotriose shown to be similar to cellulose III11, 1-deoxycellotetraose correlates with cellulose IV11 and 1-deoxycellopentose shows isostructurality similar to that of cellulose II. Chapter Five contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project and relevant crystallographic information.

Highly ordered mesoporous cobalt oxide nanostructures: synthesis, characterisation, magnetic properties, and applications for electrochemical energy devices.

PubMed

Wang, Guoxiu; Liu, Hao; Horvat, Josip; Wang, Bei; Qiao, Shizhang; Park, Jinsoo; Ahn, Hyojun

2010-09-24

Highly ordered mesoporous Co(3)O(4) nanostructures were prepared using KIT-6 and SBA-15 silica as hard templates. The structures were confirmed by small angle X-ray diffraction, high resolution transmission electron microscopy, and N(2) adsorption-desorption isotherm analysis. Both KIT-6 cubic and SBA-15 hexagonal mesoporous Co(3)O(4) samples exhibited a low Néel temperature and bulk antiferromagnetic coupling due to geometric confinement of antiferromagnetic order within the nanoparticles. Mesoporous Co(3)O(4) electrode materials have demonstrated the high lithium storage capacity of more than 1200 mAh g(-1) with an excellent cycle life. They also exhibited a high specific capacitance of 370 F g(-1) as electrodes in supercapacitors.

Fraxinus paxiana bark mediated photosynthesis of silver nanoparticles and their size modulation using swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Sharma, Hemant; Vendamani, V. S.; Pathak, Anand P.; Tiwari, Archana

2015-12-01

Photosynthesis of silver nanoparticles is presented using bark extracts of Fraxinus paxiana var. sikkimensis. The synthesized nanoparticles are characterised by UV-Vis absorption, photoluminescence, powder X-ray diffraction and scanning and transmission electron microscopy. In addition, the bark samples are irradiated with 100 MeV silver ions and the subsequent structural modifications are analyzed. The swift heavy ion irradiated Fraxinus paxiana var. sikkimensis bark is also used for the synthesis of silver nanoparticles. It is illustrated that the irradiated bark assists in synthesizing smaller nanoparticles of homogenous size distribution as compared to when the pristine bark is used. The newly synthesized silver nanoparticles are also used to demonstrate the antimicrobial activities on Escherichia coli bacteria.

Synthesis and characterisation of co-evaporated tin sulphide thin films

NASA Astrophysics Data System (ADS)

Koteeswara Reddy, N.; Ramesh, K.; Ganesan, R.; Ramakrishna Reddy, K. T.; Gunasekhar, K. R.; Gopal, E. S. R.

2006-04-01

Tin sulphide films were grown at different substrate temperatures by a thermal co-evaporation technique. The crystallinity of the films was evaluated from X-ray diffraction studies. Single-phase SnS films showed a strong (040) orientation with an orthorhombic crystal structure and a grain size of 0.12 μm. The films showed an electrical resistivity of 6.1 Ω cm with an activation energy of 0.26 eV. These films exhibited an optical band gap of 1.37 eV and had a high optical absorption coefficient (>104 cm-1) above the band-gap energy. The results obtained were analysed to evaluate the potentiality of the co-evaporated SnS films as an absorber layer in solar photovoltaic devices.

Co(II) and Cd(II) Complexes Derived from Heterocyclic Schiff-Bases: Synthesis, Structural Characterisation, and Biological Activity

PubMed Central

Ahmed, Riyadh M.; Yousif, Enaam I.; Al-Jeboori, Mohamad J.

2013-01-01

New monomeric cobalt and cadmium complexes with Schiff-bases, namely, N′-[(E)-(3-hydroxy-4-methoxyphenyl)methylidene]furan-2-carbohydrazide (L1) and N′-[(E)-(3-hydroxy-4-methoxyphenyl)methylidene]thiophene-2-carbohydrazide (L2) are reported. Schiff-base ligands L1 and L2 were derived from condensation of 3-hydroxy-4-methoxybenzaldehyde (iso-vanillin) with furan-2-carboxylic acid hydrazide and thiophene-2-carboxylic acid hydrazide, respectively. Complexes of the general formula [M(L)2]Cl2 (where M = Co(II) or Cd(II), L = L1 or L2) have been obtained from the reaction of the corresponding metal chloride with the ligands. The ligands and their metal complexes were characterised by spectroscopic methods (FTIR, UV-Vis, 1H, and 13C NMR spectra), elemental analysis, metal content, magnetic measurement, and conductance. These studies revealed the formation of four-coordinate complexes in which the geometry about metal ion is tetrahedral. Biological activity of the ligands and their metal complexes against gram positive bacterial strain Bacillus (G+) and gram negative bacteria Pseudomonas (G−) revealed that the metal complexes become less resistive to the microbial activities as compared to the free ligands. PMID:24027449

Synthesis and Characterisation of Biocompatible Polymer-Conjugated Magnetic Beads for Enhancement Stability of Urease.

PubMed

Doğaç, Yasemin Ispirli; Teke, Mustafa

2016-04-01

We reported natural polymer-conjugated magnetic featured urease systems for removal of urea effectively. The optimum temperature (20-60 °C), optimum pH (3.0-10.0), kinetic parameters, thermal stability (4-70 °C), pH stability (4.0-9.0), operational stability (0-250 min), reusability (18 times) and storage stability (24 weeks) were studied for characterisation of the urease-encapsulated biocompatible polymer-conjugated magnetic beads. Also, the surface groups and chemical structure of the magnetic beads were determined by using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The all urease-encapsulated magnetic beads protected their stability of 30-45 % relative activity at 70 °C. A significant increase was observed at their pH stability compared with the free urease for both acidic and alkaline medium. Besides this, their repeatability activity were approximately 100 % during 4(th) run. They showed residual activity of 50 % after 16 weeks. The importance of this work is enhancement stability of immobilised urease by biocompatible polymer-conjugated magnetic beads for the industrial application based on removal of urea.

Characterisation and changes in the antioxidant system of chloroplasts and chromoplasts isolated from green and mature pepper fruits.

PubMed

Martí, M C; Camejo, D; Olmos, E; Sandalio, L M; Fernández-García, N; Jiménez, A; Sevilla, F

2009-07-01

Purification and characterisation of pepper (Capsicum annuum L) chloroplasts and chromoplasts isolated from commercial green, red and yellow mature fruits were undertaken. Induction of the synthesis of several antioxidants in organelles isolated from mature fruits was found. The ultrastructure of organelles and the presence and activity of SOD isozymes and enzymes involved in the ASC-GSH cycle, together with the non-enzymatic antioxidant content and some oxidative parameters, were analysed. It was found that lipids, rather than proteins, seem to be a target for oxidation in the chromoplasts. The ascorbate and glutathione contents were elicited during differentiation of chloroplasts into chromoplasts in both red and yellow fruits. The activity of SOD and of components of the ASC-GSH cycle was up-regulated, suggesting that these enzymes may play a role in the protection of plastids and could act as modulators of signal molecules such as O(2) ( -) and H(2)O(2) during fruit maturation. The presence of an Mn-SOD in chromoplasts isolated from yellow pepper fruits was also investigated in terms of structural and antioxidant differences between the two cultivars.

Biomimetic routes to nanoscale-toughened oxide ceramics

NASA Astrophysics Data System (ADS)

Deschaume, Olivier

In this work, a novel anion exchange technique has been developed and optimised in order to prepare extra-pure, hydroxide-free solutions of aluminium polyoxocations (A113 and A130) as well as for the preparation of nanosized, highly monodisperse aluminium hydroxide particles in the particle size range 20-200nm. In order for the evolution and composition of the resulting systems to be monitored, an array of characterisation techniques including 27A1 NMR, dynamic light scattering, po-tentiometry, conductometry and UV-Vis spectroscopy, have been implemented and complemented with successful data treatment strategies. The quantitative data obtained indicates that the static anion exchange method is a soft, environmentally friendly, low-cost, energy-saving and convenient procedure for the preparation of Al- containing model systems. The A1 species obtained can be used for high-precision model studies on A1 speciation, and serve as nanosize precursors to a variety of Al-containing materials. The use of these pure A1 precursors has a clear advantage in materials synthesis arising from an improved understanding and better control of A1 speciation. In a second development of the project, the model systems have been used in a nanotectonic approach to biomimetic materials synthesis, with possible applications to the optimisation of Al-containing materials such as ceramics or composite films. Bearing this aim in mind, the interactions of the prepared aluminium species with the model protein BSA and a bioelastomer, elastin, were monitored and the resulting composite materials characterised. The methodology developed for the synthesis and characterisation of pure A1 species and A1 species/biomolecule systems is a robust base for further studies spanning research fields such as Chemistry, Biology or Environmental sciences, and possess a large potential for application to industrial products and processes.

Characterisation of aqueous waste produced during the clandestine production of amphetamine following the Leuckart route utilising solid-phase extraction gas chromatography-mass spectrometry and capillary electrophoresis with contactless conductivity detection.

PubMed

Hauser, Frank M; Hulshof, Janneke W; Rößler, Thorsten; Zimmermann, Ralf; Pütz, Michael

2018-04-18

Chemical waste from the clandestine production of amphetamine is of forensic and environmental importance due to its illegal nature which often leads to dumping into the environment. In this study, 27 aqueous amphetamine waste samples from controlled Leuckart reactions performed in Germany, the Netherlands, and Poland were characterised to increase knowledge about the chemical composition and physicochemical characteristics of such waste. Aqueous waste samples from different reaction steps were analysed to determine characteristic patterns which could be used for classification. Conductivity, pH, density, ionic load, and organic compounds were determined using different analytical methods. Conductivity values ranged from 1 to over 200 mS/cm, pH values from 0 to 14, and densities from 1.0 to 1.3 g/cm 3 . A capillary electrophoresis method with contactless conductivity detection (CE-C 4 D) was developed and validated to quantify chloride, sulphate, formate, ammonium, and sodium ions which were the most abundant ions in the investigated waste samples. A solid-phase extraction sample preparation was used prior to gas chromatography-mass spectrometry analysis to determine the organic compounds. Using the characterisation data of the known samples, it was possible to assign 16 seized clandestine waste samples from an amphetamine production to the corresponding synthesis step. The data also allowed us to draw conclusions about the synthesis procedure and used chemicals. The presented data and methods could support forensic investigations by showing the probative value of synthesis waste when investigating the illegal production of amphetamine. It can also act as starting point to develop new approaches to tackle the problem of clandestine waste dumping. Copyright © 2018 John Wiley & Sons, Ltd.

Synthesis, characterisation and optical studies of new tetraethyl- rubyrin-graphene oxide covalent adducts

NASA Astrophysics Data System (ADS)

Garg, Kavita; Shanmugam, Ramakrishanan; Ramamurthy, Praveen C.

2018-02-01

Tetrathia-rubyrin and graphene oxide (GO) covalent adduct was synthesized, characterised and optical properties were studied. GO-Rubyrin adducts showed fluorescence quenching of rubyrin due to electron or energy transfer from rubyrin to graphene oxide, which also reflected in UV-vis absorbance spectroscopy. The non-linear optical responses were measured through Z scan technique in nano-second regime. The enhanced optical non-linearity was observed after attachment of GO with rubyrin, can be ascribed to the photo-induced electron or energy transfer from the electron rich rubyrin moiety to the electron deficient GO.

Characterisation of Nd2O3 thick gate dielectric for silicon

NASA Astrophysics Data System (ADS)

Dakhel, A. A.

2004-03-01

Thin neodymium films were prepared by the reactive synthesis method on Si (P) substrates to form MOS devices. The oxide films were characterised by UV absorption spectroscopy, X-ray fluorescence (EDXRF) and X-ray diffraction (XRD). The ac conductance and capacitance of the devices were studied as a function of frequency in the range 100 Hz-100 kHz, of temperature in the range 293-473 K and of gate voltage. It was proved that a suitable formalism to explain the frequency dependence of the ac conductivity and capacitance of the insulator is controlled by a universal power law based on the relaxation processes of the hopping or tunnelling of the current carriers between equilibrium sites. The temperature dependence of the ac conductance at the accumulation state shows a small activation energy of about 0.07 eV for a MOS device with amorphous neodymium oxide. The temperature dependence of the accumulation capacitance for a MOS structure with crystalline neodymium oxide shows a maximum at about 390 K; such a maximum was not observed for the structure with amorphous neodymium oxide. The method of capacitance-gate voltage (C-Vg) measurements was used to investigate the effect of annealing in air and in vacuum on the surface density of states (Nss) at the insulator/semiconductor (I/S) interface. It was concluded that the density of surface states in the mid-gap increases by about five times while the density of the trapped charges in the oxide layer decreases by about eight times when the oxide crystallises into a polycrystalline structure.

Thalassaemia.

PubMed

Higgs, Douglas R; Engel, James Douglas; Stamatoyannopoulos, George

2012-01-28

Thalassaemia is one of the most common genetic diseases worldwide, with at least 60,000 severely affected individuals born every year. Individuals originating from tropical and subtropical regions are most at risk. Disorders of haemoglobin synthesis (thalassaemia) and structure (eg, sickle-cell disease) were among the first molecular diseases to be identified, and have been investigated and characterised in detail over the past 40 years. Nevertheless, treatment of thalassaemia is still largely dependent on supportive care with blood transfusion and iron chelation. Since 1978, scientists and clinicians in this specialty have met regularly in an international effort to improve the management of thalassaemia, with the aim of increasing the expression of unaffected fetal genes to improve the deficiency in adult β-globin synthesis. In this Seminar we discuss important advances in the understanding of the molecular and cellular basis of normal and abnormal expression of globin genes. We will summarise new approaches to the development of tailored pharmacological agents to alter regulation of globin genes, the first trial of gene therapy for thalassaemia, and future prospects of cell therapy. Copyright © 2012 Elsevier Ltd. All rights reserved.

Comparison of Conventional and Microwave-assisted Synthesis of Benzimidazole Derivative from Citronellal in Kaffir lime oil (Citrus hystrix DC.)

NASA Astrophysics Data System (ADS)

Warsito, W.; Noorhamdani, A. S.; Suratmo; Dwi Sapri, R.; Alkaroma, D.; Azhar, A. Z.

2018-04-01

Simple method has been used for the synthesis of benzimidazole derivative from citronellal in kaffir lime oil under microwave irradiation. These compounds were synthesized also by conventional heating for comparison. In addtion, microwave-assited synthesis was also compared between using to dichloromethane and methanol solvents with variation of reaction time for 30 to 70 minutes and 4 to 12 h for conventional heating. The 2-citronellyl benzimidazole compound synthesized were characterised by FT-IR, GC-MS, 1H and 13C NMR spectroscopy. Comparison between conventional and microwave-assisted synthesis was done by comparing between correlation of reaction time and percentage yield. The time optimum of microwave-assisted and conventional synthesis using dichloromethane solvent respectively at 60 minutes (yield 19.23%) and 8 hours (yield 11.54%). In addition, microwave-assited synthesis increasing 157.81 times compared by conventional heating. While using methanol solvent tends to increase linearly however the percentage of yield only 0.77 times of synthesis using dichloromethane solvent.

Sol-gel synthesis and characterisation of nano-scale hydroxyapatite

NASA Astrophysics Data System (ADS)

Bilton, M.; Brown, A. P.; Milne, S. J.

2010-07-01

Hydroxyapatite (HAp) forms the main mineral component of bone and teeth. This naturally occurring HAp is in the form of nano-metre sized crystallites of Ca10(PO4)6(OH)2 that contain a number of cation and anion impurities, for example CO32-, F-, Na+, Mg2+ and Sr2+. Synthetic nano-sized HAp particles exhibit favourable biocompatibility and bioactivity and in order to better match the composition to natural HAp there is great interest in producing a range of chemically modified powders. In this study, two HAp powders have been synthesised via a water-based low-temperature sol-gel method and a third, commercial powder from Sigma-Aldrich have been analysed. Subsequent powder calcination has been carried out within the temperature range of 500-700 °C and the products characterised by bulk chemical analysis, X-ray diffraction and electron microscopy. Energy dispersive X-ray spectroscopy (EDX) in the TEM has been used to assess the composition of individual HAp particles. In order to do this accurately it is first necessary to account for the sensitivity of the HAp structure and composition to irradiation by the high energy electron beam of the TEM. This was done by monitoring the estimated Ca/P ratio derived from TEM-EDX of stoichiometric HAp under increasing levels of electron fluence. A fluence threshold (at a given beam energy) was established below which the measured Ca/P ratio can be considered to be stable. Subsequent elemental analysis at or below this threshold has enabled the variation in composition between particles both within and between synthesis batches to be accurately assessed. Compositional variability between particles is also evident, even in the commercial powder, but is far greater in the powders prepared by the sol-gel method.

Lysozyme encapsulated gold nanoclusters: effects of cluster synthesis on natural protein characteristics.

PubMed

Russell, B A; Jachimska, B; Komorek, P; Mulheran, P A; Chen, Y

2017-03-08

The study of gold nanoclusters (AuNCs) has seen much interest in recent history due to their unique fluorescence properties and environmentally friendly synthesis method using proteins as a growth scaffold. The differences in the physicochemical properties of lysozyme encapsulated AuNCs in comparison to natural lysozyme are characterised in order to determine the effects AuNCs have on natural protein behaviour. The hydrodynamic radius (dynamic light scattering), light absorbance (UV-Vis), electrophoretic mobility, relative density, dynamic viscosity, adsorption (quartz crystal microbalance) and circular dichroism (CD) characteristics of the molecules were studied. It was found that lysozyme forms small dimer/trimer aggregates upon the synthesis of AuNCs within the protein. The diameter of Ly-AuNCs was found to be 8.0 nm across a pH range of 2-11 indicating dimer formation, but larger aggregates with diameters >20 nm were formed between pH 3 and 6. The formation of larger aggregates limits the use of Ly-AuNCs as a fluorescent probe in this pH range. A large shift in the protein's isoelectric point was also observed, shifting from 11.0 to 4.0 upon AuNC synthesis. This resulted in major changes to the adsorption characteristics of lysozyme, observed using a QCM. A monolayer of 8 nm was seen for Ly-AuNCs at pH 4, offering further evidence that the proteins form small aggregates, unlike the natural monomer form of lysozyme. The adsorption of Ly-AuNCs was seen to decrease as pH was increased; this is in major contrast to the lysozyme adsorption behaviour. A decrease in the α-helix content was observed from 25% in natural lysozyme to 1% in Ly-AuNCs. This coincided with an increase in the β-sheet content after AuNC synthesis indicating that the natural structure of lysozyme was lost. The formation of protein dimers, the change in the protein surface charge from positive to negative, and secondary structure alteration caused by the AuNC synthesis must be considered before attempting to utilise Ly-AuNCs as in vivo probes.

Investigating the internal structure of galaxies and clusters through strong gravitational lensing

NASA Astrophysics Data System (ADS)

Jigish Gandhi, Pratik; Grillo, Claudio; Bonamigo, Mario

2018-01-01

Gravitational lensing studies have radically improved our understanding of the internal structure of galaxies and cluster-scale systems. In particular, the combination of strong lensing and stellar dynamics or stellar population synthesis models have made it possible to characterize numerous fundamental properties of the galaxies as well as dark matter halos and subhalos with unprecedented robustness and accuracy. Here we demonstrate the usefulness and accuracy of strong lensing as a probe for characterising the properties of cluster members as well as dark matter halos, to show that such characterisation carried out via lensing analyses alone is as viable as those carried out through a combination of spectroscopy and lensing analyses.Our study uses focuses on the early-type galaxy cluster MACS J1149.5+2223 at redshift 0.54 in the Hubble Frontier Fields (HFF) program, where the first magnified and spatially resolved multiple images of supernova (SN) “Refsdal” and its late-type host galaxy at redshift 1.489 were detected. The Refsdal system is unique in being the first ever multiply-imaged supernova, with it’s first four images appearing in an Einstein Cross configuration around one of the cluster members in 2015. In our lensing analyses we use HST data of the multiply-imaged SN Refsdal to constrain the dynamical masses, velocity dispersions, and virial radii of individual galaxies and dark matter halos in the MACS J1149.5+2223 cluster. For our lensing models we select a sample of 300 cluster members within approximately 500 kpc from the BCG, and a set of reliable multiple images associated with 18 distinct knots in the SN host spiral galaxy, as well as multiple images of the supernova itself. Our results provide accurate measurements of the masses, velocity dispersions, and radii of the cluster’s dark matter halo as well as three chosen members galaxies, in strong agreement with those obtained by Grillo et al 2015, demonstrating the usefulness of strong lensing in characterising the properties of cluster-scale systems.

Cyclic tetraureas with variable flexibility--synthesis, crystal structures and properties.

PubMed

Meshcheryakov, Denys; Arnaud-Neu, Françoise; Böhmer, Volker; Bolte, Michael; Cavaleri, Julien; Hubscher-Bruder, Véronique; Thondorf, Iris; Werner, Sabine

2008-09-21

Macrocyclic molecules containing several amide or urea functions may serve as anion receptors. We describe the synthesis of 32-membered macrocycles, in which four rigid xanthene units (X) and/or diphenyl ether units (D) as flexible analogues are linked via urea groups. All six possible combinations of these units (XXXX, XXXD, XXDD, XDXD, XDDD and DDDD) were synthesized and two examples were characterised by single-crystal X-ray analyses (DDDD and two structures for XXXD). Both macrocycles showed distinct differences in their overall conformation and consequently in their hydrogen-bonding pattern. Hydrogen-bonded solvent molecules are found for both compounds and intramolecular hydrogen bonds for the two structures of XXXD, but surprisingly no direct intermolecular hydrogen bonds between the macrocyclic tetraurea molecules. The interaction with various anions was studied by (1)H NMR spectroscopy. Stability constants for all tetramers were determined by UV spectroscopy for complexes with chloride, bromide, acetate and dihydrogenphosphate in acetonitrile-THF (3:1). The strongest binding was found for XXXD and acetate (log beta = 7.4 +/- 0.2), the weakest for XXXX and acetate (log beta = 5.1 +/- 0.5). MD simulations in chloroform and acetonitrile boxes show that all molecules except DDDD adopt very similar conformations characterized by an up-down-up-down arrangement of the spacer groups. Clustered solvation shells of acetonitrile molecules around XXXX and DDDD suggest their preorganization for spherical/planar and tetrahedral/bidentate anions, respectively, which in turn was corroborated by simulation of the corresponding complexes with chloride and dihydrogenphosphate.

Synthesis and characterisation of PuPO4 - a potential analytical standard for EPMA actinide quantification

NASA Astrophysics Data System (ADS)

Wright, K. E.; Popa, K.; Pöml, P.

2018-01-01

Transmutation nuclear fuels contain weight percentage quantities of actinide elements, including Pu, Am and Np. Because of the complex spectra presented by actinide elements using electron probe microanalysis (EPMA), it is necessary to have relatively pure actinide element standards to facilitate overlap correction and accurate quantitation. Synthesis of actinide oxide standards is complicated by their multiple oxidation states, which can result in inhomogeneous standards or standards that are not stable at atmospheric conditions. Synthesis of PuP4 results in a specimen that exhibits stable oxidation-reduction chemistry and is sufficiently homogenous to serve as an EPMA standard. This approach shows promise as a method for producing viable actinide standards for microanalysis.

Synthesis and properties of hydroxy acrylic resin with high solid content

NASA Astrophysics Data System (ADS)

Yu, Zhen; Hu, Mingguang; Cui, Han; Xiao, Jijun

2017-10-01

Manufacturers of automotive repair finishes are tending to reduce more and more the level of volatile organic compounds in their paints in order to comply with increasingly strict environmental legislation. A high solid hydroxy acrylic resin was synthesised using CARDURA E10 and a type of hydroxyacrylic acid resin, its' acid value, hydroxylvalue, viscosity, structure, morphology was measured and film-forming properties after curing were characterised. The results show that the addition of CARDURA E10 in the copolymer composition significantly reduced the viscosity of the polymer system, improved the solid content of the resin and the physical properties of the coating. The hydroxyl acrylate resin with solid content of 90% and excellent comprehensive performance were successfully prepared by controlling the initiator dosage, polymerization temperature and monomer ratio.

Studies toward the synthesis of linear triazole linked pseudo oligosaccharides and the use of ferrocene as analytical probe.

PubMed

Schmidt, Magnus S; Götz, Kathrin H; Koch, Wolfgang; Grimm, Tanja; Ringwald, Markus

2016-04-29

Three different building blocks have been synthesised and used for the synthesis of linear triazole linked pseudo oligosaccharides with copper(I)-catalysed cycloaddition (CuAAC). Ethynylferrocene has been used as analytical probe to improve the UV/Vis properties and HPLC methods have been used and optimised for the analysis of the pseudo oligosaccharides. The smallest ones have been isolated and characterised by analytical HPLC, NMR, ESI-MS and elemental analysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tungsten phosphanylarylthiolato complexes [W{PhP(2-SC6H4)2-kappa3S,S',P} 2] and [W{P(2-SC6H4)3-kappa4S,S',S",P}2]: synthesis, structures and redox chemistry.

PubMed

Hildebrand, Alexandra; Lönnecke, Peter; Silaghi-Dumitrescu, Luminita; Hey-Hawkins, Evamarie

2008-09-14

PhP(2-SHC6H4)2 (PS2H2) reacts with WCl6 with reduction of tungsten to give the air-sensitive tungsten(IV) complex [W{PhP(2-SC6H4)2-kappa(3)S,S',P}2] (1). 1 is oxidised in air to [WO{PhPO(2-SC6H4)2-kappa(3)S,S',O}{PhP(2-SC6H4)2-kappa(3)S,S',P}] (2). The attempted synthesis of 2 by reaction of 1 with iodosobenzene as oxidising agent was unsuccessful. [W{P(2-SC6H4)3-kappa(4)S,S',S",P}2] (3) was formed in the reaction of P(2-SHC6H4)3 (PS3H3) with WCl6. The W(VI) complex 3 contains two PS3(3-) ligands, each coordinated in a tetradentate fashion resulting in a tungsten coordination number of eight. The reaction of 3 with AgBF4 yields the dinuclear tungsten complex [W2{P(2-SC6H4)3-kappa(4)S,S',S",P}3]BF4 (4). Complexes 1-4 were characterised by spectral methods and X-ray structure determination.

Modified microwave method for the synthesis of visible light-responsive TiO2/MWCNTs nanocatalysts

PubMed Central

2013-01-01

Recently, TiO2/multi-walled carbon nanotube (MWCNT) hybrid nanocatalysts have been a subject of high interest due to their excellent structures, large surface areas and peculiar optical properties, which enhance their photocatalytic performance. In this work, a modified microwave technique was used to rapidly synthesise a TiO2/MWCNT nanocatalyst with a large surface area. X-ray powder diffraction, field-emission scanning electron microscopy, transmission electron microscopy and Brunauer-Emmett-Teller measurements were used to characterise the structure, morphology and the surface area of the sample. The photocatalytic activity of the hybrid nanocatalysts was evaluated through a comparison of the degradation of methylene blue dye under irradiation with ultraviolet and visible light. The results showed that the TiO2/MWCNT hybrid nanocatalysts degraded 34.9% of the methylene blue (MB) under irradiation with ultraviolet light, whereas 96.3% of the MB was degraded under irradiation with visible light. PMID:23919496

Structure and biocatalytic scope of thermophilic flavin-dependent halogenase and flavin reductase enzymes.

PubMed

Menon, Binuraj R K; Latham, Jonathan; Dunstan, Mark S; Brandenburger, Eileen; Klemstein, Ulrike; Leys, David; Karthikeyan, Chinnan; Greaney, Michael F; Shepherd, Sarah A; Micklefield, Jason

2016-10-04

Flavin-dependent halogenase (Fl-Hal) enzymes have been shown to halogenate a range of synthetic as well as natural aromatic compounds. The exquisite regioselectively of Fl-Hal enzymes can provide halogenated building blocks which are inaccessible using standard halogenation chemistries. Consequently, Fl-Hal are potentially useful biocatalysts for the chemoenzymatic synthesis of pharmaceuticals and other valuable products, which are derived from haloaromatic precursors. However, the application of Fl-Hal enzymes, in vitro, has been hampered by their poor catalytic activity and lack of stability. To overcome these issues, we identified a thermophilic tryptophan halogenase (Th-Hal), which has significantly improved catalytic activity and stability, compared with other Fl-Hal characterised to date. When used in combination with a thermostable flavin reductase, Th-Hal can efficiently halogenate a number of aromatic substrates. X-ray crystal structures of Th-Hal, and the reductase partner (Th-Fre), provide insights into the factors that contribute to enzyme stability, which could guide the discovery and engineering of more robust and productive halogenase biocatalysts.

Preparation and characterisation of a novel hydrogel based on Auricularia polytricha β-glucan and its bio-release property for vitamin B12 delivery.

PubMed

Zhu, Kai; Chen, Xiaoyuan; Yu, Da; He, Yue; Song, Guanglei

2018-05-01

This study investigates a novel hydrogel synthesis method and its bio-release property. This hydrogel, with a three-dimensional network structure based on Auricularia polytricha β-glucan, was characterised by means of Fourier transform infrared spectroscopy, 1 H NMR and scanning electron microscopy. Vitamin B 12 (VB 12 , cobalamin) as a hydrophilic functional food component was entrapped into these hydrogels. The in vitro release profile of VB 12 was established in simulated gastric fluid (SGF) and simulated intestinal fluid (SIF). The results showed that the hydrogel had medium pore size from 30 to 300 µm, and the swelling ratio increased with the degree of substitution. The hydrogel demonstrated good stability in SGF and bio-release capability in SIF for VB 12 . The accumulated release rate is about 80% in SIF and below 20% in SGF, which indicated the significant different release property in stomach and intestine. The Auricularia polytricha β-glucan-based hydrogel has a good swelling ratio, pepsin stability and pancrelipase-catalysed biodegradation property. The bio-release rate is significantly different in SIF and SGF, which indicated that this hydrogel could be a good intestinal target carrier of VB 12 . © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Characterisation of a Zn / Ni Plating Bath

DTIC Science & Technology

2009-09-03

accelerated corrosion in the first stages which is then slowed down by its own product of corrosion, Zn(OH)212. Zinc hydroxide dehydrates in time to form ZnO ... Electrochemistry , 1991, 21, 642 [5] – Alfantasi, A.M., A study on the synthesis, characterization ans properties of pulse-plated ultrafine- grained Zn-Ni alloy

Modelling, analysis and validation of microwave techniques for the characterisation of metallic nanoparticles

NASA Astrophysics Data System (ADS)

Sulaimalebbe, Aslam

In the last decade, the study of nanoparticle (NP) systems has become a large and interesting research area due to their novel properties and functionalities, which are different from those of the bulk materials, and also their potential applications in different fields. It is vital to understand the behaviour and properties of nano-materials aiming at implementing nanotechnology, controlling their behaviour and designing new material systems with superior performance. Physical characterisation of NPs falls into two main categories, property and structure analysis, where the properties of the NPs cannot be studied without the knowledge of size and structure. The direct measurement of the electrical properties of metal NPs presents a key challenge and necessitates the use of innovative experimental techniques. There have been numerous reports of two/four point resistance measurements of NPs films and also electrical conductivity of NPs films using the interdigitated microarray (IDA) electrode. However, using microwave techniques such as open ended coaxial probe (OCP) and microwave dielectric resonator (DR) for electrical characterisation of metallic NPs are much more accurate and effective compared to other traditional techniques. This is because they are inexpensive, convenient, non-destructive, contactless, hazardless (i.e. at low power) and require no special sample preparation. This research is the first attempt to determine the microwave properties of Pt and Au NP films, which were appealing materials for nano-scale electronics, using the aforementioned microwave techniques. The ease of synthesis, relatively cheap, unique catalytic activities and control over the size and the shape were the main considerations in choosing Pt and Au NPs for the present study. The initial phase of this research was to implement and validate the aperture admittance model for the OCP measurement through experiments and 3D full wave simulation using the commercially available Ansoft High Frequency Structure Simulator (HFSS), followed by the electrical characterisation of synthesised Pt NP films using the novel miniature fabricated OCP technique. The results obtained from this technique provided the inspiration to synthesise and evaluate the microwave properties of Au NPs. The findings from this technique provided the motivation to characterise both the Pt and Au NP films using the DR technique. Unlike the OCP technique, the DR method is highly sensitive but the achievable measurement accuracy is limited since this technique does not have broadband frequency capability like the OCP method. The results obtained from the DR technique show a good agreement with the theoretical prediction. In the last phase of this research, a further validation of the aperture admittance models on different types OCP (i.e. RG-405 and RG-402 cables and SMA connector) have been carried out on the developed 3D full wave models using HFSS software, followed by the development of universal models for the aforementioned OCPs based on the same 3D full wave models.

The synthesis and characterisation of MDMA derived from a catalytic oxidation of material isolated from black pepper reveals potential route specific impurities.

PubMed

Plummer, Christopher M; Breadon, Thomas W; Pearson, James R; Jones, Oliver A H

2016-05-01

This work examines the chemical synthesis of 3,4-methylenedioxy-N-methylamphetamine (MDMA) from piperonal prepared via a catalytic ruthenium tetroxide oxidation of piperine extracted from black pepper. A variety of oxidation conditions were experimented with including different solvent systems and co-oxidants. A sample of prepared piperonal was successfully converted into MDMA via 3,4-methylenedioxyphenyl-2-nitropropene (MDP2NP) and 3,4-methylenedioxyphenyl-2-propanone (MDP2P) and the impurities within each product characterised by GC-MS to give a contaminant profile of the synthetic pathway. Interestingly, it was discovered that a chlorinated analogue of piperonal (6-chloropiperonal) was created during the oxidation process by an as yet unknown mechanism. This impurity reacted alongside piperonal to give chlorinated analogues of each precursor, ultimately yielding 2-chloro-4,5-methylenedioxymethamphetamine (6-Cl-MDMA) as an impurity within the MDMA sample. The methodology developed is a simple way to synthesise a substantial amount of precursor material with easy to obtain reagents. The results also show that chlorinated MDMA analogues, previously thought to be deliberately included adulterants, may in fact be route specific impurities with potential application in determining the origin and synthesis method of seized illicit drugs. Copyright © 2016 The Chartered Society of Forensic Sciences. Published by Elsevier Ireland Ltd. All rights reserved.

Structure and properties of ZrB2, ZrSiB and ZrAlSiB cathode materials and coatings obtained by their magnetron sputtering

NASA Astrophysics Data System (ADS)

Iatsyuk, I. V.; Lemesheva, M. V.; Kiryukhantsev-Korneev, Ph V.; Levashov, E. A.

2018-04-01

The ceramic ZrB2, ZrSiB, and ZrAlSiB cathodes were manufactured by means of self-propagating high-temperature synthesis (SHS). The parameters of SHS process including dependence of the combustion temperature and rate on the initial temperature of the reaction mixtures, as well as values of effective activation energy were estimated. Cathodes were subjected to the magnetron sputtering in the argon atmosphere. The structure and properties of cathodes and coatings were studied by means of X-ray diffraction, scanning electron microscopy, energy-dispersive and glow discharge optical emission spectroscopy. Bulk ceramic samples and coatings were characterised in terms of their hardness, elastic modulus, elastic recovery, density, and residual porosity. Results obtained shows that cathodes posses homogeneous structure with low porosity level in range 2-6% and hardness between 10 and 17 GPa. Coatings demonstrate dense defect-free structure and contain nanocrystallites of h-ZrB2 phase. The grain size and hardness decrease from 8 down to 2 nm and from 37 down to 16 GPa with the addition of the silicon and aluminum dopes.

Synthesis, spectral and thermal studies of pyridyl adducts of Zn(II) and Cd(II) dithiocarbamates, and their use as single source precursors for ZnS and CdS nanoparticles.

PubMed

Onwudiwe, Damian C; Strydom, Christien A; Oluwafemi, Oluwatobi S; Hosten, Eric; Jordaan, Anine

2014-06-21

The synthesis, spectroscopic characterisation, and thermal studies of pyridyl adducts of Zn(II) and Cd(II) complexes of N-ethyl-N-phenyl dithiocarbamate, represented as [ZnL2py] and [CdL2py2], are reported. Single-crystal X-ray structural analysis of the Zn compound showed that it is five-coordinate with four sulphurs from dithiocarbamate and one nitrogen from pyridine in a distorted square pyramidal geometry. The thermogravimetric studies indicate that the zinc and cadmium compounds undergo fast weight loss, and the temperature at maximum rate of decomposition is at 277 °C and 265 °C respectively, to give the metal (Zn or Cd) sulphide residues. These compounds were used as single molecule precursors to produce nanocrystalline MS (M = Zn, Cd) after thermolysis in hexadecylamine. The morphological and optical properties of the resulting MS nanocrystallites were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV-Vis absorption and photoluminescence (PL) spectroscopy, and powdered X-ray diffraction (XRD). By varying the growth time, the temporal evolution of the optical properties and morphology of the nanocrystals were investigated.

Synthesis and toxicity test of magnetic nanoparticle via biocompatible microemulsion system as template for application in targeted drug delivery

NASA Astrophysics Data System (ADS)

Kader, Razinah Abdul; Rose, Laili Che; Suhaimi, Hamdan; Manickam, Mariessa Soosai

2017-09-01

This work reports the preparation of magnetic nanoparticles (FeNPs) using biocompatible W/O microemulsion for biomedical applications. W/O microemulsion was formed using decane as oil phase, water, tween 80 as non-ionic surfactant and hexanol as organic solvent. The synthesized FeNPs were characterised by using Fourier Transform Infrared Resonance Spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The FTIR showed that Fe-O bond exist on 581cm-1 having strong magnetic strength whereas SEM showed the morphology surface of magnetic nanoparticles (FeNPs). Furthermore, analysis of XRD pattern magnetic nanoparticles (FeNPs) reveals a cubic iron oxide phase with good crystallize structure. Furthermore, toxicity test on human liver cells proved that it is 70% safe on human and proved to be a safety nanomedicine.

Identification and characterization of potential impurities of donepezil.

PubMed

Krishna Reddy, K V S R; Moses Babu, J; Kumar, P Anil; Chandrashekar, E R R; Mathad, Vijayavitthal T; Eswaraiah, S; Reddy, M Satyanarayana; Vyas, K

2004-09-03

Five unknown impurities ranging from 0.05 to 0.2% in donepezil were detected by a simple isocratic reversed-phase high performance liquid chromatography (HPLC). These impurities were isolated from crude sample of donepezil using isocratic reversed-phase preparative high performance liquid chromatography. Based on the spectral data (IR, NMR and MS), the structures of these impurities were characterised as 5,6-dimethoxy-2-(4-pyridylmethyl)-1-indanone (impurity I), 4-(5,6-dimethoxy-2,3-dihydro-1H-2-indenylmethyl) piperidine (impurity II), 2-(1-benzyl-4-piperdylmethyl)-5,6-dimethoxy-1-indanol (impurity III) 1-benzyl-4(5,6-dimethoxy-2,3-dihydro-1H-2-indenylmethyl) piperidine (impurity IV) and 1,1-dibenzyl-4(5,6-dimethoxy-1-oxo-2,3-dihydro-2H-2-indenylmethyl)hexahydropyridinium bromide (impurity V). The synthesis of these impurities and their formation was discussed.

Synthesis and antioxidant properties of a new lipophilic ascorbic acid analogue.

PubMed

Cotelle, Philippe; Cotelle, Nicole; Teissier, Elisabeth; Vezin, Hervé

2003-03-20

4-(4-Hydroxyphenyl)-5-(4-hydroxyphenylmethyl)-2-hydroxyfurane-2-one 1 was prepared by an acidic dimerisation of 4-hydroxyphenylpyruvic acid and some of its antioxidant and spectroscopic properties have been measured and compared to that of ascorbic acid. 1 is as good an antioxidant as ascorbic acid in the DPPH (2,2-diphenyl-1-picryl hydrazyl radical) test and the inhibition of hydroxyl radical and a powerful inhibitor of the Cu(2+) or AAPH (2,2'-azobis-(2-amidinopropane) dihydrochloride) induced oxidation of human LDL. 1 gives a stable radical characterised by its ESR spectrum similarly to ascorbic acid but in lower concentration and with a different reactivity towards nitroxides. Theoretical calculations allow us to propose the structure for the radical formed from 1, to explain its lower stability than ascorbyl radical and to evaluate the lipophilicity of 1.

Novel unsymmetrical P/O substituted ferrocene ligands and the first structurally characterised hydroxyferrocene derivative.

PubMed

Atkinson, Robert C J; Gibson, Vernon C; Long, Nicholas J; White, Andrew J P; Williams, David J

2004-06-21

Two new unsymmetrical 1'-substituted hydroxyferrocene ligands featuring either phosphine or phosphine oxide substituents have been synthesised and the phosphine oxide derivative has been structurally characterised. A nickel complex of the hydroxyl/phosphine ligand has been formed, along with preliminary evaluation of the complex for catalysis of ethylene polymerisation.

Isoflavonoids of the leguminosae.

PubMed

Veitch, Nigel C

2013-07-01

This account describes 275 new isoflavonoids published between 2008 and 2011 as constituents of the Leguminosae, commenting on their source, identification, biological activity, synthesis, and ecological or chemosystematic significance. Applications of hyphenated analytical techniques to the characterisation of Leguminosae isoflavonoids are also reviewed, together with advances in biosynthetic studies. A checklist of new compounds by species is given, and 226 references are cited.

The State of Agricultural Extension: An Overview and New Caveats for the Future

ERIC Educational Resources Information Center

Benson, Amanda; Jafry, Tahseen

2013-01-01

Purpose: This review paper presents an overview of changes in agricultural extension on a global scale and helps to characterise on-going developments in extension practice. Design/methodology/approach: Through a critique and synthesis of literature the paper focuses on global political changes which have led to widespread changes from production-…

Environmental, physical and structural characterisation of geopolymer matrixes synthesised from coal (co-)combustion fly ashes.

PubMed

Alvarez-Ayuso, E; Querol, X; Plana, F; Alastuey, A; Moreno, N; Izquierdo, M; Font, O; Moreno, T; Diez, S; Vázquez, E; Barra, M

2008-06-15

The synthesis of geopolymer matrixes from coal (co-)combustion fly ashes as the sole source of silica and alumina has been studied in order to assess both their capacity to immobilise the potentially toxic elements contained in these coal (co-)combustion by-products and their suitability to be used as cement replacements. The geopolymerisation process has been performed using (5, 8 and 12 M) NaOH solutions as activation media and different curing time (6-48 h) and temperature (40-80 degrees C) conditions. Synthesised geopolymers have been characterised with regard to their leaching behaviour, following the DIN 38414-S4 [DIN 38414-S4, Determination of leachability by water (S4), group S: sludge and sediments. German standard methods for the examination of water, waste water and sludge. Institut für Normung, Berlin, 1984] and NEN 7375 [NEN 7375, Leaching characteristics of moulded or monolithic building and waste materials. Determination of leaching of inorganic components with the diffusion test. Netherlands Normalisation Institute, Delft, 2004] procedures, and to their structural stability by means of compressive strength measurements. In addition, geopolymer mineralogy, morphology and structure have been studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. It was found that synthesised geopolymer matrixes were only effective in the chemical immobilisation of a number of elements of environmental concern contained in fly ashes, reducing (especially for Ba), or maintaining their leachable contents after the geopolymerisation process, but not for those elements present as oxyanions. Physical entrapment does not seem either to contribute in an important way, in general, to the immobilisation of oxyanions. The structural stability of synthesised geopolymers was mainly dependent on the glass content of fly ashes, attaining at the optimal activation conditions (12 M NaOH, 48 h, 80 degrees C) compressive strength values about 60 MPa when the fly ash glass content was higher than 90%.

The application of inelastic neutron scattering to explore the significance of a magnetic transition in an iron based Fischer-Tropsch catalyst that is active for the hydrogenation of CO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warringham, Robbie; McFarlane, Andrew R.; Lennon, David, E-mail: David.Lennon@Glasgow.ac.uk

2015-11-07

An iron based Fischer-Tropsch synthesis catalyst is evaluated using CO hydrogenation at ambient pressure as a test reaction and is characterised by a combination of inelastic neutron scattering (INS), powder X-ray diffraction, temperature-programmed oxidation, Raman scattering, and transmission electron microscopy. The INS spectrum of the as-prepared bulk iron oxide pre-catalyst (hematite, α-Fe{sub 2}O{sub 3}) is distinguished by a relatively intense band at 810 cm{sup −1}, which has previously been tentatively assigned as a magnon (spinon) feature. An analysis of the neutron scattering intensity of this band as a function of momentum transfer unambiguously confirms this assignment. Post-reaction, the spinon featuremore » disappears and the INS spectrum is characterised by the presence of a hydrocarbonaceous overlayer. A role for the application of INS in magnetic characterisation of iron based FTS catalysts is briefly considered.« less

Extracellular synthesis gold nanotriangles using biomass of Streptomyces microflavus.

PubMed

Soltani Nejad, Meysam; Khatami, Mehrdad; Shahidi Bonjar, Gholam Hosein

2016-02-01

Applications of nanotechnology and nano-science have ever-expanding breakthroughs in medicine, agriculture and industries in recent years; therefore, synthesis of metals nanoparticle (NP) has special significance. Synthesis of NPs by chemical methods are long, costly and hazardous for environment so biosynthesis has been developing interest for researchers. In this regard, the extracellular biosynthesis of gold nanotriangles (AuNTs) performed by use of the soil Streptomycetes. Streptomycetes isolated from rice fields of Guilan Province, Iran, showed biosynthetic activity for producing AuNTs via in vitro experiments. Among all 15 Streptomyces spp. isolates, isolate No. 5 showed high biosynthesis activity. To determine the bacterium taxonomical identity at genus level, its colonies characterised morphologically by use of scanning electron microscope. The polymerase chain reaction (PCR) molecular analysis of active isolate represented its identity partially. In this regard, 16S rRNA gene of the isolate was amplified using universal bacterial primers FD1 and RP2. The PCR products were purified and sequenced. Sequence analysis of 16S rDNA was then conducted using National Center for Biotechnology Information Basic Local Alignment Search Tool method. The AuNTs obtained were characterised by ultraviolet-visible spectroscopy, atomic force microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction spectroscopy analyses. The authors results indicated that Streptomyces microflavus isolate 5 bio-synthesises extracellular AuNTs in the range of 10-100 nm. Synthesised SNPs size ranged from 10 to 100 nm. In comparison with chemical methods for synthesis of metal NPs, the biosynthesis of AuNTs by Streptomyces source is a fast, simple and eco-friendly method. The isolate is a good candidate for further investigations to optimise its production efficacy for further industrial goals in biosynthesis of AuNTs.

Smart poly(oligo(propylene glycol) methacrylate) hydrogel prepared by gamma radiation

NASA Astrophysics Data System (ADS)

Suljovrujic, E.; Micic, M.

2015-01-01

The synthesis of poly(oligo(propylene glycol) methacrylate) (POPGMA) from functionalised oligo(propylene glycol) methacrylate (OPGMA) monomers by gamma radiation-induced radical polymerisation is reported for the first time; POPGMA homopolymeric hydrogel with oligo(propylene glycol) (OPG) pendant chains, as a non-linear PPGMA-analogue, was synthesised from an monomer-solvent (OPGMA375-water/ethanol) mixture at different irradiation doses (5, 10, 25, and 40 kGy). Determination of the gel fraction was conducted after synthesis. The swelling properties of the POPGMA hydrogel were preliminarily investigated over wide pH (2.2-9.0) and temperature (4-70 °C) ranges. Additional characterisation of structure and properties was conducted by UV-vis and Fourier transform infrared (FTIR) spectroscopy as well as by differential scanning calorimetry (DSC). In order to evaluate the potential for biomedical applications, biocompatibility (cytocompatibility and haemolytic activity) studies were performed as well. Sol-gel conversion was relatively high for all irradiation doses, indicating radiation-induced synthesis as a good method for fabricating this hydrogel. Thermoresponsiveness and variations in swelling capacity as a result of thermosensitive OPG pendant chains with a lower critical solution temperature (LCST) were mainly observed below room temperature; thus, the volume phase transition temperature (VPTT) of POPGMA homopolymeric hydrogel is about 15 °C. Furthermore, POPGMA has satisfactory biocompatibility. The results indicate that the hydrogels with propylene glycol pendant chains can be easily prepared by gamma radiation and have potential for different applications as smart and biocompatible polymers.

Synthesis and characterisation of mucoadhesive thiolated polyallylamine.

PubMed

Duggan, Sarah; Hughes, Helen; Owens, Eleanor; Duggan, Elaine; Cummins, Wayne; O' Donovan, Orla

2016-02-29

The thiolation of polyallylamine (PAAm) for use in mucoadhesive drug delivery has been achieved. PAAm was reacted with different ratios of Traut's reagent, yielding products with thiol contents ranging from 134-487μmol/g. Full mucoadhesive characterisation of the thiolated PAAm samples was conducted using swelling studies, mucoadhesive testing on porcine intestinal tissue and rheology. Both swelling and cohesive properties of the thiolated PAAm products were vastly improved in comparison to an unmodified PAAm control. The swelling abilities of the thiolated samples were high and the degree of thiolation of the products affected the initial rate of swelling. High levels of mucoadhesion were demonstrated by the thiolated PAAm samples, with adhesion times of greater than 24h measured for all three samples and, thus, thiol content did not appear to influence mucoadhesion. Rheological studies of the thiolated PAAm samples showed an increase in G' and G″ values upon the addition of a mucin solution which was not observed in the unmodified control, again highlighting the mucoadhesive interactions between these thiolated polymers and mucin. The synthesis of thiolated PAAm by reaction with Traut's reagent and resulting mucoadhesive properties demonstrates its potential for use a mucoadhesive drug delivery device. Copyright © 2016 Elsevier B.V. All rights reserved.

Combining two-directional synthesis and tandem reactions. Part 21: Exploitation of a dimeric macrocycle for chain terminus differentiation and synthesis of an sp(3)-rich library.

PubMed

Storr, Thomas E; Cully, Sarah J; Rawling, Michael J; Lewis, William; Hamza, Daniel; Jones, Geraint; Stockman, Robert A

2015-06-01

The application of a tandem condensation/cyclisation/[3+2]-cycloaddition/elimination reaction gives an sp(3)-rich tricyclic pyrazoline scaffold with two ethyl esters in a single step from a simple linear starting material. The successive hydrolysis and cyclisation (with Boc anhydride) of these 3-dimensional architectures, generates unprecedented 16-membered macrocyclic bisanhydrides (characterised by XRD). Selective amidations could then be achieved by ring opening with a primary amine followed by HATU-promoted amide coupling to yield an sp(3)-rich natural product-like library. Copyright © 2015 Elsevier Ltd. All rights reserved.

In vitro characterisation of a sol-gel derived in situ silica-coated silicate and carbonate co-doped hydroxyapatite nanopowder for bone grafting.

PubMed

Latifi, Seyed Mohsen; Fathi, Mohammadhossein; Sharifnabi, Ali; Varshosaz, Jaleh

2017-06-01

Design and synthesis of materials with better properties and performance are essential requirements in the field of biomaterials science that would directly improve patient quality of life. For this purpose, in situ silica-coated silicate and carbonate co-doped hydroxyapatite (Sc/S.C.HA) nanopowder was synthesized via the sol-gel method. Characterisation of the prepared nanopowder was carried out by XRD, FTIR, TEM, SEM, EDX, ICP, zeta potential, acid dissolution test, and cell culture test. The substitution of the silicate and carbonate ions into hydroxyapatite structure was confirmed by FTIR analysis. XRD analysis showed that silica is an amorphous phase, which played a role in covering the surface of the S.C.HA nanoparticles as confirmed by acid dissolution test. Low thickness and low integrity of the amorphous silica surface layer facilitated ions release from S.C.HA nanoparticles into physiological saline solution. Zeta potential of the prepared nanopowder suspended in physiological saline solution was -27.3±0.2mV at pH7.4. This negatively charged surface, due to the presence of amorphous silica layer upon the S.C.HA nanoparticles, not only had an accelerating effect on in vitro biomineralization of apatite, but also had a positive effect on cell attachment. Copyright © 2017 Elsevier B.V. All rights reserved.

In vitro synthesis and characterisation of three fenoterol sulfoconjugates detected in fenoterol post-administration urine samples.

PubMed

Orlovius, A K; Guddat, S; Gütschow, M; Thevis, M; Schänzer, W

2013-11-01

Fenoterol, a fast-acting β2-adrenergic agonist, is used in the therapy of obstructive pulmonary diseases and for the inhibition of premature labour obstetrics. Doping control for β2-agonists, which are prohibited in sports by the World Anti-Doping Agency, is commonly performed by liquid chromatography/mass spectrometry after hydrolysis of phase II metabolites. The continuing development of analytical procedures has led to direct injection of urine samples without sample preparation becoming a viable tool. For the detection of substances without sample preparation, including hydrolysis, detailed information of the phase II metabolism of the substances is essential. In this study, human S9 fractions of different tissues and two recombinant sulfotransferases were investigated for their potential to form fenoterol sulfoconjugates, which were characterised in detail. Two mono-sulfoconjugates and one bis-sulfoconjugate were synthesised and their structures confirmed by liquid chromatography–high-resolution/high-accuracy mass spectrometry. All of the metabolites were identified as esterified phenolic compounds. Excretion studies with orally and inhalatively administered fenoterol proved the occurrence of the sulfoconjugates in vivo. Inhalatively administered fenoterol resulted in the detection of the two monosulfoconjugates in low amounts in urine due to the lower inhalation dose of fenoterol compared to the oral dose. After oral uptake of fenoterol, the two mono-sulfoconjugates and a fenoterol bis-sulfoconjugate were detected in urine. This is the first report of the bis-sulfoconjugate.

Continuous flow chemical vapour deposition of carbon nanotube sea urchins.

PubMed

de La Verpilliere, Jean; Jessl, Sarah; Saeed, Khuzaimah; Ducati, Caterina; De Volder, Michael; Boies, Adam

2018-04-26

Hybrid structures consisting of functional materials enhanced by carbon nanotubes (CNTs) have potential for a variety of high impact applications, as shown by the impressive progress in sensing and mechanical applications enabled by CNT-enhanced materials. The hierarchical organisation of CNTs with other materials is key to the design of macroscale devices benefiting from the unique properties of individual CNTs, provided CNT density, morphology and binding with other materials are optimized. In this paper, we provide an analysis of a continuous aerosol process to create a hybrid hierarchical sea urchin structure with CNTs organized around a functional metal oxide core. We propose a new mechanism for the growth of these carbon nanotube sea urchins (CNTSU) and give new insight into their chemical composition. To corroborate the new mechanism, we examine the influence of CNT growth conditions on CNTSU morphology and demonstrate a new in-line characterisation technique to continuously monitor aerosol CNT growth during synthesis, which enables industrial-scale production optimization. Based upon the new formation mechanism we describe the first substrate-based chemical vapour deposition growth of CNTSUs which increases CNT length and improves G to D ratio, which also allows for the formation of CNTSU carpets with unique structures.

Synthesis and characterization of the tetranuclear iron(III) complex of a new asymmetric multidentate ligand. A structural model for purple acid phosphatases.

PubMed

Boudalis, Athanassios K; Aston, Robyn E; Smith, Sarah J; Mirams, Ruth E; Riley, Mark J; Schenk, Gerhard; Blackman, Allan G; Hanton, Lyall R; Gahan, Lawrence R

2007-11-28

The ligand, 2-((2-hydroxy-5-methyl-3-((pyridin-2-ylmethylamino)methyl)benzyl)(2-hydroxybenzyl)amino)acetic acid (H(3)HPBA), which contains a donor atom set that mimics that of the active site of purple acid phosphatase is described. Reaction of H(3)HPBA with iron(III) or iron(II) salts results in formation of the tetranuclear complex, [Fe(4)(HPBA)(2)(OAc)(2)(mu-O)(mu-OH)(OH(2))(2)]ClO(4) x 5H(2)O. X-Ray structural analysis reveals the cation consists of four iron(III) ions, two HPBA(3-) ligands, two bridging acetate ligands, a bridging oxide ion and a bridging hydroxide ion. Each binucleating HPBA(3-) ligand coordinates two structurally distinct hexacoordinate iron(III) ions. The two metal ions coordinated to a HPBA(3-) ligand are linked to the two iron(III) metal ions of a second, similar binuclear unit by intramolecular oxide and hydroxide bridging moieties to form a tetramer. The complex has been further characterised by elemental analysis, mass spectrometry, UV-vis and MCD spectroscopy, X-ray crystallography, magnetic susceptibility measurements and variable-temperature Mössbauer spectroscopy.

Ferrocenyl-functionalised terpyridines and their transition-metal complexes: syntheses, structures and spectroscopic and electrochemical properties.

PubMed

Siemeling, Ulrich; Vor der Brüggen, Jens; Vorfeld, Udo; Neumann, Beate; Stammler, Anja; Stammler, Hans-George; Brockhinke, Andreas; Plessow, Regina; Zanello, Piero; Laschi, Franco; Fabrizi de Biani, Fabrizia; Fontani, Marco; Steenken, Steen; Stapper, Marion; Gurzadyan, Gagik

2003-06-16

Terpyridine ligands of the type Fc'-X-tpy (Fc'=ferrocenyl or octamethylferrocenyl, X=rigid spacer, tpy'=4'-substituted 2,2':6',2''-terpyridine) were prepared, crystallographically characterised and used for the synthesis of di- and trinuclear bis(terpyridine) complexes of RuII, FeII and ZnII. Donor-sensitiser dyads and triads based on RuII were thoroughly investigated by (spectro)electrochemistry, UV/Vis, transient absorption and luminescence spectroscopy, and an energy level scheme was derived on the basis of the data collected. Intramolecular quenching of the photoexcited RuII complexes by the redox-active Fc' groups can occur reductively and by energy transfer. Both the redox potential of the donor Fc' and the nature of the spacer X have a decisive influence on excited-state lifetimes and emission properties of the complexes. Some of the compounds show room-temperature luminescence, which is unprecedented for ferrocenyl-functionalised compounds of this kind.

Exploring the Photovoltaic Properties of Metal Bipyridine Complexes (Metal = Fe, Zn, Cr, and Ru) by Density Functional Theory

NASA Astrophysics Data System (ADS)

Irfan, Ahmad; Abbas, Ghulam

2018-03-01

The synthesis and characterisation of mononuclear Fe complexes were carried out by using bipyridine (Compound 1) at ambient conditions. Additionally, three more derivatives were designed by substituting the central Fe metal with Zn, Cr, and Ru (Compound 2, Compound 3, and Compound 4), respectively. The ground state geometry calculations were carried out by using density functional theory (DFT) at B3LYP/6-31G** (LANL2DZ) level of theory. We shed light on the frontier molecular orbitals, electronic properties, photovoltaic parameters, and structure-property relationship. The open-circuit voltage is a promising parameter that considerably affects the photovoltaic performance; thus, we have estimated its value by considering the complexes as donors whereas TiO2 and/or Si were used as acceptors. The solar cell performance behaviour was also studied by shedding light on the band alignment and energy level offset.

Characterisation of the Interaction between Toroidal Vortex Structures and Flame Front Propagation

NASA Astrophysics Data System (ADS)

Long, E. J.; Hargrave, G. K.; Jarvis, S.; Justham, T.; Halliwell, N.

2006-07-01

Experimental laser diagnostic data is presented for flame characterisation during interactions with toroidal vortices generated in the wake of an annular obstacle. A novel twin section combustion chamber has been utilised to allow the controlled formation of stable eddy structures into which a flame front can propagate. High speed laser sheet visualisation was employed to record the flow field and flame front temporal development and high-speed digital particle image velocimetry was used to quantify the velocity field of the unburnt mixture ahead of the flame front. Results provide characterisation of the toroidal vortex/flame front interaction for a range of vortex scales of and recirculation strengths.

Magnetic nanoparticles through organometallic synthesis: evolution of the magnetic properties from isolated nanoparticles to organised nanostructures.

PubMed

Dumestre, Fréderic; Martinez, Susana; Zitoun, David; Fromen, Marie-Claire; Casanove, Marie-José; Lecante, Pierre; Respaud, Marc; Serres, Arnaud; Benfield, Robert E; Amiens, Catherine; Chaudret, Bruno

2004-01-01

Co and NiFe nanoparticles (2.7 to 3.3 nm mean diameter) of narrow size distribution have been obtained through the decomposition of organometallic precursors in organic solutions of long alkyl chain ligands, namely oleic acid and hexadecylamine. Materials of various volume fractions were produced. The particles have been structurally characterised by WAXS. Both adopt the bulk structure: HCP in the case of cobalt; a mixture of FCC and BCC for NiFe. Their aptitude to self-assemble either on flat supports or in bulk solid state has been investigated by means of TEM and SAXS. This study suggests the crystallisation of the nanoparticles upon solvent evaporation, especially a local FCC arrangement was observed for the NiFe material. Magnetic measurements (SQUID) confirm this tendency. The blocking temperature depends on the metal volume fraction, i.e. on the anisotropy generated by the dipolar couplings (Ki). We show that, for dense samples, the particles of high intrinsic anisotropy, Ku, (Co) still display an individual behaviour while the soft ones (NiFe) display a collective behaviour.

The first proton sponge-based amino acids: synthesis, acid-base properties and some reactivity.

PubMed

Ozeryanskii, Valery A; Gorbacheva, Anastasia Yu; Pozharskii, Alexander F; Vlasenko, Marina P; Tereznikov, Alexander Yu; Chernov'yants, Margarita S

2015-08-21

The first hybrid base constructed from 1,8-bis(dimethylamino)naphthalene (proton sponge or DMAN) and glycine, N-methyl-N-(8-dimethylamino-1-naphthyl)aminoacetic acid, was synthesised in high yield and its hydrobromide was structurally characterised and used to determine the acid-base properties via potentiometric titration. It was found that the basic strength of the DMAN-glycine base (pKa = 11.57, H2O) is on the level of amidine amino acids like arginine and creatine and its structure, zwitterionic vs. neutral, based on the spectroscopic (IR, NMR, mass) and theoretical (DFT) approaches has a strong preference to the zwitterionic form. Unlike glycine, the DMAN-glycine zwitterion is N-chiral and is hydrolytically cleaved with the loss of glycolic acid on heating in DMSO. This reaction together with the mild decarboxylative conversion of proton sponge-based amino acids into 2,3-dihydroperimidinium salts under air-oxygen was monitored with the help of the DMAN-alanine amino acid. The newly devised amino acids are unique as they combine fluorescence, strongly basic and redox-active properties.

Synthesis, structural characterisation and antibacterial activity of Ag+-doped fluorapatite nanomaterials prepared by neutralization method

NASA Astrophysics Data System (ADS)

Stanić, Vojislav; Radosavljević-Mihajlović, Ana S.; Živković-Radovanović, Vukosava; Nastasijević, Branislav; Marinović-Cincović, Milena; Marković, Jelena P.; Budimir, Milica D.

2015-05-01

Silver doped fluorapatite nanopowders were synthesised by neutralization method, which consists of dissolving Ag2O in solution of HF and H3PO4 and addition to suspension of Ca(OH)2. The powder XRD, SEM and FTIR studies indicated the formation of a fluorapatite nanomaterials with average length of the particles is about 80 nm and a width of about 15 nm. The FTIR studies show that carbonate content in samples is very small and carbonte ions substitute both phosphate and hydroxyl groups in the crystal structure of samples, forming AB-type fluorapatite. Antibacterial studies have demonstrated that all Ag+-doped fluorapatite samples exhibit bactericidal effect against pathogens: Staphylococcus aureus, Micrococcus luteus and Kllebsiela pneumoniae. Antibacterial activity increased with the increase of Ag+ in the samples. The atomic force microscopy studies revealed extensive damage to the bacterial cell envelops in the presence of Ag+-doped fluorapatite particles which may lead to their death. The synthesized Ag+-doped fluorapatite nanomaterials are promising as antibacterial biomaterials in orthopedics and dentistry.

Mixed valence transition metal 2D-oxides: Comparison between delafossite and crednerite compounds

NASA Astrophysics Data System (ADS)

Martin, Christine; Poienar, Maria

2017-08-01

Transition metal oxides offer large opportunities to study relationships between structures and properties. Indeed these compounds crystallize in numerous frameworks corresponding to different dimensionalities and, accordingly, show a huge variety of properties (as high Tc superconductivity, colossal magnetoresistivity, multiferroicity..). The control of the oxidation state of the transition metal, via the monitoring of the oxygen content, is of prime importance to understand and optimize the properties, due to the strong coupling that exists between the lattice and the charges and spins of the transition metals. In this large playground for chemists, we reinvestigated several 2D-compounds derived from delafossite structure. Considering this paper as a very short review, we report here the results obtained on CuMO2 compounds (with M = Cr, Mn or Mn+Cu) by using a combination of techniques, as X-ray, neutrons and/or electrons diffraction on poly-crystals for structural characterisations that are correlated with electrical and/or magnetic properties. The complementarity of studies is also addressed by the synthesis and characterization of single crystals in addition to poly-crystals. Moreover the comparison of the structures of similar Cr and Mn based oxides highlights the crucial role of the Jahn-Teller effect of trivalent manganese to lift the degeneracy, which is responsible of the magnetic frustration in CuCrO2.

Synthesis and characterisation of novel low temperature ceramic and its implementation as substrate in dual segment CDRA

NASA Astrophysics Data System (ADS)

Kumari, Preeti; Tripathi, Pankaj; Sahu, Bhagirath; Singh, S. P.; Parkash, Om; Kumar, Devendra

2018-02-01

Li2O-(2-3x)MgO-(x)Al2O3-P2O5 (LMAP) (x = 0.00-0.08) ceramic system was prepared through solid state synthesis route at different sintering temperatures (800-925 °C). A small addition of Al2O3 (x = 0.02) in LMAP ceramics lowers the sintering temperature by more than 100 °C with good relative density of 94.13%. The sintered samples were characterized in terms of density, apparent porosity, water absorption, crystal structure, micro-structure and microwave dielectric properties. Silver compatibility test is also performed for its use as electrode material in low temperature co-fired ceramic (LTCC) application. To check the performance of the prepared LTCC as substrate, a microstrip-fed aperture-coupled dual segment cylindrical dielectric resonator antenna (DS-CDRA) is designed using LMAP (x = 0.02) ceramic as substrate material and Barium Strontium Titanate with 10 wt% of PbO-BaO-B2O3-SiO2 glass (BSTG) and Teflon as the components of resonating material. The simulation study of the DS-CDRA is performed using the Ansys High Frequency Structure Simulator (HFSS) software. A conductive coating of silver is used on the substrate. The simulated and measured -10 dB reflection coefficient bandwidths of 910 MHz (9.07-9.98 GHz at resonant frequency of 9.49 GHz) and 1080 MHz (8.68-9.76 GHz at resonant frequency of 9.36 GHz), respectively are achieved. The measured results of the fabricated antenna are found in good agreement with the simulation results. The prepared material can find potential applications in radar and radio navigation as well as radio astronomy and military satellite communication.

Synthesis of 5-(ethylsulfonyl)-2-methoxyaniline: An important pharmacological fragment of VEGFR2 and other inhibitors

PubMed Central

Murár, Miroslav; Addová, Gabriela

2013-01-01

Summary Background: 5-(Ethylsulfonyl)-2-methoxyaniline (5) is part of the structure in 131 compounds possessing different biological activities. In most cases, they have antitumor properties (112 compounds). Other compounds are described as cardiovascular agents, ion-channel blockers, nervous-system blockers, anti-inflammatory agents, or antidiabetic, antiosteoporotic and hypolipemic species. Compound 5 is a precursor of different protein-kinase inhibitors or enzyme modulators (EGFR, PDGFR, ckit, CDK 2 and 4, MMPs 2, 3, 9 and 13, etc.). The structure of 5 represents a fragment for several powerful inhibitors of VEGFR2, a key angiogenic receptor. Antiangiogenic inhibitors slow down or stop new blood-vessel formation from pre-existing vasculature. Some antiangiogenic drugs inhibiting the VEGFR2 receptor are successfully used in clinics for the treatment of several types of tumours in synergy with chemotherapy (e.g., Nexavar® from Bayer, Sutent® from Pfizer and Votrient® from GlaxoSmithKline, approved by the FDA in 2005, 2006 and 2009, respectively). The structure of 5 is an important pharmacophoric fragment of potent VEGFR2 inhibitors (e.g., AAZ from PDB complex 1Y6A, enzymatic IC50 = 22 nM). Up to now, 25 VEGFR2 inhibitors possessing a fragment of 5 can be found in the literature. Despite the high significance of 5-(ethylsulfonyl)-2-methoxyaniline (5) its preparation has not yet been described. Results: Here we have developed a convenient synthesis of important polyheterosubstituted aniline 5 starting from commercially available 4-methoxybenzene-1-sulfonyl chloride (1) in four steps and 59% overall yield. The target 5-(ethylsulfonyl)-2-methoxyaniline (5) and its synthetic intermediates 2–4 together with a new compound 5-(ethylsulfonyl)-2-methoxy-1,3-dinitrobenzene (4a) have been precisely physicochemically characterised. PMID:23399884

Sustainable and Continuous Synthesis of Enantiopure l-Amino Acids by Using a Versatile Immobilised Multienzyme System.

PubMed

Velasco-Lozano, Susana; da Silva, Eunice S; Llop, Jordi; López-Gallego, Fernando

2018-02-16

The enzymatic synthesis of α-amino acids is a sustainable and efficient alternative to chemical processes, through which achieving enantiopure products is difficult. To more address this synthesis efficiently, a hierarchical architecture that irreversibly co-immobilises an amino acid dehydrogenase with polyethyleneimine on porous agarose beads has been designed and fabricated. The cationic polymer acts as an irreversible anchoring layer for the formate dehydrogenase. In this architecture, the two enzymes and polymer colocalise across the whole microstructure of the porous carrier. This multifunctional heterogeneous biocatalyst was kinetically characterised and applied to the enantioselective synthesis of a variety of canonical and noncanonical α-amino acids in both discontinuous (batch) and continuous modes. The co-immobilised bienzymatic system conserves more than 50 % of its initial effectiveness after five batch cycles and 8 days of continuous operation. Additionally, the environmental impact of this process has been semiquantitatively calculated and compared with the state of the art. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and synthesis of binucleating macrocyclic clefts derived from Schiff-base calixpyrroles.

PubMed

Givaja, Gonzalo; Volpe, Manuel; Leeland, James W; Edwards, Michael A; Young, Thomas K; Darby, S Barnie; Reid, Stuart D; Blake, Alexander J; Wilson, Claire; Wolowska, Joanna; McInnes, Eric J L; Schröder, Martin; Love, Jason B

2007-01-01

The syntheses, characterisation and complexation reactions of a series of binucleating Schiff-base calixpyrrole macrocycles are described. The acid-templated [2+2] condensations between meso-disubstituted diformyldipyrromethanes and o-phenylenediamines generate the Schiff-base pyrrolic macrocycles H(4)L(1) to H(4)L(6) upon basic workup. The single-crystal X-ray structures of both H(4)L(3).2 EtOH and H(4)L(6).H2O confirm that [2+2] cyclisation has occurred, with either EtOH or H2O hydrogen-bonded within the macrocyclic cleft. A series of complexation reactions generate the dipalladium [Pd2(L)] (L=L(1) to L(5)), dinickel [Ni2(L(1))] and dicopper [Cu2(L)] (L=L(1) to L(3)) complexes. All of these complexes have been structurally characterised in the solid state and are found to adopt wedged structures that are enforced by the rigidity of the aryl backbone to give a cleft reminiscent of the structures of Pacman porphyrins. The binuclear nickel complexes [Ni2(mu-OMe)2Cl2(HOMe)2(H(4)L(1))] and [Ni2(mu-OH)2Cl2(HOMe)(H(4)L(5))] have also been prepared, although in these cases the solid-state structures show that the macrocyclic ligand remains protonated at the pyrrolic nitrogen atoms, and the Ni(II) cations are therefore co-ordinated by the imine nitrogen atoms only to give an open conformation for the complex. The dicopper complex [Cu2(L(3))] was crystallised in the presence of pyridine to form the adduct [Cu2(py)(L(3))], in which, in the solid state, the pyridine ligand is bound within the binuclear molecular cleft. Reaction between H(4)L(1) and [Mn(thf){N(SiMe(3))2}2] results in clean formation of the dimanganese complex [Mn2(L(1))], which, upon crystallisation, formed the mixed-valent complex [Mn2(mu-OH)(L(1))] in which the hydroxo ligand bridges the metal centres within the molecular cleft.

Porous nanocrystalline silicon supported bimetallic Pd-Au catalysts: preparation, characterization and direct hydrogen peroxide synthesis

NASA Astrophysics Data System (ADS)

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-03-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterised by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 at selectivity of 50 % and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at -10 °C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process.

Preparation and characterisation of carbon-free Cu(111) films on sapphire for graphene synthesis

NASA Astrophysics Data System (ADS)

Lehnert, J.; Spemann, D.; Surjuse, S.; Mensing, M.; Grüner, C.; With, P.; Schumacher, P.; Finzel, A.; Hirsch, D.; Rauschenbach, B.

2018-03-01

This work presents an investigation of carbon formed on polycrystalline Cu(111) thin films prepared by ion beam sputtering at room temperature on c-plane Al2O3 after thermal treatment in a temperature range between 300 and 1020°C. The crystallinity of the Cu films was studied by XRD and RBS/channeling and the surface was characterised by Raman spectroscopy, XPS and AFM for each annealing temperature. RBS measurements revealed the diffusion of the Cu into the Al2O3 substrate at high temperatures of > 700°C. Furthermore, a cleaning procedure using UV ozone treatment is presented to remove the carbon from the surface which yields essentially carbon-free Cu films that open the possibility to synthesize graphene of well-controlled thickness (layer number).

Systematic searching for theory to inform systematic reviews: is it feasible? Is it desirable?

PubMed

Booth, Andrew; Carroll, Christopher

2015-09-01

In recognising the potential value of theory in understanding how interventions work comes a challenge - how to make identification of theory less haphazard? To explore the feasibility of systematic identification of theory. We searched PubMed for published reviews (1998-2012) that had explicitly sought to identify theory. Systematic searching may be characterised by a structured question, methodological filters and an itemised search procedure. We constructed a template (BeHEMoTh - Behaviour of interest; Health context; Exclusions; Models or Theories) for use when systematically identifying theory. The authors tested the template within two systematic reviews. Of 34 systematic reviews, only 12 reviews (35%) reported a method for identifying theory. Nineteen did not specify how they identified studies containing theory. Data were unavailable for three reviews. Candidate terms include concept(s)/conceptual, framework(s), model(s), and theory/theories/theoretical. Information professionals must overcome inadequate reporting and the use of theory out of context. The review team faces an additional concern in lack of 'theory fidelity'. Based on experience with two systematic reviews, the BeHEMoTh template and procedure offers a feasible and useful approach for identification of theory. Applications include realist synthesis, framework synthesis or review of complex interventions. The procedure requires rigorous evaluation. © 2015 Health Libraries Group.

Synthesis and characterisation of hetero-bimetallic organometallic phenylalanine and PNA monomer derivatives.

PubMed

Gasser, Gilles; Brosch, Oliver; Ewers, Alexandra; Weyhermüller, Thomas; Metzler-Nolte, Nils

2009-06-14

The rational, sequential synthesis of two hetero-bimetallic derivatives of the amino acid phenylalanine and one thymine (T) peptide nucleic acid (PNA) monomer is reported. Ferrocene carboxylic acid and (eta-ethene)bis(triphenylphosphine)platinum(0) were successfully reacted with propargylamide amino acid (1a and 1b) or a T PNA monomer derivative (6) to give the expected three bimetallic compounds 4a, 4b and 9 in good yield. An enzymatic route using cross-linked enzyme crystals (CLEC) of subtilopeptidase A in organic solvents gave the ferrocene carboxylate phenylalanine propargylamide precursor (Fc-CO-Phe-NH-CH(2)-CCH, 3a) in comparable yield and purity to the traditional deprotection-peptide coupling sequence. (31)P NMR spectra of these bioorganometallics showed two doublets with (195)Pt satellites corresponding to two chemically different (31)P atoms. Interestingly, in the case of the T PNA monomer derivative 9, these signals were also doubled in a 60 : 40 ratio as a consequence of the existence of two slowly interconverting isomers in solution. Furthermore, the single-crystal X-ray structures of 3a and the hetero-bimetallic phenylalanine derivative 4b were determined, showing the presence of the two organometallics moieties separated by ca. 8.5 A in 4b as well as illustrating the stability of such compounds.

Synthesis, characterisation, and in vitro cellular uptake kinetics of nanoprecipitated poly(2-methacryloyloxyethyl phosphorylcholine)- b-poly(2-(diisopropylamino)ethyl methacrylate) (MPC-DPA) polymeric nanoparticle micelles for nanomedicine applications

NASA Astrophysics Data System (ADS)

Salvage, Jonathan P.; Smith, Tia; Lu, Tao; Sanghera, Amendeep; Standen, Guy; Tang, Yiqing; Lewis, Andrew L.

2016-10-01

Nanoscience offers the potential for great advances in medical technology and therapies in the form of nanomedicine. As such, developing controllable, predictable, and effective, nanoparticle-based therapeutic systems remains a significant challenge. Many polymer-based nanoparticle systems have been reported to date, but few harness materials with accepted biocompatibility. Phosphorylcholine (PC) based biomimetic materials have a long history of successful translation into effective commercial medical technologies. This study investigated the synthesis, characterisation, nanoprecipitation, and in vitro cellular uptake kinetics of PC-based polymeric nanoparticle micelles (PNM) formed by the biocompatible and pH responsive block copolymer poly(2-methacryloyloxyethyl phosphorylcholine)- b-poly(2-(diisopropylamino)ethyl methacrylate) (MPC-DPA). Atom transfer radical polymerisation (ATRP), and gel permeation chromatography (GPC) were used to synthesise and characterise the well-defined MPC100-DPA100 polymer, revealing organic GPC, using evaporative light scatter detection, to be more accurate than aqueous GPC for this application. Subsequent nanoprecipitation investigations utilising photon correlation spectroscopy (PCS) revealed PNM size increased with polymer concentration, and conferred Cryo-stability. PNM diameters ranged from circa 64-69 nm, and increased upon hydrophobic compound loading, circa 65-71 nm, with loading efficiencies of circa 60 % achieved, whilst remaining monodisperse. In vitro studies demonstrated that the PNM were of low cellular toxicity, with colony formation and MTT assays, utilising V79 and 3T3 cells, yielding comparable results. Investigation of the in vitro cellular uptake kinetics revealed rapid, 1 h, cellular uptake of MPC100-DPA100 PNM delivered fluorescent probes, with fluorescence persistence for 48 h. This paper presents the first report of these novel findings, which highlight the potential of the system for nanomedicine application development.

New investigations around CYP11A1 and its possible involvement in an androstenone QTL characterised in Large White pigs

PubMed Central

2011-01-01

Background Previously, in boars with extreme androstenone levels, differential expression of the CYP11A1 gene in the testes has been characterised. CYP11A1 is located in a region where a QTL influencing boar fat androstenone levels has been detected in a Large White pig population. Clarifying the role of CYP11A1 in boar taint is important because it catalyses the initial step of androstenone synthesis and also of steroid synthesis. Results A genome-wide association study located CYP11A1 at approximately 1300 kb upstream from SNP H3GA0021967, defining the centre of the region containing the QTL for androstenone variation. In this study, we partially sequenced the CYP11A1 gene and identified several new single nucleotide polymorphisms (SNP) within it. Characterisation of one animal, heterozygous for CYP11A1 testicular expression but homozygous for a haplotype of a large region containing CYP11A1, revealed that variation of CYP11A1 expression is probably regulated by a mutation located downstream from the SNP H3GA0021967. We analysed CYP11A1 expression in LW families according to haplotypes of the QTL region's centre. Effects of haplotypes on CYP11A1 expression and on androstenone accumulation were not concordant. Conclusion This study shows that testicular expression of CYP11A1 is not solely responsible for the QTL influencing boar fat androstenone levels. As a conclusion, we propose to refute the hypothesis that a single mutation located near the centre of the QTL region could control androstenone accumulation in fat by regulating the CYP11A1 expression. PMID:21504607

Characterising the progress in HIV/AIDS research in the Middle East and North Africa

PubMed Central

Saba, Hanan F; Kouyoumjian, Silva P; Mumtaz, Ghina R; Abu-Raddad, Laith J

2013-01-01

Objectives The Middle East and North Africa (MENA) region is perceived to have limited HIV data. The objective of this study was to quantitatively characterise the progress in HIV research in this region since the discovery of the epidemic. Methods Four indices were defined and implemented to measure the progress of HIV research using the PubMed, Embase, MENA HIV/AIDS Epidemiology Synthesis Project and US Census Bureau HIV/AIDS Surveillance databases. The four indices provide complementary measures to characterise different aspects of the progress of HIV research. Results A total of 2118, 2352, 683 and 4889 records were identified through the PubMed, the Embase, the Synthesis Project and the HIV Prevalence indices, respectively. The proportion of the total global HIV records that relate to MENA is 1.2%. Overall, the indices show steady progress in the number of new records every year, with an accelerated pace in the last few years. The rate of progress in MENA was also higher than the rate of progress in HIV records globally. There is no evidence so far of stabilisation or a peak in the number of new records year by year. About half of the records were produced after the year 2005. The number of records shows large heterogeneity across countries. Conclusions MENA has witnessed a rapid growth in HIV research over the last decade. However, there are still large gaps in HIV scientific evidence in the region, and the progress is far from being uniform across countries. Ongoing and future research needs to be geared towards academic standard and production of scientific publications. PMID:23596206

Greener synthesis of Cu-MOF-74 and its catalytic use for the generation of vanillin.

PubMed

Flores, J Gabriel; Sánchez-González, Elí; Gutiérrez-Alejandre, Aída; Aguilar-Pliego, Julia; Martínez, Ana; Jurado-Vázquez, Tamara; Lima, Enrique; González-Zamora, Eduardo; Díaz-García, Manuel; Sánchez-Sánchez, Manuel; Ibarra, Ilich A

2018-03-26

A greener synthesis of Cu-MOF-74 was obtained, for the first time, in methanol as the unique solvent and at room temperature. Full characterisation of the MOF material showed its purity and also its nanocrystalline nature. Complete activation (150 °C for 1 h and 10-3 bar) of Cu-MOF-74 afforded unsaturated Cu metal sites and this was corroborated by in situ DRIFT spectroscopy. The access to these Cu open metal sites was tested for the catalytic transformation of trans-ferulic acid to vanillin (yield of 71% and 97% selectivity) and a plausible catalytic reaction mechanism was postulated based on quantum chemical calculations.

Single-nucleotide polymorphisms and mRNA expression for melatonin synthesis rate-limiting enzyme in recurrent depressive disorder.

PubMed

Gałecki, Piotr; Szemraj, Janusz; Bartosz, Grzegorz; Bieńkiewicz, Małgorzata; Gałecka, Elzbieta; Florkowski, Antoni; Lewiński, Andrzej; Karbownik-Lewińska, Małgorzata

2010-05-01

Depressive disorder (DD) is characterised by disturbances in blood melatonin concentration. It is well known that melatonin is involved in the control of circadian rhythms, sleep included. The use of melatonin and its analogues has been found to be effective in depression therapy. Melatonin synthesis is a multistage process, where the last stage is catalysed by acetylserotonin methyltransferase (ASMT), the reported rate-limiting melatonin synthesis enzyme. Taking into account the significance of genetic factors in depression development, the gene for ASMT may become an interesting focus for studies in patients with recurrent DD. The goal of the study was to evaluate two single-nucleotide polymorphisms (SNPs) (rs4446909; rs5989681) of the ASMT gene, as well as mRNA expression for ASMT in recurrent DD-affected patients. We genotyped two polymorphisms in a group of 181 recurrent DD patients and in 149 control subjects. The study was performed using the polymerase chain reaction/restriction fragment length polymorphism method. The distribution of genotypes in both studied SNPs in the ASMT gene differed significantly between DD and healthy subjects. The presence of AA genotype of rs4446909 polymorphism and of GG genotype of rs5989681 polymorphism was associated with lower risk for having recurrent DD. In turn, patients with depression were characterised by reduced mRNA expression for ASMT. In addition, ASMT transcript level in both recurrent DD patients and in healthy subjects depended significantly on genotype distributions in both polymorphisms. In conclusion, our results suggest the ASMT gene as a susceptibility gene for recurrent DD.

Liquid metals: fundamentals and applications in chemistry.

PubMed

Daeneke, T; Khoshmanesh, K; Mahmood, N; de Castro, I A; Esrafilzadeh, D; Barrow, S J; Dickey, M D; Kalantar-Zadeh, K

2018-04-03

Post-transition elements, together with zinc-group metals and their alloys belong to an emerging class of materials with fascinating characteristics originating from their simultaneous metallic and liquid natures. These metals and alloys are characterised by having low melting points (i.e. between room temperature and 300 °C), making their liquid state accessible to practical applications in various fields of physical chemistry and synthesis. These materials can offer extraordinary capabilities in the synthesis of new materials, catalysis and can also enable novel applications including microfluidics, flexible electronics and drug delivery. However, surprisingly liquid metals have been somewhat neglected by the wider research community. In this review, we provide a comprehensive overview of the fundamentals underlying liquid metal research, including liquid metal synthesis, surface functionalisation and liquid metal enabled chemistry. Furthermore, we discuss phenomena that warrant further investigations in relevant fields and outline how liquid metals can contribute to exciting future applications.

The Characterisation of an Alkali-Stable Maltogenic Amylase from Bacillus lehensis G1 and Improved Malto-Oligosaccharide Production by Hydrolysis Suppression

PubMed Central

Abdul Manas, Nor Hasmaliana; Pachelles, Samson; Mahadi, Nor Muhammad; Illias, Rosli Md.

2014-01-01

A maltogenic amylase (MAG1) from alkaliphilic Bacillus lehensis G1 was cloned, expressed in Escherichia coli, purified and characterised for its hydrolysis and transglycosylation properties. The enzyme exhibited high stability at pH values from 7.0 to 10.0. The hydrolysis of β-cyclodextrin (β-CD) produced malto-oligosaccharides of various lengths. In addition to hydrolysis, MAG1 also demonstrated transglycosylation activity for the synthesis of longer malto-oligosaccharides. The thermodynamic equilibrium of the multiple reactions was shifted towards synthesis when the reaction conditions were optimised and the water activity was suppressed, which resulted in a yield of 38% transglycosylation products consisting of malto-oligosaccharides of various lengths. Thin layer chromatography and high-performance liquid chromatography analyses revealed the presence of malto-oligosaccharides with a higher degree of polymerisation than maltoheptaose, which has never been reported for other maltogenic amylases. The addition of organic solvents into the reaction further suppressed the water activity. The increase in the transglycosylation-to-hydrolysis ratio from 1.29 to 2.15 and the increased specificity toward maltopentaose production demonstrated the enhanced synthetic property of the enzyme. The high transglycosylation activity of maltogenic amylase offers a great advantage for synthesising malto-oligosaccharides and rare carbohydrates. PMID:25221964

Post photosynthetic carbon partitioning to sugar alcohols and consequences for plant growth.

PubMed

Dumschott, Kathryn; Richter, Andreas; Loescher, Wayne; Merchant, Andrew

2017-12-01

The occurrence of sugar alcohols is ubiquitous among plants. Physiochemical properties of sugar alcohols suggest numerous primary and secondary functions in plant tissues and are often well documented. In addition to functions arising from physiochemical properties, the synthesis of sugar alcohols may have significant influence over photosynthetic, respiratory, and developmental processes owing to their function as a large sink for photosynthates. Sink strength is demonstrated by the high concentrations of sugar alcohols found in plant tissues and their ability to be readily transported. The plant scale distribution and physiochemical function of these compounds renders them strong candidates for functioning as stress metabolites. Despite this, several aspects of sugar alcohol biosynthesis and function are poorly characterised namely: 1) the quantitative characterisation of carbon flux into the sugar alcohol pool; 2) the molecular control governing sugar alcohol biosynthesis on a quantitative basis; 3) the role of sugar alcohols in plant growth and ecology; and 4) consequences of sugar alcohol synthesis for yield production and yield quality. We highlight the need to adopt new approaches to investigating sugar alcohol biosynthesis using modern technologies in gene expression, metabolic flux analysis and agronomy. Combined, these approaches will elucidate the impact of sugar alcohol biosynthesis on growth, stress tolerance, yield and yield quality. Copyright © 2017 Elsevier Ltd. All rights reserved.

Asymmetric cellular responses in primary human myoblasts using sera of different origin and specification

PubMed Central

Rullman, Eric; Lilja, Mats; Mandić, Mirko; Melin, Michael; Olsson, Karl; Gustafsson, Thomas

2018-01-01

For successful growth and maintenance of primary myogenic cells in vitro, culture medium and addition of sera are the most important factors. At present it is not established as to what extent sera of different origin and composition, supplemented in media or serum-free media conditions influence myoblast function and responses to different stimuli. By assessing markers of proliferation, differentiation/fusion, quiescence, apoptosis and protein synthesis the aim of the current study was to elucidate how primary human myoblasts and myotubes are modulated by different commonly used serum using FCS (foetal calf serum), (CS-FCS charcoal-stripped FCS, a manufacturing process to remove hormones and growth factors from sera), HS (horse serum) as well as in serum free conditions (DMEM). To characterise the biological impact of the different serum, myoblasts were stimulated with Insulin (100 nM) and Vitamin D (100 nM; 1α,25(OH)2D3, 1α,25-Dihydroxycholecalciferol, Calcitriol), two factors with characterised effects on promoting fusion and protein synthesis or quiescence, respectively in human myoblasts/myotubes. We demonstrate that sera of different origin/formulation differentially affect myoblast proliferation and myotube protein synthesis. Importantly, we showed that quantifying the extent to which Insulin effects myoblasts in vitro is highly dependent upon serum addition and which type is present in the media. Upregulation of mRNA markers for myogenic fusion, Myogenin, with Insulin stimulation, relative to DMEM, appeared dampened at varying degrees with serum addition and effects on p70S6K phosphorylation as a marker of protein synthesis could not be identified unless serum was removed from media. We propose that these asymmetric molecular and biochemical responses in human myoblasts reflect the variable composition of mitogenic and anabolic factors in each of the sera. The results have implications for both the reproducibility and interpretation of results from experimental models in myoblast cells/myotubes. PMID:29401478

GP0.4 from bacteriophage T7: in silico characterisation of its structure and interaction with E. coli FtsZ.

PubMed

Simpkin, Adam J; Rigden, Daniel J

2016-07-13

Proteins produced by bacteriophages can have potent antimicrobial activity. The study of phage-host interactions can therefore inform small molecule drug discovery by revealing and characterising new drug targets. Here we characterise in silico the predicted interaction of gene protein 0.4 (GP0.4) from the Escherichia coli (E. coli) phage T7 with E. coli filamenting temperature-sensitive mutant Z division protein (FtsZ). FtsZ is a tubulin homolog which plays a key role in bacterial cell division and that has been proposed as a drug target. Using ab initio, fragment assembly structure modelling, we predicted the structure of GP0.4 with two programs. A structure similarity-based network was used to identify a U-shaped helix-turn-helix candidate fold as being favoured. ClusPro was used to dock this structure prediction to a homology model of E. coli FtsZ resulting in a favourable predicted interaction mode. Alternative docking methods supported the proposed mode which offered an immediate explanation for the anti-filamenting activity of GP0.4. Importantly, further strong support derived from a previously characterised insertion mutation, known to abolish GP0.4 activity, that is positioned in close proximity to the proposed GP0.4/FtsZ interface. The mode of interaction predicted by bioinformatics techniques strongly suggests a mechanism through which GP0.4 inhibits FtsZ and further establishes the latter's druggable intrafilament interface as a potential drug target.

Characterisation of methionine adenosyltransferase from Mycobacterium smegmatis and M. tuberculosis

PubMed Central

Berger, Bradley J; Knodel, Marvin H

2003-01-01

Background Tuberculosis remains a serious world-wide health threat which requires the characterisation of novel drug targets for the development of future antimycobacterials. One of the key obstacles in the definition of new targets is the large variety of metabolic alterations that occur between cells in the active growth and chronic/dormant phases of tuberculosis. The ideal biochemical target should be active in both growth phases. Methionine adenosyltransferase, which catalyses the formation of S-adenosylmethionine from methionine and ATP, is involved in polyamine biosynthesis during active growth and is also required for the methylation and cyclopropylation of mycolipids necessary for survival in the chronic phase. Results The gene encoding methionine adenosyltransferase has been cloned from Mycobacterium tuberculosis and the model organism M. smegmatis. Both enzymes retained all amino acids known to be involved in catalysing the reaction. While the M. smegmatis enzyme could be functionally expressed, the M. tuberculosis homologue was insoluble and inactive under a large variety of expression conditions. For the M. smegmatis enzyme, the Vmax for S-adenosylmethionine formation was 1.30 μmol/min/mg protein and the Km for methionine and ATP was 288 μM and 76 μM respectively. In addition, the enzyme was competitively inhibited by 8-azaguanine and azathioprine with a Ki of 4.7 mM and 3.7 mM respectively. Azathioprine inhibited the in vitro growth of M. smegmatis with a minimal inhibitory concentration (MIC) of 500 μM, while the MIC for 8-azaguanine was >1.0 mM. Conclusion The methionine adenosyltransferase from both organisms had a primary structure very similar those previously characterised in other prokaryotic and eukaryotic organisms. The kinetic properties of the M. smegmatis enzyme were also similar to known prokaryotic methionine adenosyltransferases. Inhibition of the enzyme by 8-azaguanine and azathioprine provides a starting point for the synthesis of higher affinity purine-based inhibitors. PMID:12809568

Radiation synthesis of biocompatible hydrogels of dextran methacrylate

NASA Astrophysics Data System (ADS)

Szafulera, Kamila; Wach, Radosław A.; Olejnik, Alicja K.; Rosiak, Janusz M.; Ulański, Piotr

2018-01-01

The aim of this work was to synthesize biocompatible dextran-based hydrogels through crosslinking initiated by ionizing radiation. A series of derivatives of dextran has been synthesized by coupling of methacrylated glycidyl to the structure of this polysaccharide, yielding dextran methacrylate (Dex-MA) of the degree of methacrylate substitution (DS) up to 1.13 as characterised by FTIR and NMR spectroscopy. Chemically crosslinked hydrogels were formed by electron-beam irradiation of Dex-MA in aqueous solution in the absence of low-molecular-weight additives such as catalysts, monomers or crosslinking agents. Crosslinking of Dex-MA in aqueous solutions of 20 g/l and above was an efficient process, the gels were formed at doses as low as 0.5 kGy (experiments conducted up to 100 kGy) and were characterised by high content of insoluble fraction (70-100%). Due to high crosslinking density the equilibrium degree of swelling of fabricated gels was controlled principally by the initial concentration of Dex-MA solution subjected to irradiation, and it was in the range of 20 to over 100 g of water absorbed by gram of gel. Cytocompatibility of hydrogels was examined using XTT assay through evaluation of the cell viability being in indirect contact with hydrogels. The results indicated that hydrogels of Dex-MA of the average DS below 1 were not cytotoxic. Altogether, our data demonstrate that irradiation of methacrylated dextran in aqueous solution is an efficient method of fabrication of biocompatible hydrogels, which applications in regeneration medicine are anticipated.

Direct and continuous synthesis of VO2 nanoparticles

NASA Astrophysics Data System (ADS)

Powell, M. J.; Marchand, P.; Denis, C. J.; Bear, J. C.; Darr, J. A.; Parkin, I. P.

2015-11-01

Monoclinic VO2 nanoparticles are of interest due to the material's thermochromic properties, however, direct synthesis routes to VO2 nanoparticles are often inaccessible due to the high synthesis temperatures or long reaction times required. Herein, we present a two-step synthesis route for the preparation of monoclinic VO2 nanoparticles using Continuous Hydrothermal Flow Synthesis (CHFS) followed by a short post heat treatment step. A range of particle sizes, dependent on synthesis conditions, were produced from 50 to 200 nm by varying reaction temperatures and the residence times in the process. The nanoparticles were characterised by powder X-ray diffraction, Raman and UV/Vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The nanoparticles were highly crystalline with rod and sphere-like morphologies present in TEM micrographs, with the size of both the rod and spherical particles being highly dependent on both reaction temperature and residence time. SEM micrographs showed the surface of the powders produced from the CHFS process to be highly uniform. The samples were given a short post synthesis heat treatment to ensure that they were phase pure monoclinic VO2, which led to them exhibiting a large and reversible switch in optical properties (at near-IR wavelengths), which suggests that if such materials can be incorporated into coatings or in composites, they could be used for fenestration in architectural applications.

Direct and continuous synthesis of VO2 nanoparticles.

PubMed

Powell, M J; Marchand, P; Denis, C J; Bear, J C; Darr, J A; Parkin, I P

2015-11-28

Monoclinic VO2 nanoparticles are of interest due to the material's thermochromic properties, however, direct synthesis routes to VO2 nanoparticles are often inaccessible due to the high synthesis temperatures or long reaction times required. Herein, we present a two-step synthesis route for the preparation of monoclinic VO2 nanoparticles using Continuous Hydrothermal Flow Synthesis (CHFS) followed by a short post heat treatment step. A range of particle sizes, dependent on synthesis conditions, were produced from 50 to 200 nm by varying reaction temperatures and the residence times in the process. The nanoparticles were characterised by powder X-ray diffraction, Raman and UV/Vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The nanoparticles were highly crystalline with rod and sphere-like morphologies present in TEM micrographs, with the size of both the rod and spherical particles being highly dependent on both reaction temperature and residence time. SEM micrographs showed the surface of the powders produced from the CHFS process to be highly uniform. The samples were given a short post synthesis heat treatment to ensure that they were phase pure monoclinic VO2, which led to them exhibiting a large and reversible switch in optical properties (at near-IR wavelengths), which suggests that if such materials can be incorporated into coatings or in composites, they could be used for fenestration in architectural applications.

[Synthesis and physico-chemical characterisation of some new derivatives of rutoside and clofibric acid].

PubMed

Lupaşcu, D; Profire, Lenuţa; Dănilă, Gh

2006-01-01

Fibrates are drugs with efficacy in reducing blood cholesterol levels and especially, triglyceride plasma levels. Unfortunately, fibrates have a poor water-solubility and showed some adverse reactions at long treatment. The objective of this study was to obtain some new clofibric acid derivatives with rutin; some of these compounds contain a guanidine moiety, known as effective at cardiovascular level. All the compounds are soluble in water.

Synthesis and DNA interaction of a mixed proflavine-phenanthroline Tröger base.

PubMed

Baldeyrou, Brigitte; Tardy, Christelle; Bailly, Christian; Colson, Pierre; Houssier, Claude; Charmantray, Franck; Demeunynck, Martine

2002-04-01

We report the synthesis of an asymmetric Tröger base containing the two well characterised DNA binding chromophores, proflavine and phenanthroline. The mode of interaction of the hybrid molecule was investigated by circular and linear dichroism experiments and a biochemical assay using DNA topoisomerase I. The data are compatible with a model in which the proflavine moiety intercalates between DNA base pairs and the phenanthroline ring occupies the DNA groove. DNase I cleavage experiments were carried out to investigate the sequence preference of the hybrid ligand and a well resolved footprint was detected at a site encompassing two adjacent 5'-GTC.5-GAC triplets. The sequence preference of the asymmetric molecule is compared to that of the symmetric analogues.

Cellular and molecular maturation in fetal and adult ovine calcaneal tendons

PubMed Central

Russo, Valentina; Mauro, Annunziata; Martelli, Alessandra; Di Giacinto, Oriana; Di Marcantonio, Lisa; Nardinocchi, Delia; Berardinelli, Paolo; Barboni, Barbara

2015-01-01

Processes of development during fetal life profoundly transform tendons from a plastic tissue into a highly differentiated structure, characterised by a very low ability to regenerate after injury in adulthood. Sheep tendon is frequently used as a translational model to investigate cell-based regenerative approaches. However, in contrast to other species, analytical and comparative baseline studies on the normal developmental maturation of sheep tendons from fetal through to adult life are not currently available. Thus, a detailed morphological and biochemical study was designed to characterise tissue maturation during mid- (2 months of pregnancy: 14 cm of length) and late fetal (4 months: 40 cm of length) life, through to adulthood. The results confirm that ovine tendon morphology undergoes profound transformations during this period. Endotenon was more developed in fetal tendons than in adult tissues, and its cell phenotype changed through tendon maturation. Indeed, groups of large rounded cells laying on smaller and more compacted ones expressing osteocalcin, vascular endothelial growth factor (VEGF) and nerve growth factor (NGF) were identified exclusively in fetal mid-stage tissues, and not in late fetal or adult tendons. VEGF, NGF as well as blood vessels and nerve fibers showed decreased expression during tendon development. Moreover, the endotenon of mid- and late fetuses contained identifiable cells that expressed several pluripotent stem cell markers [Telomerase Reverse Transcriptase (TERT), SRY Determining Region Y Box-2 (SOX2), Nanog Homeobox (NANOG) and Octamer Binding Transcription Factor-4A (OCT-4A)]. These cells were not identifiable in adult specimens. Ovine tendon development was also accompanied by morphological modifications to cell nuclei, and a progressive decrease in cellularity, proliferation index and expression of connexins 43 and 32. Tendon maturation was similarly characterised by modulation of several other gene expression profiles, including Collagen type I, Collagen type III, Scleraxis B, Tenomodulin, Trombospondin 4 and Osteocalcin. These gene profiles underwent a dramatic reduction in adult tissues. Transforming growth factor-1 expression (involved in collagen synthesis) underwent a similar decrease. In conclusion, these morphological studies carried out on sheep tendons at different stages of development and aging offer normal structural and molecular baseline data to allow accurate evaluation of data from subsequent interventional studies investigating tendon healing and regeneration in ovine experimental models. PMID:25546075

Characterisation of transition state structures for protein folding using 'high', 'medium' and 'low' {Phi}-values.

PubMed

Geierhaas, Christian D; Salvatella, Xavier; Clarke, Jane; Vendruscolo, Michele

2008-03-01

It has been suggested that Phi-values, which allow structural information about transition states (TSs) for protein folding to be obtained, are most reliably interpreted when divided into three classes (high, medium and low). High Phi-values indicate almost completely folded regions in the TS, intermediate Phi-values regions with a detectable amount of structure and low Phi-values indicate mostly unstructured regions. To explore the extent to which this classification can be used to characterise in detail the structure of TSs for protein folding, we used Phi-values divided into these classes as restraints in molecular dynamics simulations. This type of procedure is related to that used in NMR spectroscopy to define the structure of native proteins from the measurement of inter-proton distances derived from nuclear Overhauser effects. We illustrate this approach by determining the TS ensembles of five proteins and by showing that the results are similar to those obtained by using as restraints the actual numerical Phi-values measured experimentally. Our results indicate that the simultaneous consideration of a set of low-resolution Phi-values can provide sufficient information for characterising the architecture of a TS for folding of a protein.

Characterisation of transition state structures for protein folding using ‘high’, ‘medium’ and ‘low’ Φ-values

PubMed Central

Geierhaas, Christian D.; Salvatella, Xavier; Clarke, Jane; Vendruscolo, Michele

2008-01-01

It has been suggested that Φ-values, which allow structural information about transition states (TSs) for protein folding to be obtained, are most reliably interpreted when divided into three classes (high, medium and low). High Φ-values indicate almost completely folded regions in the TS, intermediate Φ-values regions with a detectable amount of structure and low Φ-values indicate mostly unstructured regions. To explore the extent to which this classification can be used to characterise in detail the structure of TSs for protein folding, we used Φ-values divided into these classes as restraints in molecular dynamics simulations. This type of procedure is related to that used in NMR spectroscopy to define the structure of native proteins from the measurement of inter-proton distances derived from nuclear Overhauser effects. We illustrate this approach by determining the TS ensembles of five proteins and by showing that the results are similar to those obtained by using as restraints the actual numerical Φ-values measured experimentally. Our results indicate that the simultaneous consideration of a set of low-resolution Φ-values can provide sufficient information for characterising the architecture of a TS for folding of a protein. PMID:18299294

Synthesis by sol-gel process, structural and optical properties of nanoparticles of zinc oxide doped vanadium

NASA Astrophysics Data System (ADS)

El Ghoul, J.; Barthou, C.; El Mir, L.

2012-06-01

We report the elaboration of vanadium-doped ZnO nanoparticles prepared by a sol-gel processing technique. In our approach, the water for hydrolysis was slowly released by esterification reaction followed by a supercritical drying in ethyl alcohol. Vanadium doping concentration of 10 at.% has been investigated. After treatment in air at different temperatures, the obtained nanopowder was characterised by various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and photoluminescence (PL). Analysis by scanning electron microscopy at high resolution shows that the grain size increases with increasing temperature. Thus, in the case of thermal treatment at 500 °C in air, the powder with an average particle size of 25 nm shows a strong luminescence band in the visible range. The intensity and energy position of the obtained PL band depends on the temperature measurement increase. The mechanism of this emission band is discussed.

Studies on frequency dependent electrical and dielectric properties of sintered zinc oxide pellets: effects of Al-doping

NASA Astrophysics Data System (ADS)

Tewari, S.; Ghosh, A.; Bhattacharjee, A.

2016-11-01

Sintered pellets of zinc oxide (ZnO), both undoped and Al-doped are prepared through a chemical process. Dopant concentration of Aluminium in ZnO [Al/Zn in weight percentage (wt%)] is varied from 0 to 3 wt%. After synthesis structural characterisation of the samples are performed with XRD and SEM-EDAX which confirm that all the samples are of ZnO having polycrystalline nature with particle size from 108.6 to 116 nm. Frequency dependent properties like a.c. conductivity, capacitance, impedance and phase angle are measured in the frequency range 10 Hz to 100 kHz as a function of temperature (in the range 25-150 °C). Nature of a.c. conductivity in these samples indicates hopping type of conduction arising from localised defect states. The frequency and temperature dependent properties under study are found to be as per correlated barrier hoping model. Dielectric and impedance properties studied in the samples indicate distributed relaxation, showing decrease of relaxation time with temperature.

Synthesis and Analysis of the Structure, Diffusion and Cytotoxicity of Heterocyclic Platinum(IV) Complexes.

PubMed

Macias, Freddy J; Deo, Krishant M; Pages, Benjamin J; Wormell, Paul; Clegg, Jack K; Zhang, Yingjie; Li, Feng; Zheng, Gang; Sakoff, Jennette; Gilbert, Jayne; Aldrich-Wright, Janice R

2015-11-16

We have developed six dihydroxidoplatinum(IV) compounds with cytotoxic potential. Each derived from active platinum(II) species, these complexes consist of a heterocyclic ligand (HL) and ancillary ligand (AL) in the form [Pt(HL)(AL)(OH)2](2+), where HL is a methyl-functionalised variant of 1,10-phenanthroline and AL is the S,S or R,R isomer of 1,2-diaminocyclohexane. NMR characterisation and X-ray diffraction studies clearly confirmed the coordination geometry of the octahedral platinum(IV) complexes. The self-stacking of these complexes was determined using pulsed gradient stimulated echo nuclear magnetic resonance. The self-association behaviour of square planar platinum(II) complexes is largely dependent on concentration, whereas platinum(IV) complexes do not aggregate under the same conditions, possibly due to the presence of axial ligands. The cytotoxicity of the most active complex, exhibited in several cell lines, has been retained in the platinum(IV) form. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and in vitro evaluation of new derivatives of 2-substituted-6-fluorobenzo[d]thiazoles as cholinesterase inhibitors.

PubMed

Imramovský, Aleš; Pejchal, Vladimír; Štěpánková, Šárka; Vorčáková, Katarína; Jampílek, Josef; Vančo, Ján; Šimůnek, Petr; Královec, Karel; Brůčková, Lenka; Mandíková, Jana; Trejtnar, František

2013-04-01

A series of novel cholinesterase inhibitors based on 2-substituted 6-fluorobenzo[d]thiazole were synthesised and characterised by IR, (1)H, (13)C and (19)F NMR spectroscopy and HRMS. Purity was checked by elemental analyses. The novel carbamates were tested for their ability to inhibit acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). The toxicity of the most active compounds was investigated using a standard in vitro test with HepG2 cells, and the ratio between biological activity and toxicity was determined. In addition, the toxicity of the most active compounds was evaluated against MCF7 cells using the xCELLigence system. Structure-activity relationships reflecting the dependence of cholinesterase inhibitors on the lipophilicity of the compounds as well as on the Taft polar and steric substituent constants are discussed. The specific orientation of the inhibitors in the binding site of acetylcholinesterase was determined using molecular docking of the most active compound. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mechanochemical synthesis and intercalation of Ca(II)Fe(III)-layered double hydroxides

NASA Astrophysics Data System (ADS)

Ferencz, Zs.; Szabados, M.; Varga, G.; Csendes, Z.; Kukovecz, Á.; Kónya, Z.; Carlson, S.; Sipos, P.; Pálinkó, I.

2016-01-01

A mechanochemical method (grinding the components without added water - dry grinding, followed by further grinding in the presence of minute amount of water or NaOH solution - wet grinding) was used in this work for the preparation and intercalation of CaFe-layered double hydroxides (LDHs). Both the pristine LDHs and the amino acid anion (cystinate and tyrosinate) intercalated varieties were prepared by the two-step grinding procedure in a mixer mill. By systematically changing the conditions of the preparation method, a set of parameters could be determined, which led to the formation of close to phase-pure LDH. The optimisation procedure was also applied for the intercalation processes of the amino acid anions. The resulting materials were structurally characterised by a range of methods (X-ray diffractometry, scanning electron microscopy, energy dispersive analysis, thermogravimetry, X-ray absorption and infra-red spectroscopies). It was proven that this simple mechanochemical procedure was able to produce complex organic-inorganic nanocomposites: LDHs intercalated with amino acid anions.

The bipyridine adducts of N-phenyldithiocarbamato complexes of Zn(II) and Cd(II); synthesis, spectral, thermal decomposition studies and use as precursors for ZnS and CdS nanoparticles

NASA Astrophysics Data System (ADS)

Onwudiwe, Damian C.; Strydom, Christien A.

2015-01-01

Bipyridine adducts of N-phenyldithiocarbamato complexes, [ML12L2] (M = Cd(II), Zn(II); L1 = N-phenyldithiocarbamate, L2 = 2,2‧ bipyridine), have been synthesized and characterised. The decomposition of these complexes to metal sulphides has been investigated by thermogravimetric analysis (TGA). The complexes were used as single-source precursors to synthesize MS (M = Zn, Cd) nanoparticles (NPs) passivated by hexadecyl amine (HDA). The growth of the nanoparticles was carried out at two different temperatures: 180 and 220 °C, and the optical and structural properties of the nanoparticles were studied using UV-Vis spectroscopy, photoluminescence spectroscopy (PL), transmission emission microscopy (TEM) and powdered X-ray diffraction (p-XRD). Nanoparticles, whose average diameters are 2.90 and 3.54 nm for ZnS, and 8.96 and 9.76 nm for CdS grown at 180 and 220 °C respectively, were obtained.

Molecular ways to nanoscale particles and films

NASA Astrophysics Data System (ADS)

Shen, H.; Mathur, S.

2002-06-01

Chemical routes for the synthesis of nanoparticles and films are proving to be highly efficient and versatile in tailoring the elemental combination and intrinsic properties of the target materials. The use of molecular compounds allows a controlled interaction of atoms or molecules, when compared to the solid-state methods, resulting in the formation of compositionally homogeneous deposits or uniform solid particles. Assembling all the elements forming the material in a single molecular compound, the so-called single-source approach augments the formation of nanocrystalline phases at low temperatures with atomically precise structures. To this end, we have shown that predefined reaction (decomposition) chemistry of precursors enforces a molecular level homogeneity in the obtained materials. Following the single-step conversions of appropriate molecular sources, we have obtained films and nanoparticles of oxides (Fe3O4, BaTiO3, ZnAl2O4, CoAl2O4), metal/oxide composites (Ge/GeO2) and ceramic-ceramic composites (LnAIO3/AI2O3; Ln = Pr, Nd). For a comparative evaluation, CoAl2O4 nanoparticles were prepared by both single- and multi-component routes; whereas the single-source approach yielded monophasic high purity spinels, phase contamination, due to monometal phases, was observed in the ceramic obtained from multicomponent mixture. An account of the size-controlled synthesis and characterisation of the new ceramics and composites is presented.

Polycrystalline ZnO and Mn-doped ZnO nanorod arrays with variable dopant content via a template based synthesis from Zn(II) and Mn(II) Schiff base type single source molecular precursors

NASA Astrophysics Data System (ADS)

Pashchanka, Mikhail; Hoffmann, Rudolf C.; Burghaus, Olaf; Corzilius, Björn; Cherkashinin, Gennady; Schneider, Jörg J.

2011-01-01

The synthesis and full characterisation of pure and Mn-doped polycrystalline zinc oxide nanorods with tailored dopant content are obtained via a single source molecular precursor approach using two Schiff base type coordination compounds is reported. The infiltration of precursor solutions into the cylindrical pores of a polycarbonate template and their thermal conversion into a ceramic green body followed by dissolution of the template gives the desired ZnO and Mn-doped ZnO nanomaterial as compact rods. The ZnO nanorods have a mean diameter between 170 and 180 nm or 60-70 nm, depending on the template pore size employed, comprising a length of 5-6 μm. These nanorods are composed of individual sub-5 nm ZnO nanocrystals. Exact doping of these hierarchically structured ZnO nanorods was achieved by introducing Mn(II) into the ZnO host lattice with the precursor complex Diaquo-bis[2-(meth-oxyimino)-propanoato]manganese, which allows to tailor the exact Mn(II) doping content of the ZnO rods. Investigation of the Mn-doped ZnO samples by XRD, TEM, XPS, PL and EPR, reveals that manganese occurs exclusively in its oxidation state + II and is distributed within the volume as well as on the surface of the ZnO host.

Molecular characterisation of a mosaicism with a complex chromosome rearrangement: evidence for coincident chromosome healing by telomere capture and neo‐telomere formation

PubMed Central

Chabchoub, Elyes; Rodríguez, Laura; Galán, Enrique; Mansilla, Elena; Martínez‐Fernandez, Maria Luisa; Martínez‐Frías, Maria Luisa; Fryns, Jean‐Pierre; Vermeesch, Joris Robert

2007-01-01

Background Broken chromosomes must acquire new telomeric “caps” to be structurally stable. Chromosome healing can be mediated either by telomerase through neo‐telomere synthesis or by telomere capture. Aim To unravel the mechanism(s) generating complex chromosomal mosaicisms and healing broken chromosomes. Methods G banding, array comparative genomic hybridization (aCGH), fluorescence in‐situ hybridisation (FISH) and short tandem repeat analysis (STR) was performed on a girl presenting with mental retardation, facial dysmorphism, urogenital malformations and limb anomalies carrying a complex chromosomal mosaicism. Results & discussion The karyotype showed a de novo chromosome rearrangement with two cell lines: one cell line with a deletion 9pter and one cell line carrying an inverted duplication 9p and a non‐reciprocal translocation 5pter fragment. aCGH, FISH and STR analysis enabled the deduction of the most likely sequence of events generating this complex mosaic. During embryogenesis, a double‐strand break occurred on the paternal chromosome 9. Following mitotic separation of both broken sister chromatids, one acquired a telomere vianeo‐telomere formation, while the other generated a dicentric chromosome which underwent breakage during anaphase, giving rise to the del inv dup(9) that was subsequently healed by chromosome 5 telomere capture. Conclusion Broken chromosomes can coincidently be rescued by both telomere capture and neo‐telomere synthesis. PMID:17172463

Sport science integration: An evolutionary synthesis.

PubMed

Balagué, N; Torrents, C; Hristovski, R; Kelso, J A S

2017-02-01

The aim of the paper is to point out one way of integrating the supposedly incommensurate disciplines investigated in sports science. General, common principles can be found among apparently unrelated disciplines when the focus is put on the dynamics of sports-related phenomena. Dynamical systems approaches that have recently changed research in biological and social sciences among others, offer key concepts to create a common pluricontextual language in sport science. This common language, far from being homogenising, offers key synthesis between diverse fields, respecting and enabling the theoretical and experimental pluralism. It forms a softly integrated sports science characterised by a basic dynamic explanatory backbone as well as context-dependent theoretical flexibility. After defining the dynamic integration in living systems, unable to be captured by structural static approaches, we show the commonalities between the diversity of processes existing on different levels and time scales in biological and social entities. We justify our interpretation by drawing on some recent scientific contributions that use the same general principles and concepts, and diverse methods and techniques of data analysis, to study different types of phenomena in diverse disciplines. We show how the introduction of the dynamic framework in sport science has started to blur the boundaries between physiology, biomechanics, psychology, phenomenology and sociology. The advantages and difficulties of sport science integration and its consequences in research are also discussed.

Non-Noble Metal Oxide Catalysts for Methane Catalytic Combustion: Sonochemical Synthesis and Characterisation

PubMed Central

Jędrzejczyk, Roman J.; Dziedzicka, Anna; Kuterasiński, Łukasz; Sitarz, Maciej

2017-01-01

The aim of this study was to obtain nanocrystalline mixed metal-oxide–ZrO2 catalysts via a sonochemically-induced preparation method. The effect of a stabiliser’s addition on the catalyst parameters was investigated by several characterisation methods including X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The sonochemical preparation method allowed us to manufacture the catalysts with uniformly dispersed metal-oxide nanoparticles at the support surface. The catalytic activity was tested in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was higher than that of the reference catalysts prepared by the incipient wetness method without ultrasonic irradiation. The cobalt and chromium mixed zirconia catalysts revealed their high activities, which are comparable with those presented in the literature. PMID:28686190

Characterisation of serpin polymers in vitro and in vivo.

PubMed

Belorgey, Didier; Irving, James A; Ekeowa, Ugo I; Freeke, Joanna; Roussel, Benoit D; Miranda, Elena; Pérez, Juan; Robinson, Carol V; Marciniak, Stefan J; Crowther, Damian C; Michel, Claire H; Lomas, David A

2011-03-01

Neuroserpin is a member of the serine protease inhibitor or serpin superfamily of proteins. It is secreted by neurones and plays an important role in the regulation of tissue plasminogen activator at the synapse. Point mutations in the neuroserpin gene cause the autosomal dominant dementia familial encephalopathy with neuroserpin inclusion bodies or FENIB. This is one of a group of disorders caused by mutations in the serpins that are collectively known as the serpinopathies. Others include α(1)-antitrypsin deficiency and deficiency of C1 inhibitor, antithrombin and α(1)-antichymotrypsin. The serpinopathies are characterised by delays in protein folding and the retention of ordered polymers of the mutant serpin within the cell of synthesis. The clinical phenotype results from either a toxic gain of function from the inclusions or a loss of function, as there is insufficient protease inhibitor to regulate important proteolytic cascades. We describe here the methods required to characterise the polymerisation of neuroserpin and draw parallels with the polymerisation of α(1)-antitrypsin. It is important to recognise that the conditions in which experiments are performed will have a major effect on the findings. For example, incubation of monomeric serpins with guanidine or urea will produce polymers that are not found in vivo. The characterisation of the pathological polymers requires heating of the folded protein or alternatively the assessment of ordered polymers from cell and animal models of disease or from the tissues of humans who carry the mutation. Copyright © 2010 Elsevier Inc. All rights reserved.

Linking composition of extracellular polymeric substances (EPS) to the physical structure and hydraulic resistance of membrane biofilms.

PubMed

Desmond, Peter; Best, James P; Morgenroth, Eberhard; Derlon, Nicolas

2018-04-01

The effect of extracellular polymeric substances (EPS) on the meso-scale physical structure and hydraulic resistance of membrane biofilms during gravity driven membrane (GDM) filtration was investigated. Biofilms were developed on the surface of ultrafiltration membranes during dead-end filtration at ultra-low pressure (70 mbar). Biofilm EPS composition (total protein, polysaccharide and eDNA) was manipulated by growing biofilms under contrasting nutrient conditions. Nutrient conditions consisted of (i) a nutrient enriched condition with a nutrient ratio of 100:30:10 (C: N: P), (ii) a phosphorus limitation (C: N: P ratio: 100:30:0), and (iii) a nitrogen limitation (C: N: P ratio: 100:0:10). The structure of the biofilm was characterised at meso-scale using Optical Coherence Tomography (OCT). Biofilm composition was analysed with respect to total organic carbon, total cellular mass and extracellular concentrations of proteins, polysaccharides, and eDNA. 2D-confocal Raman mapping was used to characterise the functional group composition and micro-scale distribution of the biofilms EPS. Our study reveals that the composition of the EPS matrix can determine the meso-scale physical structure of membrane biofilms and in turn its hydraulic resistance. Biofilms grown under P limiting conditions were characterised by dense and homogeneous physical structures with high concentrations of polysaccharides and eDNA. Biofilm grown under nutrient enriched or N limiting conditions were characterised by heterogeneous physical structures with lower concentrations of polysaccharides and eDNA. For P limiting biofilms, 2D-confocal Raman microscopy revealed a homogeneous spatial distribution of anionic functional groups in homogeneous biofilm structures with higher polysaccharide and eDNA concentrations. This study links EPS composition, physical structure and hydraulic resistance of membrane biofilms, with practical relevance for the hydraulic performances of GDM ultrafiltration. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ellipsometric porosimetry on pore-controlled TiO2 layers

NASA Astrophysics Data System (ADS)

Rosu, Dana-Maria; Ortel, Erik; Hodoroaba, Vasile-Dan; Kraehnert, Ralph; Hertwig, Andreas

2017-11-01

The practical performance of surface coatings in applications like catalysis, water splitting or batteries depends critically on the coating materials' porosity. Determining the porosity in a fast and non-destructive way is still an unsolved problem for industrial thin-films technology. As a contribution to calibrated, non-destructive, optical layer characterisation, we present a multi-method comparison study on porous TiO2 films deposited by sol-gel synthesis on Si wafers. The ellipsometric data were collected on a range of samples with different TiO2 layer thickness and different porosity values. These samples were produced by templated sol-gel synthesis resulting in layers with a well-defined pore size and pore density. The ellipsometry measurement data were analysed by means of a Bruggeman effective medium approximation (BEMA), with the aim to determine the mixture ratio of void and matrix material by a multi-sample analysis strategy. This analysis yielded porosities and layer thicknesses for all samples as well as the dielectric function for the matrix material. Following the idea of multi-method techniques in metrology, the data was referenced to imaging by electron microscopy (SEM) and to a new EPMA (electron probe microanalysis) porosity approach for thin film analysis. This work might lead to a better metrological understanding of optical porosimetry and also to better-qualified characterisation methods for nano-porous layer systems.

Synthesis, characterisation and biomedical applications of curcumin conjugated chitosan microspheres.

PubMed

Saranya, T S; Rajan, V K; Biswas, Raja; Jayakumar, R; Sathianarayanan, S

2018-04-15

Curcumin is a diaryl heptanoid of curcuminoids class obtained from Curcuma longa. It possesses various biological activities like anti-inflammatory, hypoglycemic, antioxidant, wound-healing, and antimicrobial activities. Chitosan is a biocompatible, biodegradable and non-toxic natural polymer which enhances the adhesive property of the skin. Chemical conjugation will leads to sustained release action and to enhance the bioavailability. This study aims to synthesis and characterize biocompatible curcumin conjugated chitosan microspheres for bio-medical applications. The Schiff base reaction was carried out for the preparation of curcumin conjugated chitosan by microwave method and it was characterised using FTIR and NMR. Curcumin conjugated chitosan microspheres (CCCMs) were prepared by wet milling solvent evaporation method. SEM analysis showed these CCCMs were 2-5μm spherical particles. The antibacterial activities of the prepared CCCMs were studied against Staphylococcus aureus and Escherichia coli, the zone of inhibition was 28mm and 23mm respectively. Antioxidant activity of the prepared CCCMs was also studied by DPPH and H 2 O 2 method it showed IC 50 esteem value of 216μg/ml and 228μg/ml, and anti-inflammatory activity results showed that CCCMs having IC 50 value of 45μg/ml. The results conclude that the CCCMs having a good antibacterial, antioxidant and anti-inflammatory activities. This, the prepared CCCMs have potential application in preventing skin infections. Copyright © 2017. Published by Elsevier B.V.

Microbiological characterisation of Burkholderia cepacia isolates from cystic fibrosis patients: investigation of the exopolysaccharides produced.

PubMed

Lagatolla, Cristina; Skerlavaj, Silvia; Dolzani, Lucilla; Tonin, Enrico A; Monti Bragadin, Carlo; Bosco, Marco; Rizzo, Roberto; Giglio, Luisella; Cescutti, Paola

2002-03-19

Eleven strains of Burkholderia cepacia were isolated directly from clinical specimens: 10 from sputum of cystic fibrosis patients, and one from a vaginal swab. They were biochemically identified using API20NE and confirmed by a PCR-based assay. The genomovar characterisation obtained by specific PCR amplification revealed seven strains belonging to genomovar I, three belonging to genomovar IIIA and one belonging to genomovar IV. All isolates were also typed by ribotyping and random amplification of polymorphic DNA analysis. Some of the characterised strains were examined for the ability to produce exopolysaccharides, with the aim of correlating the genomovar with the exopolysaccharide structure. The polysaccharides were analysed by means of methylation analysis and 1H-NMR spectroscopy in order to determine structural similarities. It was shown that different strains are capable of producing chemically different polysaccharides.

Characterisation of a novel enterobacteria phage, CAjan, isolated from rat faeces.

PubMed

Carstens, Alexander B; Kot, Witold; Lametsch, Rene; Neve, Horst; Hansen, Lars H

2016-08-01

In this study, we describe the isolation and characterisation of the novel enterobacteria phage CAjan. This phage belongs to the order Caudovirales and the family Siphoviridae. The phage possesses a linear, double-stranded DNA genome consisting of 59,670 bp with a G+C content of 44.7 % and 91 predicted open reading frames (ORFs). Putative functions were assigned to 39 of the ORFs (37.4 %). The phage structural genes were furthermore functionally characterised by LC MS/MS. CAjan, together with Escherichia phage Seurat and Escherichia phage slur01, represent a novel and genetically distinct clade of Siphoviridae phages that could be considered to constitute a new phage genus. Despite limited sequence similarity, the phages in this group share a number of other common features, including genome structure and the presence of queuosine biosynthesis genes.

Synthesis and solid-state characterisation of 4-substituted methylidene oxindoles

PubMed Central

2013-01-01

Background 4-substituted methylidene oxindoles are pharmacologically important. Detailed analysis and comparison of all the interactions present in crystal structures is necessary to understand how these structures arise. The XPac procedure allows comparison of complete crystal structures of related families of compounds to identify assemblies that are mainly the result of close-packing as well as networks of directed interactions. Results Five 4-substituted methylidene oxindoles have been synthesized by the Knoevenagel condensation of oxindole with para-substituted aromatic aldehydes and were characterized in the solid state by x-ray crystallography. Hence, the structures of (3E)-3-(4-Bromobenzylidene)-1,3-dihydro-2H-indol-2-one, 3a, (3E)-3-(4-Chlorobenzylidene)-1,3-dihydro-2H-indol-2-one, 3b, (3E)-3-(4-Methoxybenzylidene)-1,3-dihydro-2H-indol-2-one, 3c, (3E)-3-(4-Methylbenzylidene)-1,3-dihydro-2H-indol-2-one, 3d and (3E)-3-(4-Nitrobenzylidene)-1,3-dihydro-2H-indol-2-one, 3e, were elucidated using single crystal X-ray crystallography. Conclusions A hydrogen bonded dimer molecular assembly or supramolecular construct was identified in all the crystal structures examined along with a further four 1D supramolecular constructs which were common to at least two of the family of structures studied. The 1D supramolecular constructs indicate that once the obvious strong interaction is satisfied to form hydrogen bonded dimer it is the conventionally weaker interactions, such as steric bulk and edge-to-face interactions which compete to influence the final structure formation. PMID:24517531

Catalytic-site mapping of pyruvate formate lyase. Hypophosphite reaction on the acetyl-enzyme intermediate affords carbon-phosphorus bond synthesis (1-hydroxyethylphosphonate).

PubMed

Plaga, W; Frank, R; Knappe, J

1988-12-15

Pyruvate formate-lyase of Escherichia coli cells, a homodimeric protein of 2 x 85 kDa, is distinguished by the property of containing a stable organic free radical (g = 2.0037) in its resting state. The enzyme (E-SH) achieves pyruvate conversion to acetyl-CoA via two distinct half-reactions (E-SH + pyruvate in equilibrium E-S-acetyl + formate; E-S-acetyl + CoA in equilibrium E-SH + acetyl-CoA), the first of which has been proposed to involve reversible homolytic carbon-carbon bond cleavage [J. Knappe et al. (1984) Proc. Natl Acad. Sci. USA 81, 1332-1335]. Present studies identified Cys-419 as the covalent-catalytic cysteinyl residue via CNBr fragmentation of E-S-[14C]acetyl and radio-sequencing of the isolated peptide CB-Ac (amino acid residues 406-423). Reaction of the formate analogue hypophosphite with E-S-acetyl was investigated and found to produce 1-hydroxyethylphosphonate with a thioester linkage to the adjacent Cys-418. The structure was determined from the chymotryptic peptide CH-P (amino acid residues 415-425), using 31P-NMR spectroscopy (delta = 44 ppm) and by chemical characterisation through degradation into 1-hydroxyethylphosphonate with phosphodiesterase or bromine. This novel P-C-bond synthesis involves the enzyme-based free radical and is proposed to resemble the physiological C-C-bond synthesis (pyruvate production) from formate and E-S-acetyl. These findings are interpreted as proof of a radical mechanism for the action of pyruvate formate-lyase. The central Cys-418/Cys-419 pair of the active site shows a distinctive thiolate property even in the inactive (nonradical) form of the enzyme, as determined using an iodoacetate probe.

A Novel Synthesis Routine for Woodwardite and Its Affinity towards Light (La, Ce, Nd) and Heavy (Gd and Y) Rare Earth Elements.

PubMed

Consani, Sirio; Balić-Žunić, Tonci; Cardinale, Anna Maria; Sgroi, Walter; Giuli, Gabriele; Carbone, Cristina

2018-01-14

A synthetic Cu-Al-SO₄ layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu 1-x Al x (SO₄) x/2 (OH)₂·nH₂O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO₄ LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO₄ LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5-8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis.

A Novel Synthesis Routine for Woodwardite and Its Affinity towards Light (La, Ce, Nd) and Heavy (Gd and Y) Rare Earth Elements

PubMed Central

Consani, Sirio; Balić-Žunić, Tonci; Cardinale, Anna Maria; Sgroi, Walter; Giuli, Gabriele; Carbone, Cristina

2018-01-01

A synthetic Cu-Al-SO4 layered double hydroxide (LDH), analogue to the mineral woodwardite [Cu1−xAlx(SO4)x/2(OH)2·nH2O], with x < 0.5 and n ≤ 3x/2, was synthesised by adding a solution of Cu and Al sulphates to a solution with NaOH. The pH values were kept constant at 8.0 and 10.0 by a continuous addition of NaOH. The material obtained had poor crystallinity, turbostratic structure, and consisted of nanoscopic crystallites. The analyses performed in order to characterise the obtained materials (X-ray diffraction (XRD), thermogravimetry (TG), and Fourier Transform Infra-Red (FTIR) spectroscopy) showed that the Cu-Al-SO4 LDH is very similar to woodwardite, although it has a smaller layer spacing, presumably due to a lesser water content than in natural samples. The synthesis was performed by adding light rare earth elements (LREEs) (La, Ce, and Nd) and heavy rare earth elements (HREEs) (Gd and Y) in order to test the affinity of the Cu-Al-SO4 LDH to the incorporation of REEs. The concentration of rare earth elements (REEs) in the solid fraction was in the range of 3.5–8 wt %. The results showed a good affinity for HREE and Nd, especially for materials synthesised at pH 10.0, whereas the affinities for Ce and La were much lower or non-existent. The thermal decomposition of the REE-doped materials generates a mixture of Cu, Al, and REE oxides, making them interesting as precursors in REE oxide synthesis. PMID:29342887

Synthesis of the Galactosyl Derivative of Gluconic Acid With the Transglycosylation Activity of β-Galactosidase

PubMed Central

2017-01-01

Summary Bionic acids are bioactive compounds demonstrating numerous interesting properties. They are widely produced by chemical or enzymatic oxidation of disaccharides. This paper focuses on the galactosyl derivative of gluconic acid as a result of a new method of bionic acid synthesis which utilises the transglycosylation properties of β-galactosidase and introduces lactose as a substrate. Products obtained in such a process are characterised by different structures (and, potentially, properties) than those resulting from traditional oxidation of disaccharides. The aim of this study is to determine the effect of selected parameters (concentration and ratio of substrates, dose of the enzyme, time, pH, presence of salts) on the course of the reaction carried out with the enzymatic preparation Lactozym, containing β-galactosidase from Kluyveromyces lactis. Research has shown that increased dry matter content in the baseline solution (up to 50%, by mass per volume) and an addition of NaCl contribute to higher yield. On the other hand, reduced content of the derivative is a result of increased pH from 7.0 to 9.0 and an addition of magnesium and manganese salts. Moreover, exceeding the β-galactosidase dose over approx. 35 000 U per 100 g of lactose also leads to reduced yield of the process. The most favourable molar ratio of sodium gluconate to lactose is 2.225:0.675. Depending on the conditions of the synthesis, the product concentration ranged between 17.3 and 118.3 g/L of the reaction mixture, which corresponded to the mass fraction of 6.64–23.7% of dry matter. The data obtained as a result of the present study may be useful for designing an industrial process. PMID:28867957

One-step colloidal synthesis of biocompatible water-soluble ZnS quantum dot/chitosan nanoconjugates

NASA Astrophysics Data System (ADS)

Ramanery, Fábio P.; Mansur, Alexandra AP; Mansur, Herman S.

2013-12-01

Quantum dots (QDs) are luminescent semiconductor nanocrystals with great prospective for use in biomedical and environmental applications. Nonetheless, eliminating the potential cytotoxicity of the QDs made with heavy metals is still a challenge facing the research community. Thus, the aim of this work was to develop a novel facile route for synthesising biocompatible QDs employing carbohydrate ligands in aqueous colloidal chemistry with optical properties tuned by pH. The synthesis of ZnS QDs capped by chitosan was performed using a single-step aqueous colloidal process at room temperature. The nanobioconjugates were extensively characterised by several techniques, and the results demonstrated that the average size of ZnS nanocrystals and their fluorescent properties were influenced by the pH during the synthesis. Hence, novel 'cadmium-free' biofunctionalised systems based on ZnS QDs capped by chitosan were successfully developed exhibiting luminescent activity that may be used in a large number of possible applications, such as probes in biology, medicine and pharmacy.

Haemocompatibility assessment of synthesised platinum nanoparticles and its implication in biology.

PubMed

Shiny, P J; Mukherjee, Amitava; Chandrasekaran, N

2014-06-01

The growing need for advanced treatment of evolving diseases has become a motivation for this study. Among the noble metals, platinum nanoparticles are of importance because of their catalytic property, antioxidant potential, minimal toxicity and diverse applications. Biological process of synthesis has retained its significance, because it is a simple one-step process yielding stable nanoparticles. Herein, we have synthesised platinum nanoparticles through a green process using the unexplored seaweed Padina gymnospora, a brown alga. The course of synthesis was monitored and the nanoparticles were characterised using UV-visible spectroscopy. The synthesised nanoparticles were studied using TEM, XRD and FTIR. The TEM and XRD studies reveal the size of the nanoparticle to be <35 nm. The catalytic nanoparticles were capable of oxidising NADH to NAD(+). The biocompatibility was tested by haemolytic assay for the furtherance of the application of platinum nanoparticles in medicine. This is the first report on the biogenic synthesis of platinum nanoparticles using seaweed.

Synthesis, characterisation, and in vitro anticancer activity of curcumin analogues bearing pyrazole/pyrimidine ring targeting EGFR tyrosine kinase.

PubMed

Ahsan, Mohamed Jawed; Khalilullah, Habibullah; Yasmin, Sabina; Jadav, Surender Singh; Govindasamy, Jeyabalan

2013-01-01

In search of potential therapeutics for cancer, we described herein the synthesis, characterization, and in vitro anticancer activity of a novel series of curcumin analogues. The anticancer effects were evaluated on a panel of 60 cell lines, according to the National Cancer Institute (NCI) screening protocol. There were 10 tested compounds among 14 synthesized compounds, which showed potent anticancer activity in both one-dose and 5-dose assays. The most active compound of the series was 3,5-bis(4-hydroxy-3-methylstyryl)-1H-pyrazole-1-yl(phenyl)methanone which showed mean growth percent of -28.71 in one-dose assay and GI₅₀ values between 0.0079 and 1.86 µM in 5-dose assay.

Kangaroo IGF-II is structurally and functionally similar to the human [Ser29]-IGF-II variant.

PubMed

Yandell, C A; Francis, G L; Wheldrake, J F; Upton, Z

1999-06-01

Kangaroo IGF-II has been purified from western grey kangaroo (Macropus fuliginosus) serum and characterised in a number of in vitro assays. In addition, the complete cDNA sequence of mature IGF-II has been obtained by reverse-transcription polymerase chain reaction. Comparison of the kangaroo IGF-II cDNA sequence with known IGF-II sequences from other species revealed that it is very similar to the human variant, [Ser29]-hIGF-II. Both the variant and kangaroo IGF-II contain an insert of nine nucleotides that encode the amino acids Leu-Pro-Gly at the junction of the B and C domains of the mature protein. The deduced kangaroo IGF-II protein sequence also contains three other amino acid changes that are not observed in human IGF-II. These amino acid differences share similarities with the changes described in many of the IGF-IIs reported for non-mammalian species. Characterisation of human IGF-II, kangaroo IGF-II, chicken IGF-II and [Ser29]-hIGF-II in a number of in vitro assays revealed that all four proteins are functionally very similar. No significant differences were observed in the ability of the IGF-IIs to bind to the bovine IGF-II/cation-independent mannose 6-phosphate receptor or to stimulate protein synthesis in rat L6 myoblasts. However, differences were observed in their abilities to bind to IGF-binding proteins (IGFBPs) present in human serum. Kangaroo, chicken and [Ser29]-hIGF-II had lower apparent affinities for human IGFBPs than did human IGF-II. Thus, it appears that the major circulating form of IGF-II in the kangaroo and a minor form of IGF-II found in human serum are structurally and functionally very similar. This suggests that the splice site that generates both the variant and major form of human IGF-II must have evolved after the divergence of marsupials from placental mammals.

Enantioselective cellular localisation of europium(iii) coordination complexes† †Electronic supplementary information (ESI) available: Complex synthesis and characterisation, selected cell images showing correspondence with commercial lysosomal or mitochondrial stains and spectral imaging profiles. See DOI: 10.1039/c7sc04422d

PubMed Central

Frawley, Andrew T.; Linford, Holly V.; Starck, Matthieu; Pal, Robert

2017-01-01

The selective mitochondrial localisation of the Λ enantiomer of three different emissive europium(iii) complexes in NIH 3T3 and MCF7 cells contrasts with the behaviour of the Δ enantiomer, for which a predominant lysosomal localisation was observed by confocal microscopy. In each case, cell uptake occurs via macropinocytosis. PMID:29675151

Characterisation of the biofouling community on a floating wave energy device.

PubMed

Nall, Christopher R; Schläppy, Marie-Lise; Guerin, Andrew J

2017-05-01

Wave energy devices are novel structures in the marine environment and, as such, provide a unique habitat for biofouling organisms. In this study, destructive scrape samples and photoquadrats were used to characterise the temperate epibenthic community present on prototypes of the Pelamis wave energy converter. The biofouling observed was extensive and diverse with 115 taxa recorded including four non-native species. Vertical zonation was identified on the sides of the device, with an algae-dominated shallow subtidal area and a deeper area characterised by a high proportion of suspension-feeding invertebrates. Differences in species composition and biomass were also observed between devices, along the length of the device and between sampling dates. This research provides an insight into the variation of biofouling assemblages on a wave energy device as well as the potential technical and ecological implications associated with biofouling on marine renewable energy structures.

Silica Nanoparticles for Intracellular Protein Delivery: a Novel Synthesis Approach Using Green Fluorescent Protein

NASA Astrophysics Data System (ADS)

Schmidt, Sarah; Tavernaro, Isabella; Cavelius, Christian; Weber, Eva; Kümper, Alexander; Schmitz, Carmen; Fleddermann, Jana; Kraegeloh, Annette

2017-09-01

In this study, a novel approach for preparation of green fluorescent protein (GFP)-doped silica nanoparticles with a narrow size distribution is presented. GFP was chosen as a model protein due to its autofluorescence. Protein-doped nanoparticles have a high application potential in the field of intracellular protein delivery. In addition, fluorescently labelled particles can be used for bioimaging. The size of these protein-doped nanoparticles was adjusted from 15 to 35 nm using a multistep synthesis process, comprising the particle core synthesis followed by shell regrowth steps. GFP was selectively incorporated into the silica matrix of either the core or the shell or both by a one-pot reaction. The obtained nanoparticles were characterised by determination of particle size, hydrodynamic diameter, ζ-potential, fluorescence and quantum yield. The measurements showed that the fluorescence of GFP was maintained during particle synthesis. Cellular uptake experiments demonstrated that the GFP-doped nanoparticles can be used as stable and effective fluorescent probes. The study reveals the potential of the chosen approach for incorporation of functional biological macromolecules into silica nanoparticles, which opens novel application fields like intracellular protein delivery.

Characterisation of structure-borne sound source using reception plate method.

PubMed

Putra, A; Saari, N F; Bakri, H; Ramlan, R; Dan, R M

2013-01-01

A laboratory-based experiment procedure of reception plate method for structure-borne sound source characterisation is reported in this paper. The method uses the assumption that the input power from the source installed on the plate is equal to the power dissipated by the plate. In this experiment, rectangular plates having high and low mobility relative to that of the source were used as the reception plates and a small electric fan motor was acting as the structure-borne source. The data representing the source characteristics, namely, the free velocity and the source mobility, were obtained and compared with those from direct measurement. Assumptions and constraints employing this method are discussed.

Structure-level fuel load assessment in the wildland-urban interface: a fusion of airborne laser scanning and spectral remote-sensing methodologies

Treesearch

Nicholas S. Skowronski; Scott Haag; Jim Trimble; Kenneth L. Clark; Michael R. Gallagher; Richard G. Lathrop

2015-01-01

Large-scale fuel assessments are useful for developing policy aimed at mitigating wildfires in the wildland-urban interface (WUI), while finer-scale characterisation is necessary for maximising the effectiveness of fuel reduction treatments and directing suppression activities. We developed and tested an objective, consistent approach for characterising hazardous fuels...

Recognition of extended linear and cyclised polyketide mimics by a type II acyl carrier protein† †Electronic supplementary information (ESI) available: Detailed experimental procedures and characterisation data for all new compounds, additional spectra and structural statistics for derivatised ACP three-dimensional structures. See DOI: 10.1039/c5sc03864b Click here for additional data file.

PubMed Central

Dong, Xu; Bailey, Christopher D.; Williams, Christopher; Crosby, John; Simpson, Thomas J.

2016-01-01

Polyketides are secondary metabolites which display both valuable pharmaceutical and agrochemical properties. Biosynthesis is performed by polyketide synthases (PKSs), and the acyl carrier protein (ACP), a small acidic protein, that transports the growing polyketide chain and is essential for activity. Here we report the synthesis of two aromatic probes and a linear octaketide mimic that have been tethered to actinorhodin ACP. These experiments were aimed at probing the ACP's capacity to sequester a non-polar versus a phenolic aromatic ring (that more closely mimics a polyketide intermediate) as well as investigations with extended polyketide chain surrogates. The binding of these mimics has been assessed using high-resolution solution NMR studies and high-resolution structure determination. These results reveal that surprisingly a PKS ACP is able to bind and sequester a bulky non-polar substrate containing an aromatic ring in a fatty acid type binding mode, but the introduction of even a small degree of polarity favours a markedly different association at a surface site that is distinct from that employed by fatty acid ACPs. PMID:28936328

Characterising RNA secondary structure space using information entropy

PubMed Central

2013-01-01

Comparative methods for RNA secondary structure prediction use evolutionary information from RNA alignments to increase prediction accuracy. The model is often described in terms of stochastic context-free grammars (SCFGs), which generate a probability distribution over secondary structures. It is, however, unclear how this probability distribution changes as a function of the input alignment. As prediction programs typically only return a single secondary structure, better characterisation of the underlying probability space of RNA secondary structures is of great interest. In this work, we show how to efficiently compute the information entropy of the probability distribution over RNA secondary structures produced for RNA alignments by a phylo-SCFG, and implement it for the PPfold model. We also discuss interpretations and applications of this quantity, including how it can clarify reasons for low prediction reliability scores. PPfold and its source code are available from http://birc.au.dk/software/ppfold/. PMID:23368905

Visual texture for automated characterisation of geological features in borehole televiewer imagery

NASA Astrophysics Data System (ADS)

Al-Sit, Waleed; Al-Nuaimy, Waleed; Marelli, Matteo; Al-Ataby, Ali

2015-08-01

Detailed characterisation of the structure of subsurface fractures is greatly facilitated by digital borehole logging instruments, the interpretation of which is typically time-consuming and labour-intensive. Despite recent advances towards autonomy and automation, the final interpretation remains heavily dependent on the skill, experience, alertness and consistency of a human operator. Existing computational tools fail to detect layers between rocks that do not exhibit distinct fracture boundaries, and often struggle characterising cross-cutting layers and partial fractures. This paper presents a novel approach to the characterisation of planar rock discontinuities from digital images of borehole logs. Multi-resolution texture segmentation and pattern recognition techniques utilising Gabor filters are combined with an iterative adaptation of the Hough transform to enable non-distinct, partial, distorted and steep fractures and layers to be accurately identified and characterised in a fully automated fashion. This approach has successfully detected fractures and layers with high detection accuracy and at a relatively low computational cost.

Electronic properties of defects in silicon and related materials

NASA Astrophysics Data System (ADS)

Mitromara, Niki

Efforts in the current semiconductor industry are focused on the production of smaller, more efficient and inexpensive devices of higher packing density. As silicon is the dominant semiconductor implemented for the fabrication of the majority of semiconductor devices, perpetual research has focused on the improvement of its properties and the realisation of the most efficient structures. This thesis presents the electrical characterisation of two different diode structures that are important for the present and future generations of electronic devices.The first part of the thesis is focused on the electrical characterisation of Ultra-Shallow Junction (USJs) Si diodes. Both p+n and n+p USJ structures that contained different implants were examined. These were very highly doped and intended to simulate the situation where a doping well is formed after heavy doping in Si for the fabrication of transistors currently used in Complementary-Metal-Oxide-Semiconductor (CMOS) technology. The implanted USJ diodes were provided by NXP, Belgium and contact deposition was performed before their electrical characterisation as part of this project. Subsequently the p+n and n+p USJ diodes were characterised by the use of Capacitance-Voltage (CV), Current-Voltage (IV), Deep Level Transient Spectroscopy (DLTS) and high resolution Laplace DLTS (LDLTS). DLTS and LDLTS are very powerful spectroscopic techniques for the profiling of defects in the bandgap of a semiconductor as well as for the identification of the electrical signatures of these defects. Transient-Enhanced Diffusion (TED) related defects were detected in these diodes as the presence of mainly carbon-related interstitial complexes was observed. In addition, certain vacancy or vacancy-dopant related levels were also discerned.The second part of this thesis presents the electrical characterisation from Schottky p-diamond/p-Si and p-diamond/n-Si p-n diodes. These diodes were readily provided, grown by the Chemical Vapour Deposition (CVD) technique, for the electrical characterisation that was performed as part of this project. The purpose of characterising both Schottky and p-n diamond on Si diodes was to detect defects near the surface of the films and near the interface with Si and hence provide a comparison between defects present at the beginning and end of growth. More defects were found near the interface with Si and the majority of observed defects were related to extended defects while the presence of grain boundaries in polycrystalline diamond was discussed.

Local structure of percolating gels at very low volume fractions

NASA Astrophysics Data System (ADS)

Griffiths, Samuel; Turci, Francesco; Royall, C. Patrick

2017-01-01

The formation of colloidal gels is strongly dependent on the volume fraction of the system and the strength of the interactions between the colloids. Here we explore very dilute solutions by the means of numerical simulations and show that, in the absence of hydrodynamic interactions and for sufficiently strong interactions, percolating colloidal gels can be realised at very low values of the volume fraction. Characterising the structure of the network of the arrested material we find that, when reducing the volume fraction, the gels are dominated by low-energy local structures, analogous to the isolated clusters of the interaction potential. Changing the strength of the interaction allows us to tune the compactness of the gel as characterised by the fractal dimension, with low interaction strength favouring more chain-like structures.

Substructural controller synthesis

NASA Technical Reports Server (NTRS)

Su, Tzu-Jeng; Craig, Roy R., Jr.

1989-01-01

A decentralized design procedure which combines substructural synthesis, model reduction, decentralized controller design, subcontroller synthesis, and controller reduction is proposed for the control design of flexible structures. The structure to be controlled is decomposed into several substructures, which are modeled by component mode synthesis methods. For each substructure, a subcontroller is designed by using the linear quadratic optimal control theory. Then, a controller synthesis scheme called Substructural Controller Synthesis (SCS) is used to assemble the subcontrollers into a system controller, which is to be used to control the whole structure.

Mechanical characterisation of agarose-based chromatography resins for biopharmaceutical manufacture.

PubMed

Nweke, Mauryn C; McCartney, R Graham; Bracewell, Daniel G

2017-12-29

Mechanical characterisation of agarose-based resins is an important factor in ensuring robust chromatographic performance in the manufacture of biopharmaceuticals. Pressure-flow profiles are most commonly used to characterise these properties. There are a number of drawbacks with this method, including the potential need for several re-packs to achieve the desired packing quality, the impact of wall effects on experimental set up and the quantities of chromatography media and buffers required. To address these issues, we have developed a dynamic mechanical analysis (DMA) technique that characterises the mechanical properties of resins based on the viscoelasticity of a 1ml sample of slurry. This technique was conducted on seven resins with varying degrees of mechanical robustness and the results were compared to pressure-flow test results on the same resins. Results show a strong correlation between the two techniques. The most mechanically robust resin (Capto Q) had a critical velocity 3.3 times higher than the weakest (Sepharose CL-4B), whilst the DMA technique showed Capto Q to have a slurry deformation rate 8.3 times lower than Sepharose CL-4B. To ascertain whether polymer structure is indicative of mechanical strength, scanning electron microscopy images were also used to study the structural properties of each resin. Results indicate that DMA can be used as a small volume, complementary technique for the mechanical characterisation of chromatography media. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Design, synthesis and antimalarial screening of some hybrid 4-aminoquinoline-triazine derivatives against pf-DHFR-TS.

PubMed

Sahu, Supriya; Ghosh, Surajit Kumar; Kalita, Junmoni; Dutta, Mayurakhi; Bhat, Hans Raj

2016-04-01

Existing antifolate antimalarial drugs have shown resistance due to the mutations at some amino acid positions of Plasmodium falciparum DHFR-TS. In the present study, to overcome this resistance, a new series of hybrid 4-aminoquinoline-triazine derivatives were designed and docked into the active site of Pf-DHFR-TS (PDB i.d. 1J3K) using validated CDOCKER protocol. Binding energy was calculated by applying CHARMm forcefield. Binding energy and the pattern of interaction of the docked compounds were analysed. Fifteen compounds were selected for synthesis based on their binding energy values and docking poses. Synthesized compounds were characterised by FTIR, (1)H NMR, (13)C NMR, mass spectroscopy and were screened for antimalarial activity against 3D7 strain of Plasmodium falciparum. Copyright © 2016 Elsevier Inc. All rights reserved.

Characterisation of RF-sputtered platinum films from industrial production plants using slow positrons

NASA Astrophysics Data System (ADS)

Osipowicz, A.; Härting, M.; Hempel, M.; Britton, D. T.; Bauer-Kugelmann, W.; Triftshäuser, W.

1999-08-01

Platinum films, used in thin film technology, produced by radio-frequency sputter deposition on aluminium oxide substrates under different conditions, have been studied by positron beam and other techniques, before and after production annealing. The defect structure in the layers has been characterised using both positron lifetime and Doppler-broadening spectroscopy, and compared with X-ray studies of crystallinity and texture.

Synthesis and characterisations of SnO2 nanorods via low temperature hydrothermal method

NASA Astrophysics Data System (ADS)

Inderan, Vicinisvarri; Lim, Shin Ye; Ong, Teng Sian; Bastien, Samuel; Braidy, Nadi; Lee, Hooi Ling

2015-12-01

In the present study, tin oxide (SnO2) nanorods were successfully synthesized through hydrothermal treatment at a relatively low temperature (180 °C) using various concentrations of metal precursor, SnCl4·5H2O (0.04 M-0.16 M) in a mixed solution of ethanol and water before bringing the pH to 13 by adding 6 M NaOH. The effect of concentration on the morphology and structure of SnO2 were comprehensively studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis) and Fourier Transform Infrared (FTIR). It was found that increasing the concentration of tin precursor from 0.04 M to 0.16 M leads to a complete conversion from nanospheres to nanoplates and finally to nanorods. The SEM results confirmed that SnO2 nanorods are obtained for concentrations up to 0.12 M. At synthesis condition of 0.12 M, SnCl4·5H2O and pH 13, single rutile nanorods with preferential growth in the [002] direction were obtained. It was found that the diameter of nanorods formed at 0.12 M is similar to that of nanoplates formed at 0.08 M (20 nm), which suggests that spear-shaped nanorods might have originated from the primary nanoparticles (the particles grown in lower concentration during hydrothermal treatment). Possible reaction mechanisms are proposed to explain the observed morphologies.

A systematic review of the relationship between subchondral bone features, pain and structural pathology in peripheral joint osteoarthritis.

PubMed

Barr, Andrew J; Campbell, T Mark; Hopkinson, Devan; Kingsbury, Sarah R; Bowes, Mike A; Conaghan, Philip G

2015-08-25

Bone is an integral part of the osteoarthritis (OA) process. We conducted a systematic literature review in order to understand the relationship between non-conventional radiographic imaging of subchondral bone, pain, structural pathology and joint replacement in peripheral joint OA. A search of the Medline, EMBASE and Cochrane library databases was performed for original articles reporting association between non-conventional radiographic imaging-assessed subchondral bone pathologies and joint replacement, pain or structural progression in knee, hip, hand, ankle and foot OA. Each association was qualitatively characterised by a synthesis of the data from each analysis based upon study design, adequacy of covariate adjustment and quality scoring. In total 2456 abstracts were screened and 139 papers were included (70 cross-sectional, 71 longitudinal analyses; 116 knee, 15 hip, six hand, two ankle and involved 113 MRI, eight DXA, four CT, eight scintigraphic and eight 2D shape analyses). BMLs, osteophytes and bone shape were independently associated with structural progression or joint replacement. BMLs and bone shape were independently associated with longitudinal change in pain and incident frequent knee pain respectively. Subchondral bone features have independent associations with structural progression, pain and joint replacement in peripheral OA in the hip and hand but especially in the knee. For peripheral OA sites other than the knee, there are fewer associations and independent associations of bone pathologies with these important OA outcomes which may reflect fewer studies; for example the foot and ankle were poorly studied. Subchondral OA bone appears to be a relevant therapeutic target. PROSPERO registration number: CRD 42013005009.

Synthesis and Characterization of Silver-Doped Mesoporous Bioactive Glass and Its Applications in Conjunction with Electrospinning

PubMed Central

Ciraldo, Francesca E.; Goldmann, Wolfgang H.

2018-01-01

Since they were first developed in 2004, mesoporous bioactive glasses (MBGs) rapidly captured the interest of the scientific community thanks to their numerous beneficial properties. MBGs are synthesised by a combination of the sol–gel method with the chemistry of surfactants to obtain highly mesoporous (pore size from 5 to 20 nm) materials that, owing to their high surface area and ordered structure, are optimal candidates for controlled drug-delivery systems. In this work, we synthesised and characterised a silver-containing mesoporous bioactive glass (Ag-MBG). It was found that Ag-MBG is a suitable candidate for controlled drug delivery, showing a perfectly ordered mesoporous structure ideal for the loading of drugs together with optimal bioactivity, sustained release of silver from the matrix, and fast and strong bacterial inhibition against both Gram-positive and Gram-negative bacteria. Silver-doped mesoporous glass particles were used in three electrospinning-based techniques to produce PCL/Ag-MBG composite fibres, to coat bioactive glass scaffolds (via electrospraying), and for direct sol electrospinning. The results obtained in this study highlight the versatility and efficacy of Ag-substituted mesoporous bioactive glass and encourage further studies to characterize the biological response to Ag-MBG-based antibacterial controlled-delivery systems for tissue-engineering applications. PMID:29710768

Synthesis and characterisation of cross-linked chitosan composites functionalised with silver and gold nanoparticles for antimicrobial applications

NASA Astrophysics Data System (ADS)

Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria

2017-12-01

We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required.

Synthesis and characterisation of cross-linked chitosan composites functionalised with silver and gold nanoparticles for antimicrobial applications

PubMed Central

Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria

2017-01-01

Abstract We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required. PMID:28804527

Synthesis and characterisation of cross-linked chitosan composites functionalised with silver and gold nanoparticles for antimicrobial applications.

PubMed

Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria

2017-01-01

We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required.

Synthesis and structural characterisation of Pd(II) and Pt(II) complexes with a flexible, ferrocene-based P,S-donor amidophosphine ligand.

PubMed

Tauchman, Jiří; Císařová, Ivana; Stěpnička, Petr

2014-01-28

1'-Diphenylphosphino-1-{[(2-(methylthio)ethyl)amino]carbonyl}ferrocene (1), accessible via amidation of 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) with 2-(methylthio)ethylamine, reacts with [PdCl2(cod)] (cod = cycloocta-1,5-diene) at a 1 : 1 metal-to-ligand ratio to give trans-[PdCl2(1-κ(2)P,S)] (trans-2) as the sole product. A similar reaction with [PtCl2(cod)] affords a mixture of cis- and trans-[PtCl2(1-κ(2)P,S)] (cis- and trans-3), which can be separated by fractional crystallisation. Complexation reactions performed with 2 equiv. of the ligand are less selective, yielding mixtures of the expected bis-phosphine complexes (i.e., trans-[PdCl2(1-κP)2], or a mixture of cis- and trans-[PtCl2(-κP)2]) with the respective monophosphine complexes. The structures of 1, trans-2, cis-3 and trans-3 determined by X-ray diffraction demonstrate the ability of the title ligand to act as a flexible cis- or trans-P,S-chelate donor (the ligand bite angles are 174.03(2)/173.05(2)° for trans-2/3 and 92.86(2)° for cis-3).

Equine interferon gamma synthesis in lymphocytes after in vivo infection and in vitro stimulation with EHV-1.

PubMed

Paillot, R; Daly, J M; Juillard, V; Minke, J M; Hannant, D; Kydd, J H

2005-08-22

Equine cytotoxic T lymphocyte (CTL) responses to equine herpesvirus-1 (EHV-1) are well characterised but little is known about the cytokine response after infection or vaccination. EHV-1 is common in horses and infects lymphocytes in vivo. This virus was used as a model to measure the synthesis of interferon gamma (IFN-gamma) by equine peripheral blood mononuclear cells (PBMC) after in vivo infection and/or in vitro stimulation with EHV-1. Both flow cytometry and ELISPOT assays were used to quantify equine IFN-gamma using a mouse anti-bovine IFN-gamma monoclonal antibody (clone CC302; shown to cross-react with recombinant equine IFN-gamma) and a rabbit anti-canine IFN-gamma polyclonal antibody. The percentage of PBMC synthesising IFN-gamma after in vitro stimulation with EHV-1 increased with age. In yearlings infected experimentally with EHV-1, PBMC showed two peaks of IFN-gamma synthesis, 11 and 56 days after infection. The IFN-gamma synthesis was principally associated with CD8(+) cells. The patterns of IFN-gamma synthesis detected by intracellular IFN-gamma staining or ELISPOT were compared with CTL data and shown to be similar. These methods were also applied successfully to frozen samples of PBMC. Measurement of equine IFN-gamma using these simple techniques can now be applied to future studies on protective cellular immune responses following virus infection and/or vaccination of horses.

Contact force structure and force chains in 3D sheared granular systems

NASA Astrophysics Data System (ADS)

Mair, Karen; Jettestuen, Espen; Abe, Steffen

2010-05-01

Faults often exhibit accumulations of granular debris, ground up to create a layer of rock flour or fault gouge separating the rigid fault walls. Numerical simulations and laboratory experiments of sheared granular materials, suggest that applied loads are preferentially transmitted across such systems by transient force networks that carry enhanced forces. The characterisation of such features is important since their nature and persistence almost certainly influence the macroscopic mechanical stability of these systems and potentially that of natural faults. 3D numerical simulations of granular shear are a valuable investigation tool since they allow us to track individual particle motions, contact forces and their evolution during applied shear, that are difficult to view directly in laboratory experiments or natural fault zones. In characterising contact force distributions, it is important to use global structure measures that allow meaningful comparisons of granular systems having e.g. different grain size distributions, as may be expected at different stages of a fault's evolution. We therefore use a series of simple measures to characterise the structure, such as distributions and correlations of contact forces that can be mapped onto a force network percolation problem as recently proposed by Ostojic and coworkers for 2D granular systems. This allows the use of measures from percolation theory to both define and characterise the force networks. We demonstrate the application of this method to 3D simulations of a sheared granular material. Importantly, we then compare our measure of the contact force structure with macroscopic frictional behaviour measured at the boundaries of our model to determine the influence of the force networks on macroscopic mechanical stability.

Controllably annealed CuO-nanoparticle modified ITO electrodes: Characterisation and electrochemical studies

NASA Astrophysics Data System (ADS)

Wang, Tong; Su, Wen; Fu, Yingyi; Hu, Jingbo

2016-12-01

In this paper, we report a facile and controllable two-step approach to produce indium tin oxide electrodes modified by copper(II) oxide nanoparticles (CuO/ITO) through ion implantation and annealing methods. After annealing treatment, the surface morphology of the CuO/ITO substrate changed remarkably and exhibited highly electroactive sites and a high specific surface area. The effects of annealing treatment on the synthesis of CuO/ITO were discussed based on various instruments' characterisations, and the possible mechanism by which CuO nanoparticles were generated was also proposed in this work. Cyclic voltammetric results indicated that CuO/ITO electrodes exhibited effective catalytic responses toward glucose in alkaline solution. Under optimal experimental conditions, the proposed CuO/ITO electrode showed sensitivity of 450.2 μA cm-2 mM-1 with a linear range of up to ∼4.4 mM and a detection limit of 0.7 μM (S/N = 3). Moreover, CuO/ITO exhibited good poison resistance, reproducibility, and stability properties.

Electrochemical and spectroscopic characterisation of amphetamine-like drugs: application to the screening of 3,4-methylenedioxymethamphetamine (MDMA) and its synthetic precursors.

PubMed

Milhazes, Nuno; Martins, Pedro; Uriarte, Eugenio; Garrido, Jorge; Calheiros, Rita; Marques, M Paula M; Borges, Fernanda

2007-07-23

A complete physicochemical characterisation of MDMA and its synthetic precursors MDA, 3,4-methylenedioxybenzaldehyde (piperonal) and 3,4-methylenedioxy-beta-methyl-beta-nitrostyrene was carried out through voltammetric assays and Raman spectroscopy combined with theoretical (DFT) calculations. The former provided important analytical redox data, concluding that the oxidative mechanism of the N-demethylation of MDMA involves the removal of an electron from the amino-nitrogen atom, leading to the formation of a primary amine and an aldehyde. The vibrational spectroscopic experiments enable to afford a rapid and reliable detection of this type of compounds, since they yield characteristic spectral patterns that lead to an unequivocal identification. Moreover, the rational synthesis of the drug of abuse 3,4-methylenedioxymethamphetamine (MDMA or "ecstasy") from one of its most relevant precursors 3,4-methylene-dioxyamphetamine (MDA), is reported. In addition, several approaches for the N-methylation of MDA, a limiting synthetic step, were attempted and the overall yields compared.

Altered molecular specificity of surfactant phosphatidycholine synthesis in patients with acute respiratory distress syndrome.

PubMed

Dushianthan, Ahilanandan; Goss, Victoria; Cusack, Rebecca; Grocott, Michael P W; Postle, Anthony D

2014-11-07

Acute respiratory distress syndrome (ARDS) is a life-threatening critical illness, characterised by qualitative and quantitative surfactant compositional changes associated with premature airway collapse, gas-exchange abnormalities and acute hypoxic respiratory failure. The underlying mechanisms for this dysregulation in surfactant metabolisms are not fully explored. Lack of therapeutic benefits from clinical trials, highlight the importance of detailed in-vivo analysis and characterisation of ARDS patients according to patterns of surfactant synthesis and metabolism. Ten patients with moderate to severe ARDS were recruited. Most (90%) suffered from pneumonia. They had an infusion of methyl-D9-choline chloride and small volume bronchoalveolar lavage fluid (BALF) was obtained at 0,6,12,24,48,72 and 96 hours. Controls were healthy volunteers, who had BALF at 24 and 48 hours after methyl-D9-choline infusion. Compositional analysis and enrichment patterns of stable isotope labelling of surfactant phosphatidylcholine (PC) was determined by electrospray ionisation mass spectrometry. BALF of patients with ARDS consisted of diminished total PC and fractional PC16:0/16:0 concentrations compared to healthy controls. Compositional analysis revealed, reductions in fractional compositions of saturated PC species with elevated levels of longer acyl chain unsaturated PC species. Molecular specificity of newly synthesised PC fraction showed time course variation, with lower PC16:0/16:0 composition at earlier time points, but achieved near equilibrium with endogenous composition at 48 hours after methyl-D9-choline infusion. The enrichment of methyl-D9-choline into surfactant total PC is nearly doubled in patients, with considerable variation between individuals. This study demonstrate significant alterations in composition and kinetics of surfactant PC extracted from ARDS patients. This novel approach may facilitate biochemical phenotyping of ARDS patients according to surfactant synthesis and metabolism, enabling individualised treatment approaches for the management of ARDS patients in the future.

Cellulose microfibrils in plants: biosynthesis, deposition, and integration into the cell wall.

PubMed

Brett, C T

2000-01-01

Cellulose occurs in all higher plants and some algae, fungi, bacteria, and animals. It forms microfibrils containing the crystalline allomorphs, cellulose I alpha and I beta. Cellulose molecules are 500-15,000 glucose units long. What controls molecular size is unknown. Microfibrils are elongated by particle rosettes in the plasma membrane (cellulose synthase complexes). The precursor, UDP-glucose, may be generated from sucrose at the site of synthesis. The biosynthetic mechanism may involve lipid-linked intermediates. Cellulose synthase has been purified from bacteria, but not from plants. In plants, disrupted cellulose synthase may form callose. Cellulose synthase genes have been isolated from bacteria and plants. Cellulose-deficient mutants have been characterised. The deduced amino acid sequence suggests possible catalytic mechanisms. It is not known whether synthesis occurs at the reducing or nonreducing end. Endoglucanase may play a role in synthesis. Nascent cellulose molecules associate by Van der Waals and hydrogen bonds to form microfibrils. Cortical microtubules control microfibril orientation, thus determining the direction of cell growth. Self-assembly mechanisms may operate. Microfibril integration into the wall occurs by interactions with matrix polymers during microfibril formation.

Modulation of interferon-γ synthesis by the effects of lignin-like enzymatically polymerized polyphenols on antigen-presenting cell activation and the subsequent cell-to-cell interactions.

PubMed

Yamanaka, Daisuke; Motoi, Masuro; Ishibashi, Ken-ichi; Miura, Noriko N; Adachi, Yoshiyuki; Ohno, Naohito

2013-12-15

Lignin-like polymerized polyphenols strongly activate lymphocytes and induce cytokine synthesis. We aimed to characterise the mechanisms of action of polymerized polyphenols on immunomodulating functions. We compared the reactivity of leukocytes from various organs to that of polymerized polyphenols. Splenocytes and resident peritoneal cavity cells (PCCs) responded to polymerized polyphenols and released several cytokines, whereas thymocytes and bone-marrow cells showed no response. Next, we eliminated antigen-presenting cells (APCs) from splenocytes to study their involvement in cytokine synthesis. We found that APC-negative splenocytes showed significantly reduced cytokine production induced by polymerized polyphenols. Additionally, adequate interferon-γ (IFN-γ) induction by polymerized polyphenols was mediated by the coexistence of APCs and T cells because the addition of T cells to PCCs increased IFN-γ production. Furthermore, inhibition of the T cell-APC interaction using neutralising antibodies significantly decreased cytokine production. Thus, cytokine induction by polymerized polyphenols was mediated by the interaction between APCs and T cells. Copyright © 2013 Elsevier Ltd. All rights reserved.

Chemical, computational and functional insights into the chemical stability of the Hedgehog pathway inhibitor GANT61.

PubMed

Calcaterra, Andrea; Iovine, Valentina; Botta, Bruno; Quaglio, Deborah; D'Acquarica, Ilaria; Ciogli, Alessia; Iazzetti, Antonia; Alfonsi, Romina; Lospinoso Severini, Ludovica; Infante, Paola; Di Marcotullio, Lucia; Mori, Mattia; Ghirga, Francesca

2018-12-01

This work aims at elucidating the mechanism and kinetics of hydrolysis of GANT61, the first and most-widely used inhibitor of the Hedgehog (Hh) signalling pathway that targets Glioma-associated oncogene homologue (Gli) proteins, and at confirming the chemical nature of its bioactive form. GANT61 is poorly stable under physiological conditions and rapidly hydrolyses into an aldehyde species (GANT61-A), which is devoid of the biological activity against Hh signalling, and a diamine derivative (GANT61-D), which has shown inhibition of Gli-mediated transcription. Here, we combined chemical synthesis, NMR spectroscopy, analytical studies, molecular modelling and functional cell assays to characterise the GANT61 hydrolysis pathway. Our results show that GANT61-D is the bioactive form of GANT61 in NIH3T3 Shh-Light II cells and SuFu -/- mouse embryonic fibroblasts, and clarify the structural requirements for GANT61-D binding to Gli1. This study paves the way to the design of GANT61 derivatives with improved potency and chemical stability.

Polymeric microcapsules with switchable mechanical properties for self-healing concrete: synthesis, characterisation and proof of concept

NASA Astrophysics Data System (ADS)

Kanellopoulos, A.; Giannaros, P.; Palmer, D.; Kerr, A.; Al-Tabbaa, A.

2017-04-01

Microcapsules, with sodium silicate solution as core, were produced using complex coacervation in a double, oil-in-water-in oil, emulsion system. The shell material was a gelatin-acacia gum crosslinked coacervate and the produced microcapsules had diameters ranging from 300 to 700 μm. The shell material designed with switchable mechanical properties. When it is hydrated exhibits soft and ‘rubbery’ behaviour and, when dried, transitions to a stiff and ‘glassy’ material. The microcapsules survived drying and rehydrating cycles and preserved their structural integrity when exposed to highly alkaline solutions that mimic the pH environment of concrete. Microscopy revealed that the shell thickness of the microcapsules varies across their perimeter from 5 to 20 μm. Thermal analysis showed that the produced microcapsules were very stable up to 190 °C. Proof of concept investigation has demonstrated that the microcapsules successfully survive and function when exposed to a cement-based matrix. Observations showed that the microcapsules survive mixing with cement and rupture successfully upon crack formation releasing the encapsulated sodium silicate solution.

Sonochemical synthesis of novel magnesium 1,2,4-triazole-1-carbodithioate nanoparticles as antifungals

NASA Astrophysics Data System (ADS)

Gumber, Khushbu; Sidhu, Anjali; Kaur, Robinpreet

2017-04-01

Novel magnesium 1,2,4-triazole-1-carbodithioates were sonochemically synthesized as water-dispersable nanoparticles owing to their water insolubility. The two-step reaction protocol was followed to synthesize the novel triazole ligand system for complexation with magnesium metal due to its low biological toxicity. Different concentrations of Poly Vinyl Pyrrolidine were used to stabilize and standardise the size of nanoparticles, which were characterised by TEM analysis. UV-Visible and infrared spectroscopies were used to analyse the metal ligand interaction, and CHNS analysis was used to propose the structure of the metal complex. The spore germination inhibition technique was used to evaluate the antifungal potential of synthesized nano-complexes against two phytopathogenic test fungi viz . A. alternata and F. moniliforme. The nanoparticles had inflicted moderate in vitro inhibition of fungal growth, which was comparable to standard fungicide Indofil M-45. The in silico toxicity of the compounds was made using the Toxtree analysis software that indicated the compounds belong to class III group of toxicity, which was same as that of commercial standards of DTC.

Bright and photostable cyanine-styryl chromophores with green and red fluorescence colour for DNA staining

NASA Astrophysics Data System (ADS)

Bohländer, Peggy R.; Wagenknecht, Hans-Achim

2015-12-01

The synthesis and optical characterisation of a series of green- and red-emitting cyanine and cyanine-styryl dyes is presented that were developed based on the cyanine-indole-quinolinium and based on the thiazole red type structure. For the green emitting fluorophores the quinolinium part was replaced by a pyridinium group. The bridge to the indole group was attached either to the 2-position or to the 4-position of the pyridinium moiety. For the red-emitting dyes the connection to the indole moiety is at the 4-position of the quinolinium part. In each set of dyes a methyl group at the indole-NH and/or a phenyl group at the 2-position of the indole part were introduced to tune the optical properties and photostability. Additionally, two dyes were modified with a cyano group to tune the photophysical properties and to enhance the photostabilities. The developed dyes show good photostabilities and bright green or red fluorescence intensities in the presence of DNA. Thus, these dyes represent important and promising candidates for fluorescent molecular imaging of nucleic acids inside living cells.

The bipyridine adducts of N-phenyldithiocarbamato complexes of Zn(II) and Cd(II); synthesis, spectral, thermal decomposition studies and use as precursors for ZnS and CdS nanoparticles.

PubMed

Onwudiwe, Damian C; Strydom, Christien A

2015-01-25

Bipyridine adducts of N-phenyldithiocarbamato complexes, [ML(1)2L(2)] (M=Cd(II), Zn(II); L(1)=N-phenyldithiocarbamate, L(2)=2,2' bipyridine), have been synthesized and characterised. The decomposition of these complexes to metal sulphides has been investigated by thermogravimetric analysis (TGA). The complexes were used as single-source precursors to synthesize MS (M=Zn, Cd) nanoparticles (NPs) passivated by hexadecyl amine (HDA). The growth of the nanoparticles was carried out at two different temperatures: 180 and 220 °C, and the optical and structural properties of the nanoparticles were studied using UV-Vis spectroscopy, photoluminescence spectroscopy (PL), transmission emission microscopy (TEM) and powdered X-ray diffraction (p-XRD). Nanoparticles, whose average diameters are 2.90 and 3.54 nm for ZnS, and 8.96 and 9.76 nm for CdS grown at 180 and 220 °C respectively, were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, characterisation and computational studies on a novel one-dimensional arrangement of Schiff-base Mn3 single-molecule magnet.

PubMed

Lin, Po-Heng; Gorelsky, Serge; Savard, Didier; Burchell, Tara J; Wernsdorfer, Wolfgang; Clérac, Rodolphe; Murugesu, Muralee

2010-09-07

The syntheses, structures and magnetic properties are reported for three new manganese complexes containing the Schiff-base ((2-hydroxy-3-methoxyphenyl)methylene)isonicotinohydrazine (H(2)hmi) ligand. Complex [Mn(II)(H(2)hmi)(2)(MeOH)(2)Cl(2)] (1) was obtained from the reaction of H(2)hmi with MnCl(2) in a MeOH-MeCN mixture. Addition of triethylamine to the previous reaction mixture followed by diethyl ether diffusion yielded a dinuclear manganese [Mn(III)(2)(hmi)(2)(OMe)(2)](infinity).2MeCN.2OEt(2) (2) compound. Upon increasing the MnCl(2)/H(2)hmi ratio, the mixed valence complex [Mn(III)(2)Mn(II)(hmi)(2)(OMe)(2)Cl(2)](infinity).MeOH (3) was obtained. Dc and ac magnetic measurements were carried out on all three samples. The ac susceptibility and field dependence of the magnetisation measurements confirmed that complex 3 exhibits a single-molecule magnet behaviour with an effective energy barrier of 8.1 K and an Arrhenius pre-exponential factor of 3 x 10(-9) s.

Green fabricated CuO nanobullets via Olea europaea leaf extract shows auspicious antimicrobial potential.

PubMed

Maqbool, Qaisar; Iftikhar, Sidra; Nazar, Mudassar; Abbas, Fazal; Saleem, Asif; Hussain, Talib; Kausar, Rizwan; Anwaar, Sadaf; Jabeen, Nyla

2017-06-01

In present investigation, copper oxide (CuO) nanostructures have been prepared via green chemistry. Olea europaea leaf extract act as strong chelating agent for tailoring physical as well as bio-medical characteristics of CuO at the nano-size. Physical characterisation such as scanning electron microscope analysis depicts the formation of homogenised spherical shape nanoparticles (NPs) with average size of 42 nm. X-ray diffraction and Fourier transform infrared spectroscopy further confirmed the crystalline pure phase and monoclinic structure. High performance liquid chromatography (HPLC) testing is performed to evaluate the relative concentration of bioactive molecules in the O. europaea leaf extract. From HPLC results capping action of organic molecules around CuO-NPs is hypothesised. The antimicrobial potency of biosynthesised CuO-NPs have been evaluated using colony forming unit (CFU) counting assay and disc diffusion method which shows a significant zone of inhibition against bacterial and fungal strains may be highly potential for future antimicrobial pharmaceutics. Furthermore, reduction of various precursors by plant extract will reduce environmental impact over chemical synthesis.

Synthesis and Characterisation of Reduced Graphene Oxide/Bismuth Composite for Electrodes in Electrochemical Energy Storage Devices.

PubMed

Wang, Jiabin; Zhang, Han; Hunt, Michael R C; Charles, Alasdair; Tang, Jie; Bretcanu, Oana; Walker, David; Hassan, Khalil T; Sun, Yige; Šiller, Lidija

2017-01-20

A reduced graphene oxide/bismuth (rGO/Bi) composite was synthesized for the first time using a polyol process at a low reaction temperature and with a short reaction time (60 °C and 3 hours, respectively). The as-prepared sample is structured with 20-50 nm diameter bismuth particles distributed on the rGO sheets. The rGO/Bi composite displays a combination of capacitive and battery-like charge storage, achieving a specific capacity value of 773 C g -1 at a current density of 0.2 A g -1 when charged to 1 V. The material not only has good power density but also shows moderate stability in cycling tests with current densities as high as 5 A g -1 . The relatively high abundance and low price of bismuth make this rGO/Bi material a promising candidate for use in electrode materials in future energy storage devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bayesian models for cost-effectiveness analysis in the presence of structural zero costs

PubMed Central

Baio, Gianluca

2014-01-01

Bayesian modelling for cost-effectiveness data has received much attention in both the health economics and the statistical literature, in recent years. Cost-effectiveness data are characterised by a relatively complex structure of relationships linking a suitable measure of clinical benefit (e.g. quality-adjusted life years) and the associated costs. Simplifying assumptions, such as (bivariate) normality of the underlying distributions, are usually not granted, particularly for the cost variable, which is characterised by markedly skewed distributions. In addition, individual-level data sets are often characterised by the presence of structural zeros in the cost variable. Hurdle models can be used to account for the presence of excess zeros in a distribution and have been applied in the context of cost data. We extend their application to cost-effectiveness data, defining a full Bayesian specification, which consists of a model for the individual probability of null costs, a marginal model for the costs and a conditional model for the measure of effectiveness (given the observed costs). We presented the model using a working example to describe its main features. © 2013 The Authors. Statistics in Medicine published by John Wiley & Sons, Ltd. PMID:24343868

Bayesian models for cost-effectiveness analysis in the presence of structural zero costs.

PubMed

Baio, Gianluca

2014-05-20

Bayesian modelling for cost-effectiveness data has received much attention in both the health economics and the statistical literature, in recent years. Cost-effectiveness data are characterised by a relatively complex structure of relationships linking a suitable measure of clinical benefit (e.g. quality-adjusted life years) and the associated costs. Simplifying assumptions, such as (bivariate) normality of the underlying distributions, are usually not granted, particularly for the cost variable, which is characterised by markedly skewed distributions. In addition, individual-level data sets are often characterised by the presence of structural zeros in the cost variable. Hurdle models can be used to account for the presence of excess zeros in a distribution and have been applied in the context of cost data. We extend their application to cost-effectiveness data, defining a full Bayesian specification, which consists of a model for the individual probability of null costs, a marginal model for the costs and a conditional model for the measure of effectiveness (given the observed costs). We presented the model using a working example to describe its main features. © 2013 The Authors. Statistics in Medicine published by John Wiley & Sons, Ltd.

Advances in research on structural characterisation of agricultural products using atomic force microscopy.

PubMed

Liu, Dongli; Cheng, Fang

2011-03-30

Atomic force microscopy (AFM) has many unique features compared with other conventional microscopies, such as high magnification with high resolution, minimal sample preparation, acquiring 2D and 3D images at the same time, observing ongoing processes directly, the possibility of manipulating macromolecules, etc. As a nanotechnology tool, AFM has been used to investigate the nanostructure of materials in many fields. This mini-review focuses mainly on its latest application to characterise the macromolecular nanostructure and surface topography of agricultural products. First the fundamentals of AFM are briefly explained. Then the macromolecular nanostructure information on agricultural products from AFM images is introduced by exploring the structure-function relationship in three aspects: agricultural product processing, agricultural product ripening and storage, and genetic and environmental factors. The surface topography characterisation of agricultural products using AFM is also discussed. The results reveal that AFM could be a powerful nanotechnology tool to acquire a deeper understanding of the mechanisms of structure and quality variations of agricultural products, which could be instructive in improving processing and storage technologies, and AFM is also helpful to reveal the essential nature of a product at nanoscale. Copyright © 2011 Society of Chemical Industry.

Coordination polymers of 5-substituted isophthalic acid

DOE PAGES

McCormick, Laura J.; Morris, Samuel A.; Slawin, Alexandra M. Z.; ...

2015-12-10

In this work, the synthesis and characterisation of five coordination polymers - Ni 2(mip) 2 (H 2O) 8 ·2H 2O (1), Zn 6(mip) 5(OH) 2(H 2O) 4 ·7.4H 2O (2), Zn 6(mip) 5(OH) 2(H 2O) 2 ·4H 2O (3), Mn(HMeOip) 2 (4), and Mn 3(tbip) 2(Htbip) 2(EtOH) 2 (5) - are reported. Preliminary nitric oxide release data on compounds 2 and 3 are also given.

Synthesis, characterisation and phase transition behaviour of temperature-responsive physically crosslinked poly (N-vinylcaprolactam) based polymers for biomedical applications.

PubMed

Halligan, Shane C; Dalton, Maurice B; Murray, Kieran A; Dong, Yixiao; Wang, Wenxin; Lyons, John G; Geever, Luke M

2017-10-01

Poly (N-vinylcaprolactam) (PNVCL) is a polymer which offers superior characteristics for various potential medical device applications. In particular it offers unique thermoresponsive capabilities, which fulfils the material technology constraints required in targeted drug delivery applications. PNVCL phase transitions can be tailored in order to suit the requirements of current and next generation devices, by modifying the contents with regard to the material composition and aqueous polymer concentration. In this study, physically crosslinked Poly (N-vinylcaprolactam)-Vinyl acetate (PNVCL-VAc) copolymers were prepared by photopolymerisation. The structure of the polymers was established by Fourier transform infrared spectroscopy, nuclear magnetic resonance and gel permeation chromatography. The polymers were further characterised using differential scanning calorimetry and swelling studies. Determination of the LCST of the polymers in aqueous solution was achieved by employing four techniques; cloud point, UV-spectrometry, differential scanning calorimetry and rheometry. Sol-gel transition was established using tube inversion method and rheological analysis. This study was conducted to determine the characteristics of PNVCL with the addition of VAc, and to establish the effects on the phase transition. The PNVCL based polymers exhibited a decrease in the LCST as the composition of VAc increased. Sol-gel transition could be controlled by altering the monomeric feed ratio and polymer concentration in aqueous milieu. Importantly all copolymers (10wt% in solution) underwent gelation between 33.6 and 35.9°C, and based on this and the other materials properties recorded in this study, these novel copolymers have potential for use as injectable in situ forming drug delivery systems for targeted drug delivery. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of nanocomposites based on hydroxyapatite/sodium alginate: Synthesis and characterisation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajkumar, M.; Meenakshisundaram, N.; Rajendran, V., E-mail: veerajendran@gmail.com

2011-05-15

In this study, a novel method was used to produce a nanostructured composite consisting of hydroxyapatite and sodium alginate by varying the composition of sodium alginate. The structure, morphology, simulated body fluid response and mechanical properties of the synthesised nanocomposites were characterised. From X-ray diffraction analysis, an increase in crystallite size and degree of crystallinity with an increase in the composition of sodium alginate up to 1.5 wt.% was observed. Further, it was found to decrease with an increase in the composition of sodium alginate. A notable peak shift from 1635 to 1607 cm{sup -1} and 1456 to 1418 cm{supmore » -1} in the Fourier transform infrared spectra of the nanocomposite was observed towards the lower wave number side when compared with pure hydroxyapatite. It reveals a strong interaction between the positively charged calcium (Ca{sup 2+}) and the negatively charged carboxyl group (COO{sup -}) in sodium alginate. Transmission electron microscopy images of pure hydroxyapatite showed a short nanorod-like morphology with an average particle size of 13 nm. Bioresorbability of the samples was observed by immersing them in simulated body fluid medium for 14 days to evaluate the changes in pH and Ca{sup 2+} ion strength. Microhardness shows an increasing trend with an increase in the composition of sodium alginate from 1.5 to 3.0 wt.%, which is similar to that in the density. - Research Highlights: {yields} We have prepared nanohydroxyapatite/sodium alginate as a composite. {yields} Effect of sodium alginate on the properties of nanohydrroxyapatite has been studied. {yields} The sodium alginate ranges from 0 to 3.75 wt.% has been used. {yields} Composites show improved biological and mechanical properties.« less

Structural and functional characterisation of a class I endochitinase of the carnivorous sundew (Drosera rotundifolia L.).

PubMed

Jopcik, Martin; Moravcikova, Jana; Matusikova, Ildiko; Bauer, Miroslav; Rajninec, Miroslav; Libantova, Jana

2017-02-01

Chitinase gene from the carnivorous plant, Drosera rotundifolia , was cloned and functionally characterised. Plant chitinases are believed to play an important role in the developmental and physiological processes and in responses to biotic and abiotic stress. In addition, there is growing evidence that carnivorous plants can use them to digest insect prey. In this study, a full-length genomic clone consisting of the 1665-bp chitinase gene (gDrChit) and adjacent promoter region of the 698 bp in length were isolated from Drosera rotundifolia L. using degenerate PCR and a genome-walking approach. The corresponding coding sequence of chitinase gene (DrChit) was obtained following RNA isolation from the leaves of aseptically grown in vitro plants, cDNA synthesis with a gene-specific primer and PCR amplification. The open reading frame of cDNA clone consisted of 978 nucleotides and encoded 325 amino acid residues. Sequence analysis indicated that DrChit belongs to the class I group of plant chitinases. Phylogenetic analysis within the Caryophyllales class I chitinases demonstrated a significant evolutionary relatedness of DrChit with clade Ib, which contains the extracellular orthologues that play a role in carnivory. Comparative expression analysis revealed that the DrChit is expressed predominantly in tentacles and is up-regulated by treatment with inducers that mimick insect prey. Enzymatic activity of rDrChit protein expressed in Escherichia coli was confirmed and purified protein exhibited a long oligomer-specific endochitinase activity on glycol-chitin and FITC-chitin. The isolation and expression profile of a chitinase gene from D. rotundifolia has not been reported so far. The obtained results support the role of specific chitinases in digestive processes in carnivorous plant species.

Radiation-induced synthesis and swelling properties of p(2-hydroxyethyl methacrylate/itaconic acid/oligo (ethylene glycol) acrylate) terpolymeric hydrogels

NASA Astrophysics Data System (ADS)

Micic, M.; Stamenic, D.; Suljovrujic, E.

2012-09-01

Since it is presumed that by incorporation of pH-responsive (IA) and temperature-responsive (OEGA) co-monomers, it is possible to prepare P(HEMA/IA/OEGA) hydrogels with dual (pH and thermo) responsiveness, the main purpose of our study is to investigate the influence of different mole fractions of IA and especially OEGA on the diversity of the swelling properties of the obtained hydrogels. For that reason, a series of terpolymeric hydrogels with different mole ratios of 2-hydroxyethyl methacrylate (HEMA), itaconic acid (IA) and oligo(ethylene glycol) acrylates (OEGA) was synthesised by gamma radiation. The obtained hydrogels were characterised by swelling studies in the wide pH (2.2-9.0) and temperature range (20-70 °C), confirming dual (pH and thermo) responsiveness and a large variation in the swelling capability. It was observed that the equilibrium swelling of P(HEMA/IA/OEGA) hydrogels, for a constant amount of IA, increased progressively with an increase in OEGA share. On the other hand, the dissociation of carboxyl groups from IA occurs at pH>4; therefore, small mole fractions of IA render good pH sensitivity and a large increase in the swelling capacity of these hydrogels at higher pH values. Additional characterisation of structure and properties was conducted by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and mechanical measurements, confirming that the inherent properties of P(HEMA/IA/OEGA) hydrogels can be significantly tuned by variation in their composition. According to all presented, it seems that the obtained hydrogels can be a beneficial synergetic combination for controlled delivery of bioactive molecules such as drugs, peptides, proteins, etc.

Sonochemical surface functionalization of exfoliated LDH: Effect on textural properties, CO2 adsorption, cyclic regeneration capacities and subsequent gas uptake for simultaneous methanol synthesis.

PubMed

Ezeh, Collins I; Huang, Xiani; Yang, Xiaogang; Sun, Cheng-Gong; Wang, Jiawei

2017-11-01

To improve CO 2 adsorption, amine modified Layered double hydroxide (LDH) were prepared via a two stage process, SDS/APTS intercalation was supported by ultrasonic irradiation and then followed by MEA extraction. The prepared samples were characterised using Scanning electron microscope-Energy dispersive X-ray spectroscopy (SEM-EDX), X-ray Photoelectron Spectroscopy (XPS), X-ray diffraction (XRD), Temperature Programmed Desorption (TPD), Brunauer-Emmett-Teller (BET), and Thermogravimetric analysis (TGA), respectively. The characterisation results were compared with those obtained using the conventional preparation method with consideration to the effect of sonochemical functionalization on textural properties, adsorption capacity, regeneration and lifetime of the LDH adsorbent. It is found that LDHs prepared by sonochemical modification had improved pore structure and CO 2 adsorption capacity, depending on sonic intensity. This is attributed to the enhanced deprotonation of activated amino functional groups via the sonochemical process. Subsequently, this improved the amine loading and effective amine efficiency by 60% of the conventional. In addition, the sonochemical process improved the thermal stability of the adsorbent and also, reduced the irreversible CO 2 uptake, CUirrev, from 0.18mmol/g to 0.03mmol/g. Subsequently, improving the lifetime and ease of regenerating the adsorbent respectively. This is authenticated by subjecting the prepared adsorbents to series of thermal swing adsorption (TSA) cycles until its adsorption capacity goes below 60% of the original CO 2 uptake. While the conventional adsorbent underwent a 10 TSA cycles before breaking down, the sonochemically functionalized LDH went further than 30 TSA cycles. Copyright © 2017 Elsevier B.V. All rights reserved.

Protein synthesis and specific dynamic action in crustaceans: effects of temperature.

PubMed

Whiteley, N M; Robertson, R F; Meagor, J; El Haj, A J; Taylor, E W

2001-03-01

Temperature influences the specific dynamic action (SDA), or rise in oxygen uptake rate after feeding, in eurythermal and stenothermal crustaceans by changing the timing and the magnitude of the response. Intra-specific studies on the eurythermal crab, Carcinus maenas, show that a reduction in acclimation temperature is associated with a decrease in SDA magnitude, resulting from an increase in SDA duration but a decrease in peak factorial scope (the factorial rise in peak SDA over prefeeding values). Inter-specific feeding studies on stenothermal polar isopods revealed marked differences in SDA response between the Antarctic species, Glyptonotus antarcticus and the Arctic species, Saduria entomon. Compared to S. entomon held at 4 and 13 degrees C, the SDA response in G. antarcticus held at 1 degrees C was characterised by a lower absolute oxygen uptake rate at peak SDA and an extended SDA duration. At peak SDA, whole animal rates of protein synthesis increased in proportion to the postprandial increase in oxygen uptake rate in the Antarctic and the Arctic species. Rates of oxygen uptake plotted against whole animal rates of protein synthesis gave similar relationships in both isopod species, indicating similar costs of protein synthesis after a meal, despite their differences in SDA response and thermal habitat.

Novel green synthetic strategy to prepare ZnO nanocrystals using rambutan (Nephelium lappaceum L.) peel extract and its antibacterial applications.

PubMed

Yuvakkumar, R; Suresh, J; Nathanael, A Joseph; Sundrarajan, M; Hong, S I

2014-08-01

In the present investigation, we report a sustainable novel green synthetic strategy to synthesis zinc oxide nanocrystals. This is the first report on sustainable biosynthesis of zinc oxide nanocrystals employing Nephelium lappaceum L., peel extract as a natural ligation agent. Green synthesis of zinc oxide nanocrystals was carried out via zinc-ellagate complex formation using rambutan peel wastes. The successful formation of zinc oxide nanocrystals was confirmed employing standard characterisation studies. A possible mechanism for the formation of ZnO nanocrystals with rambutan peel extract was also proposed. The prepared ZnO nanocrystals were coated on the cotton fabric and their antibacterial activity were analyzed. ZnO nanocrystals coated cotton showed good antibacterial activity towards Escherichia coli (E. coli), gram negative bacteria and Staphylococcus aureus (S. aureus), gram positive bacteria. Copyright © 2014 Elsevier B.V. All rights reserved.

One-pot palladium-catalyzed synthesis of sulfonyl fluorides from aryl bromides† †Electronic supplementary information (ESI) available: Experimental details and supporting characterisation data. See DOI: 10.1039/c6sc03924c Click here for additional data file.

PubMed Central

Davies, Alyn T.; Curto, John M.

2017-01-01

A mild, efficient synthesis of sulfonyl fluorides from aryl and heteroaryl bromides utilizing palladium catalysis is described. The process involves the initial palladium-catalyzed sulfonylation of aryl bromides using DABSO as an SO2 source, followed by in situ treatment of the resultant sulfinate with the electrophilic fluorine source NFSI. This sequence represents the first general method for the sulfonylation of aryl bromides, and offers a practical, one-pot alternative to previously described syntheses of sulfonyl fluorides, allowing rapid access to these biologically important molecules. Excellent functional group tolerance is demonstrated, with the transformation successfully achieved on a number of active pharmaceutical ingredients, and their precursors. The preparation of peptide-derived sulfonyl fluorides is also demonstrated. PMID:28451264

Green synthesis and antimicrobial activity of silver nanoparticles using wild medicinal mushroom Ganoderma applanatum (Pers.) Pat. from Similipal Biosphere Reserve, Odisha, India.

PubMed

Mohanta, Yugal Kishore; Singdevsachan, Sameer Kumar; Parida, Umesh Kumar; Panda, Sujogya Kumar; Mohanta, Tapan Kumar; Bae, Hanhong

2016-08-01

In the present study, green synthesis and cost effective approach of silver nanoparticles using wild medicinal mushroom Ganoderma applanatum (Pers.) Pat. from Similipal Biosphere Reserve, Odisha, India is reported. The biosynthesised AgNPs were characterised using UV-visible spectroscopy, particle analyser and scanning electron microscopy studies. It was found by dynamic light scattering analysis, that the average size and charges of the AgNPs were 133.0 ± 0.361 nm and -6.01 ± 5.30 mV, respectively. Moreover, the Fourier transform infrared study was also conducted to identify the biomolecules or functional groups responsible for the reduction of Ag and stabilisation of the AgNPs. The potential biomedical application with reference to antimicrobial activity of the synthesised AgNPs was investigated against some pathogenic microorganisms viz. Escherichia coli, Bacillus subtilis, Staphylococcus epidermidis, Vibrio cholerae, Staphylococcus aureus and Shigella flexneri.

In vitro antioxidant, antimicrobial, cytotoxic potential of gold and silver nanoparticles prepared using Embelia ribes.

PubMed

Dhayalan, Manikandan; Denison, Michael Immanuel Jesse; L, Anitha Jegadeeshwari; Krishnan, Kathiravan; N, Nagendra Gandhi

2017-02-01

In recent years, the green synthesis of gold (GNPs) and silver (SNPs) nanoparticles has gained great interest among chemists and researchers. The present study reports an eco-friendly, cost-effective, rapid and easy method for the synthesis of gold and silver nanoparticles using the seed extract of Embelia ribes (SEEr) as capping and reducing agent. The synthesised GNPs and SNPs were characterised using the following techniques: UV-vis spectroscopy, DLS, HR-TEM, FT-IR and XRD. The free radical scavenging potential of GNPs and SNPs was measured by DPPH assay and Phosphomolybdenum assay. Further, the antimicrobial activity against two micro-organisms were tested using disc diffusion method and cytotoxicity of GNPs and SNPs was determined against MCF-7 cell lines at different concentrations by MTT assay. Both the GNPs and SNPs prepared from E. ribes comparatively showed promising results thereby proving their clinical importance.

Synthesis and evaluation of a series of 6-chloro-4-methylumbelliferyl glycosides as fluorogenic reagents for screening metagenomic libraries for glycosidase activity.

PubMed

Chen, Hong-Ming; Armstrong, Zachary; Hallam, Steven J; Withers, Stephen G

2016-02-08

Screening of large enzyme libraries such as those derived from metagenomic sources requires sensitive substrates. Fluorogenic glycosides typically offer the best sensitivity but typically must be used in a stopped format to generate good signal. Use of fluorescent phenols of pKa < 7, such as halogenated coumarins, allows direct screening at neutral pH. The synthesis and characterisation of a set of nine different glycosides of 6-chloro-4-methylumbelliferone are described. The use of these substrates in a pooled format for screening of expressed metagenomic libraries yielded a "hit rate" of 1 in 60. Hits were then readily deconvoluted with the individual substrates in a single plate to identify specific activities within each clone. The use of such a collection of substrates greatly accelerates the screening process. Copyright © 2015 Elsevier Ltd. All rights reserved.

Studying the Structure and Dynamics of Biomolecules by Using Soluble Paramagnetic Probes

PubMed Central

Hocking, Henry G; Zangger, Klaus; Madl, Tobias

2013-01-01

Characterisation of the structure and dynamics of large biomolecules and biomolecular complexes by NMR spectroscopy is hampered by increasing overlap and severe broadening of NMR signals. As a consequence, the number of available NMR spectroscopy data is often sparse and new approaches to provide complementary NMR spectroscopy data are needed. Paramagnetic relaxation enhancements (PREs) obtained from inert and soluble paramagnetic probes (solvent PREs) provide detailed quantitative information about the solvent accessibility of NMR-active nuclei. Solvent PREs can be easily measured without modification of the biomolecule; are sensitive to molecular structure and dynamics; and are therefore becoming increasingly powerful for the study of biomolecules, such as proteins, nucleic acids, ligands and their complexes in solution. In this Minireview, we give an overview of the available solvent PRE probes and discuss their applications for structural and dynamic characterisation of biomolecules and biomolecular complexes. PMID:23836693

Characterisation of longitudinal variation in photonic crystal fibre

NASA Astrophysics Data System (ADS)

Francis-Jones, Robert J. A.; Mosley, Peter J.

2016-10-01

We present a method by which the degree of longitudinal variation in photonic crystal fibre (PCF) may be characterised through seeded four-wave mixing (FWM). Using an iterative numerical reconstruction, we created a model PCF that displays similar FWM phasematching properties across all measured length scales. Our results demonstrate that the structure of our PCF varies by less than 1% and that the characteristic length of the variations is approximately 15 cm.

Interface-Assisted Synthesis of 2D Materials: Trend and Challenges.

PubMed

Dong, Renhao; Zhang, Tao; Feng, Xinliang

2018-06-18

The discovery of graphene one decade ago has triggered enormous interest in developing two-dimensional materials (2DMs)-that is 2D allotropes of various elements or compounds (consisting of two or more covalently bonded elements) or molecular frameworks with periodic structures. At present, various synthesis strategies have been exploited to produce 2DMs, such as top-down exfoliation and bottom-up chemical vapor deposition and solution synthesis methods. In this review article, we will highlight the interfacial roles toward the controlled synthesis of inorganic and organic 2DMs with varied structural features. We will summarize the state-of-the-art progress on interfacial synthesis strategies and address their advancements in the structural, morphological, and crystalline control by the direction of the arrangement of the molecules or precursors at a confined 2D space. First, we will provide an overview of the interfaces and introduce their advantages and uniqueness for the synthesis of 2DMs, followed by a brief classification of inorganic and organic 2DMs achieved by interfacial synthesis. Next, the currently developed interfacial synthesis strategies combined with representative inorganic and organic 2DMs are summarized, including the description of method details, the corresponding structural features, and the insights into the advantages and limitations of the synthesis methods, along with some recommendable characterization methods for understanding the interfacial assembly of the precursors and crystal growth of 2DMs. After that, we will discuss several classes of emerging organic 2DMs with particular emphasis on the structural control by the interfacial synthesis strategies. Note that, inorganic 2DMs will not be categorized separately due to the fact that a number of review articles have covered the synthesis, structure, processing, and applications. Finally, the challenges and perspectives are provided regarding the future development of interface-assisted synthesis of 2DMs with diverse structural and functional control.

Characterising human atherosclerotic carotid plaque tissue composition and morphology using combined spectroscopic and imaging modalities.

PubMed

Barrett, Hilary E; Mulvihill, John J; Cunnane, Eoghan M; Walsh, Michael T

2015-01-01

Calcification is a marked pathological component in carotid artery plaque. Studies have suggested that calcification may induce regions of high stress concentrations therefore increasing the potential for rupture. However, the mechanical behaviour of the plaque under the influence of calcification is not fully understood. A method of accurately characterising the calcification coupled with the associated mechanical plaque properties is needed to better understand the impact of calcification on the mechanical behaviour of the plaque during minimally invasive treatments. This study proposes a comparison of biochemical and structural characterisation methods of the calcification in carotid plaque specimens to identify plaque mechanical behaviour. Biochemical analysis, by Fourier Transform Infrared (FTIR) spectroscopy, was used to identify the key components, including calcification, in each plaque sample. However, FTIR has a finite penetration depth which may limit the accuracy of the calcification measurement. Therefore, this FTIR analysis was coupled with the identification of the calcification inclusions located internally in the plaque specimen using micro x-ray computed tomography (μX-CT) which measures the calcification volume fraction (CVF) to total tissue content. The tissue characterisation processes were then applied to the mechanical material plaque properties acquired from experimental circumferential loading of human carotid plaque specimen for comparison of the methods. FTIR characterised the degree of plaque progression by identifying the functional groups associated with lipid, collagen and calcification in each specimen. This identified a negative relationship between stiffness and 'lipid to collagen' and 'calcification to collagen' ratios. However, μX-CT results suggest that CVF measurements relate to overall mechanical stiffness, while peak circumferential strength values may be dependent on specific calcification geometries. This study demonstrates the need to fully characterise the calcification structure of the plaque tissue and that a combination of FTIR and μX-CT provides the necessary information to fully understand the mechanical behaviour of the plaque tissue.

Hybrid TiO2/ZnO and TiO2/Al plasmon impregnated ZnO nanocomposite photoanodes for DSSCs: synthesis and characterisation

NASA Astrophysics Data System (ADS)

Pugazhendhi, K.; D’Almeida, Steven; Naveen Kumar, P.; Sahaya Selva Mary, J.; Tenkyong, Tenzin; Sharmila, D. J.; J, Madhavan; Merline Shyla, J.

2018-04-01

The proposed work reports the synthesis and characterisation of novel and hybrid nanocomposites TiO2/ZnO and TiO2/Al plasmon impregnated ZnO, prepared using sol-gel method. X-Ray Diffraction analysis confirmed the crystalline nature of the nanocomposites with high degree of purity and the crystallite size was found to be 22 nm (TiO2/ZnO) and 21 nm (TiO2/Al-ZnO) using Scherrer’s formula. The surface chemistry, elemental compositions and purity were investigated and established using Energy Dispersive X-ray Analysis. The specific surface area of TiO2/ZnO was observed to be 23 m2 g‑1 whereas on comparison, a slight decrease was observed in the case of TiO2/Al-ZnO to 19 m2 g‑1 from Brunauer–Emmett–Teller analysis and in addition, both the samples were identified to be mesoporous in nature. The vibrational assignments were observed using Fourier Transform Infra-Red spectroscopy and results confirmed the existence of TiO2, ZnO and Al groups. The electrical response of the nanocomposites to the incident radiation with applied electric field was examined using Field Dependent Dark and Photo conductivity studies. The observed measurements revealed that the photocurrent values are greater than the dark currents which confirmed the photoconductive nature of the nanocomposites. While both the prepared nanocomposites qualify as good candidates for usage as efficient photoanodes for DSSCs, TiO2/Al-ZnO indicates a slight edge over the other.

Identification of clinical phenotypes in knee osteoarthritis: a systematic review of the literature.

PubMed

Dell'Isola, A; Allan, R; Smith, S L; Marreiros, S S P; Steultjens, M

2016-10-12

Knee Osteoarthritis (KOA) is a heterogeneous pathology characterized by a complex and multifactorial nature. It has been hypothesised that these differences are due to the existence of underlying phenotypes representing different mechanisms of the disease. The aim of this study is to identify the current evidence for the existence of groups of variables which point towards the existence of distinct clinical phenotypes in the KOA population. A systematic literature search in PubMed was conducted. Only original articles were selected if they aimed to identify phenotypes of patients aged 18 years or older with KOA. The methodological quality of the studies was independently assessed by two reviewers and qualitative synthesis of the evidence was performed. Strong evidence for existence of specific phenotypes was considered present if the phenotype was supported by at least two high-quality studies. A total of 24 studies were included. Through qualitative synthesis of evidence, six main sets of variables proposing the existence of six phenotypes were identified: 1) chronic pain in which central mechanisms (e.g. central sensitisation) are prominent; 2) inflammatory (high levels of inflammatory biomarkers); 3) metabolic syndrome (high prevalence of obesity, diabetes and other metabolic disturbances); 4) Bone and cartilage metabolism (alteration in local tissue metabolism); 5) mechanical overload characterised primarily by varus malalignment and medial compartment disease; and 6) minimal joint disease characterised as minor clinical symptoms with slow progression over time. This study identified six distinct groups of variables which should be explored in attempts to better define clinical phenotypes in the KOA population.

New multirate sampled-data control law structure and synthesis algorithm

NASA Technical Reports Server (NTRS)

Berg, Martin C.; Mason, Gregory S.; Yang, Gen-Sheng

1992-01-01

A new multirate sampled-data control law structure is defined and a new parameter-optimization-based synthesis algorithm for that structure is introduced. The synthesis algorithm can be applied to multirate, multiple-input/multiple-output, sampled-data control laws having a prescribed dynamic order and structure, and a priori specified sampling/update rates for all sensors, processor states, and control inputs. The synthesis algorithm is applied to design two-input, two-output tip position controllers of various dynamic orders for a sixth-order, two-link robot arm model.

Characterisation of North American Brucella isolates from marine mammals.

PubMed

Whatmore, Adrian M; Dawson, Claire; Muchowski, Jakub; Perrett, Lorraine L; Stubberfield, Emma; Koylass, Mark; Foster, Geoffrey; Davison, Nicholas J; Quance, Christine; Sidor, Inga F; Field, Cara L; St Leger, Judy

2017-01-01

Extension of known ecological niches of Brucella has included the description of two novel species from marine mammals. Brucella pinnipedialis is associated predominantly with seals, while two major Brucella ceti clades, most commonly associated with porpoises or dolphins respectively, have been identified. To date there has been limited characterisation of Brucella isolates obtained from marine mammals outside Northern European waters, including North American waters. To address this gap, and extend knowledge of the global population structure and host associations of these Brucella species, 61 isolates from marine mammals inhabiting North American waters were subject to molecular and phenotypic characterisation enabling comparison with existing European isolates. The majority of isolates represent genotypes previously described in Europe although novel genotypes were identified in both B. ceti clades. Harp seals were found to carry B. pinnipedialis genotypes previously confined to hooded seals among a diverse repertoire of sequence types (STs) associated with this species. For the first time Brucella isolates were characterised from beluga whales and found to represent a number of distinct B. pinnipedialis genotypes. In addition the known host range of ST27 was extended with the identification of this ST from California sea lion samples. Finally the performance of the frequently used diagnostic tool Bruce-ladder, in differentiating B. ceti and B. pinnipedialis, was critically assessed based on improved knowledge of the global population structure of Brucella associated with marine mammals.

Characterisation of North American Brucella isolates from marine mammals

PubMed Central

Dawson, Claire; Muchowski, Jakub; Perrett, Lorraine L.; Stubberfield, Emma; Koylass, Mark; Foster, Geoffrey; Davison, Nicholas J.; Quance, Christine; Sidor, Inga F.; Field, Cara L.; St. Leger, Judy

2017-01-01

Extension of known ecological niches of Brucella has included the description of two novel species from marine mammals. Brucella pinnipedialis is associated predominantly with seals, while two major Brucella ceti clades, most commonly associated with porpoises or dolphins respectively, have been identified. To date there has been limited characterisation of Brucella isolates obtained from marine mammals outside Northern European waters, including North American waters. To address this gap, and extend knowledge of the global population structure and host associations of these Brucella species, 61 isolates from marine mammals inhabiting North American waters were subject to molecular and phenotypic characterisation enabling comparison with existing European isolates. The majority of isolates represent genotypes previously described in Europe although novel genotypes were identified in both B. ceti clades. Harp seals were found to carry B. pinnipedialis genotypes previously confined to hooded seals among a diverse repertoire of sequence types (STs) associated with this species. For the first time Brucella isolates were characterised from beluga whales and found to represent a number of distinct B. pinnipedialis genotypes. In addition the known host range of ST27 was extended with the identification of this ST from California sea lion samples. Finally the performance of the frequently used diagnostic tool Bruce-ladder, in differentiating B. ceti and B. pinnipedialis, was critically assessed based on improved knowledge of the global population structure of Brucella associated with marine mammals. PMID:28934239

Fabrication and characterisation of nanocrystalline graphite MEMS resonators using a geometric design to control buckling

NASA Astrophysics Data System (ADS)

Fishlock, S. J.; O'Shea, S. J.; McBride, J. W.; Chong, H. M. H.; Pu, S. H.

2017-09-01

The simulation, fabrication and characterisation of nanographite MEMS resonators is reported in this paper. The deposition of nanographite is achieved using plasma-enhanced chemical vapour deposition directly onto numerous substrates such as commercial silicon wafers. As a result, many of the reliability issues of devices based on transferred graphene are avoided. The fabrication of the resonators is presented along with a simple undercutting method to overcome buckling, by changing the effective stress of the structure from ~436 MPa compressive, to ~13 MPa tensile. The characterisation of the resonators using electrostatic actuation and laser Doppler vibrometry is reported, demonstrating resonator frequencies from 5-640 kHz and quality factor above 1819 in vacuum obtained.

Synthesis characterisation series of newly fabricated type II CdSe CdSe/CdTe nanocrystals and their optical properties

NASA Astrophysics Data System (ADS)

Ahmed, A. S.; Christopher, W.

2018-03-01

Nanocrystalline semiconductors exhibit different properties due to two basic factors. They possess high surface to volume ratio and the actual size of particle can determine the electronic and physical properties of the material. The small size results in an observable quantum confinement effect, defined by the increasing bandgap accompanied by the quantization of the energy levels to discrete values. In present work we have synthesized the series of cadmium selenide/cadmium telluride (CdSe/CdTe) core/shell and CdSe/CdTe/CdS core/shell/shell to investigate the biexciton energy through transient absorption measurements. These structures are type II nanocrystals are with a hole in the shell and the electron confined to the core. We specifically investigate the effect of nanoparticle shape on the electronic structure and ultrafast electronic dynamics in the band-edge exciton states of CdSe quantum dots, nanorods, and nanoplatelets. Particle size was chosen to enable straightforward comparisons of the effects of particle shape on the spectra and dynamics without retuning the laser source. In our results the Uv-vis showed only a mild redshift in the first excitonic an elongated tail with increasing shell thickness. High resolution Transmission Electron Microscopy (HRTEM) shows the slight agglomeration of the nanocrystals but still the size distribution was calculate able. Spherical small crystals ranging from 5.9 nm to 10 nm are observed. CdTe/CdSe structures were quasi spherical with a rough diameter 6 nm with some little agglomerated structure. . The spherical nanocrystals could be peanut shaped oriented along the c axis or the spherical only, which could explain the two peak emission. p-XRD results indicate the predominant wurtzite structure throughout.

A Versatile Strategy for the Semisynthetic Production of Ser65 Phosphorylated Ubiquitin and Its Biochemical and Structural Characterisation

PubMed Central

Han, Cong; Pao, Kuan-Chuan; Kazlauskaite, Agne; Muqit, Miratul M K; Virdee, Satpal

2015-01-01

Ubiquitin phosphorylation is emerging as an important regulatory layer in the ubiquitin system. This is exemplified by the phosphorylation of ubiquitin on Ser65 by the Parkinson's disease-associated kinase PINK1, which mediates the activation of the E3 ligase Parkin. Additional phosphorylation sites on ubiquitin might also have important cellular roles. Here we report a versatile strategy for preparing phosphorylated ubiquitin. We biochemically and structurally characterise semisynthetic phospho-Ser65-ubiquitin. Unexpectedly, we observed disulfide bond formation between ubiquitin molecules, and hence a novel crystal form. The method outlined provides a direct approach to study the combinatorial effects of phosphorylation on ubiquitin function. Our analysis also suggests that disulfide engineering of ubiquitin could be a useful strategy for obtaining alternative crystal forms of ubiquitin species thereby facilitating structural validation. PMID:26010437

Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compounds-synthesis, X-Ray studies and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Machura, B., E-mail: basia@ich.us.edu.pl; Switlicka, A.; Zwolinski, P.

2013-01-15

Seven novel heterobimetallic Cu/Hg polymers based on thiocyanate bridges have been synthesised and characterised by means of IR, EPR, magnetic measurements and single crystal X-Ray. Three of them, [Cu(pzH){sub 4}Hg(SCN){sub 4}]{sub n} (1) [Cu(indH){sub 4}Hg(SCN){sub 4}]{sub n} (2) and [Cu(ampy){sub 2}Hg(SCN){sub 4}]{sub n} (3), have one-dimensional coordination structure. Two compounds [Cu(pzH){sub 2}Hg(SCN){sub 4}]{sub n} (4) and [Cu(abzimH)Hg(SCN){sub 4}]{sub n} (5) form two-dimensional nets, whereas the complexes [Cu(pyCN){sub 2}Hg(SCN){sub 4}]{sub n} (6) and [Cu(pyCH(OH)(OMe)){sub 2}Hg(SCN){sub 4}]{sub n} (7) are three-dimensional coordination polymers. The chains of 1 are connected by the intermolecular N-H Bullet Bullet Bullet N hydrogen bonds to the threemore » dimensional net. In 2 the N-H Bullet Bullet Bullet S hydrogen bonds link the polymeric chains to the two dimensional layer extending along crystallographic (0 0 1) plane. The polymeric chains of compound 3 are joined by the intermolecular N-H Bullet Bullet Bullet N and N-H Bullet Bullet Bullet S hydrogen bonds to the three dimensional net. The polymeric layers of 4 are connected by the intermolecular N-H Bullet Bullet Bullet N hydrogen bonds to the three dimensional net. - Graphical abstract: Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compound-synthesis,X-Ray studies and magnetic properties. Highlights: Black-Right-Pointing-Pointer Novel heterobimetallic Cu/Hg coordination polymers were synthesised. Black-Right-Pointing-Pointer The multidimensional structures have been proved by single X-ray analysIs. Black-Right-Pointing-Pointer A variation in the crystalline architectures was observed depending on auxiliary ligands. Black-Right-Pointing-Pointer Magnetic measurements indicate weak exchange interaction between Cu(II) in the crystal lattices below 10 K.« less

Synthesis, characterisation and catalytic activity of 4, 5-imidazoledicarboxylate ligated Co(II) and Cd(II) metal-organic coordination complexes

NASA Astrophysics Data System (ADS)

Gangu, Kranthi Kumar; Maddila, Suresh; Mukkamala, Saratchandra Babu; Jonnalagadda, Sreekantha B.

2017-09-01

Two mono nuclear coordination complexes, namely, [Co(4,5-Imdc)2 (H2O)2] (1) and [Cd(4,5-Imdc)2(H2O)3]·H2O (2) were constructed using Co(II) and Cd(II) metal salts with 4,5-Imidazoledicarboxylic acid (4,5-Imdc) as organic ligand. Both 1, 2 were structurally characterized by single crystal XRD and the results reveal that 1 belongs to P21/n space group with unit cell parameters [a = 5.0514(3) Å, b = 22.5786(9) Å, c = 6.5377(3) Å, β = 111.5°] whereas, 2 belongs to P21/c space group with unit cell parameters [a = 6.9116(1) Å, b = 17.4579(2) Å, c = 13.8941(2) Å, β = 97.7°]. While Co(II) in 1 exhibited a six coordination geometry with 4,5-Imdc and water molecules, Cd(II) ion in 2 showed a seven coordination with the same ligand and solvent. In both 1 and 2, the hydrogen bond interactions with mononuclear unit generated 3D-supramolecular structures. Both complexes exhibit solid state fluorescent emission at room temperature. The efficacy of both the complexes as heterogeneous catalysts was examined in the green synthesis of six pyrano[2,3,c]pyrazole derivatives with ethanol as solvent via one-pot reaction between four components, a mixture of aromatic aldehyde, malononitrile, hydrazine hydrate and dimethyl acetylenedicarboxylate. Both 1 and 2 have produced pyrano [2,3,c]pyrazoles in impressive yields (92-98%) at room temperature in short interval of times (<20 min), with no need for any chromatographic separations. With good stability, ease of preparation and recovery plus reusability up to six cycles, both 1 and 2 prove to be excellent environmental friendly catalysts for the value-added organic transformations using green principles.

Characterising the structure of quasi-periodic mixing events in stratified turbulent Taylor-Couette flow

NASA Astrophysics Data System (ADS)

Singh, Kanwar Nain; Partridge, Jamie; Dalziel, Stuart; Caulfield, C. P.; Mathematical Underpinnings of Stratified Turbulence (MUST) Team

2017-11-01

We present results from experiments conducted to study mixing in a two-layer stably-stratified turbulent Taylor-Couette flow. It has previously been observed that there is a quasi-periodic mixing event located at the interface separating the layers. We observe, through conductivity probe measurements, that the power of the mixing event in the frequency spectrum of the density data at the interface is higher when measured near the inner cylinder than in the middle of the annular gap. This is consistent with Oglethorpe's (2014) hypothesis that the mixing structure is triggered near the inner cylinder, and then advects and decays or disperses radially. We also observe that at Ri =g/'Ro (RiΩi)2 7 , where Ri, Ro are the inner and outer cylinder radius, respectively, g ' the reduced gravity characterising the density jump between the layers and Ωi is the rotation rate of the inner cylinder, the power drops significantly at all radial locations, which is reminiscent of the onset of the enhanced flux regime as observed by Oglethorpe et al. (2013). We perform experiments to characterise the spatial extent and dynamics of this mixing structure using particle image velocimetry (PIV) giving further insights into this important mixing process. EPSRC programme Grant EP/K034529/1 & SGPC-CCT Scholarship.

The use of deconvolution techniques to identify the fundamental mixing characteristics of urban drainage structures.

PubMed

Stovin, V R; Guymer, I; Chappell, M J; Hattersley, J G

2010-01-01

Mixing and dispersion processes affect the timing and concentration of contaminants transported within urban drainage systems. Hence, methods of characterising the mixing effects of specific hydraulic structures are of interest to drainage network modellers. Previous research, focusing on surcharged manholes, utilised the first-order Advection-Dispersion Equation (ADE) and Aggregated Dead Zone (ADZ) models to characterise dispersion. However, although systematic variations in travel time as a function of discharge and surcharge depth have been identified, the first order ADE and ADZ models do not provide particularly good fits to observed manhole data, which means that the derived parameter values are not independent of the upstream temporal concentration profile. An alternative, more robust, approach utilises the system's Cumulative Residence Time Distribution (CRTD), and the solute transport characteristics of a surcharged manhole have been shown to be characterised by just two dimensionless CRTDs, one for pre- and the other for post-threshold surcharge depths. Although CRTDs corresponding to instantaneous upstream injections can easily be generated using Computational Fluid Dynamics (CFD) models, the identification of CRTD characteristics from non-instantaneous and noisy laboratory data sets has been hampered by practical difficulties. This paper shows how a deconvolution approach derived from systems theory may be applied to identify the CRTDs associated with urban drainage structures.

Structural and calorimetric studies demonstrate that the hepatocyte nuclear factor 1β (HNF1β) transcription factor is imported into the nucleus via a monopartite NLS sequence.

PubMed

Wiedmann, Mareike M; Aibara, Shintaro; Spring, David R; Stewart, Murray; Brenton, James D

2016-09-01

The transcription factor hepatocyte nuclear factor 1β (HNF1β) is ubiquitously overexpressed in ovarian clear cell carcinoma (CCC) and is a potential therapeutic target. To explore potential approaches that block HNF1β transcription we have identified and characterised extensively the nuclear localisation signal (NLS) for HNF1β and its interactions with the nuclear protein import receptor, Importin-α. Pull-down assays demonstrated that the DNA binding domain of HNF1β interacted with a spectrum of Importin-α isoforms and deletion constructs tagged with eGFP confirmed that the HNF1β (229)KKMRRNR(235) sequence was essential for nuclear localisation. We further characterised the interaction between the NLS and Importin-α using complementary biophysical techniques and have determined the 2.4Å resolution crystal structure of the HNF1β NLS peptide bound to Importin-α. The functional, biochemical, and structural characterisation of the nuclear localisation signal present on HNF1β and its interaction with the nuclear import protein Importin-α provide the basis for the development of compounds targeting transcription factor HNF1β via its nuclear import pathway. Copyright © 2016. Published by Elsevier Inc.

1,2,4,5-Benzenetetracarboxylic acid: a versatile hydrogen bonding template for controlling the regioselective topochemical synthesis of head-to-tail photodimers from stilbazole derivatives.

PubMed

Ortega, Gabriela; Hernández, Jesús; González, Teresa; Dorta, Romano; Briceño, Alexander

2018-05-16

The crystal engineering of hydrogen bonded organic assemblies based on 1,2,4,5-benzenetetracarboxylic acid (H4bta) and stilbazole derivatives (1-10) is exploited to provide regio-controlled [2 + 2] photocycloadditions in the solid state. Single crystal X-ray diffraction analyses have revealed that all the arrays are built-up from the self-assembly of the (H2bta)2- dianion with two stilbazolium cations via O-HO- and N+-HO- charge-assisted H-bonding synthons: (4-Hstilbazolium+)2(H2bta2-). The dianion displays an interesting diversity of H-bonding motifs. Such structural flexibility allowed us to obtain four structure-types defined by the preferential formation of intramolecular or intermolecular hydrogen bonds between carboxylate-carboxylic groups. In these ionic assemblies two predominant structural H-bonding patterns were observed. The first pattern is characterised by the formation of intramolecular H-bonds in the dianion, leading to discrete assemblies based on ternary arrays. The second hydrogen pattern consists of 2-D hydrogen networks built-up from the self-assembly of anions via intermolecular H-bonds that are linked to the cations. Two additional examples, in which the dianion is self-assembled in two types of ribbons, were also observed. Another supramolecular feature predominant in all these arrays is the stacking of the cations in a head-to-tail fashion, which is controlled via cation-π interactions. These arrays are photoactive in the solid state upon UV-irradiation leading to the regioselective synthesis of rctt-cyclobutane head-to-tail-isomers in high to quantitative yield. In this work, the template tolerance either to steric or electronic effects by changing the number or positions of the supramolecular interactions exerted by distinctive functional groups was also explored. In addition, assemblies bearing 2-chloro (7 and 8) and 3-chloro-4-stilbazole (1 and 9) crystallize in two different crystalline forms, leading to novel examples of supramolecular isomers with similar solid state reactivity.

Development and characterisation of hybrid polysaccharide membranes for dehydration processes.

PubMed

Meireles, Inês T; Huertas, Rosa M; Torres, Cristiana A V; Coelhoso, Isabel M; Crespo, João G

2018-07-01

The purpose of this work is the development and characterisation of new hybrid polysaccharide (FucoPol) membranes. These membranes were prepared by incorporation of a SiO 2 network homogeneously dispersed by using a sol-gel method with GPTMS as a crosslinker silica precursor. They were further crosslinked with CaCl 2 for reinforcement of mechanical properties and improvement of their permeation performance. They were characterised in terms of their structural, mechanical and thermal properties. They presented a dense and homogeneous structure, resistant to deformation, with a Tg of 43 °C and a thermal decomposition between 240 and 251 °C. The hybrid FucoPol membranes were tested for ethanol dehydration by pervaporation and also for nitrogen dehydration. They exhibited high water selectivity values, similar to PERVAP ® 4101, however they lost their stability when exposed to solutions of 10.0 wt.% water in ethanol. In contrast, these membranes were stable when applied in N 2 dehydration, leading to reproducible performance and very high water selectivities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Characterisation of branched gluco-oligosaccharides to study the mode-of-action of a glucoamylase from Hypocrea jecorina.

PubMed

Jonathan, M C; van Brussel, M; Scheffers, M S; Kabel, M A

2015-11-05

In the conversion of starch to fermentable glucose for bioethanol production, hydrolysis of amylopectin by α-amylases and glucoamylases is the slowest step. In this process, α-1,6-branched gluco-oligosaccharides accumulate and are slowly degraded. Glucoamylases that are able to degrade such branched oligosaccharides faster are economically beneficial. This research aimed at the isolation and characterisation of branched gluco-oligosaccharides produced from amylopectin digestion by α-amylase, to be used as substrates for comparing their degradation by glucoamylases. Branched gluco-oligosaccharides with a DP between five and twelve were purified using size exclusion chromatography. These structures were characterised after labelling with 2-aminobenzamide using UHPLC-MS(n) analysis. Further, the purified oligosaccharides were used to evaluate the mode-of-action of a glucoamylase from Hypocrea jecorina. The enzyme cleaves the α-1,4-linkage adjacent to the α-1,6-linkage at a lower rate than that of α-1,4-linkages in linear oligosaccharides. Hence, the branched gluco-oligosaccharides are a suitable substrate to evaluate glucoamylase activity on branched structures. Copyright © 2015 Elsevier Ltd. All rights reserved.

A methodology for creating greenways through multidisciplinary sustainable landscape planning.

PubMed

Pena, Selma Beatriz; Abreu, Maria Manuela; Teles, Rui; Espírito-Santo, Maria Dalila

2010-01-01

This research proposes a methodology for defining greenways via sustainable planning. This approach includes the analysis and discussion of culture and natural processes that occur in the landscape. The proposed methodology is structured in three phases: eco-cultural analysis; synthesis and diagnosis; and proposal. An interdisciplinary approach provides an assessment of the relationships between landscape structure and landscape dynamics, which are essential to any landscape management or land use. The landscape eco-cultural analysis provides a biophysical, dynamic (geomorphologic rate), vegetation (habitats from directive 92/43/EEC) and cultural characterisation. The knowledge obtained by this analysis then supports the definition of priority actions to stabilise the landscape and the management measures for the habitats. After the analysis and diagnosis phases, a proposal for the development of sustainable greenways can be achieved. This methodology was applied to a study area of the Azambuja Municipality in the Lisbon Metropolitan Area (Portugal). The application of the proposed methodology to the study area shows that landscape stability is crucial for greenway users in order to appreciate the landscape and its natural and cultural elements in a sustainable and healthy way, both by cycling or by foot. A balanced landscape will increase the value of greenways and in return, they can develop socio-economic activities with benefits for rural communities. Copyright 2009 Elsevier Ltd. All rights reserved.

Studies on gallium nitride doped ferrite-polypyrrole nanocomposites

NASA Astrophysics Data System (ADS)

Indrakanti, Rajani; Brahmaji Rao, V.; Udaya Kiran, C.

2018-06-01

This communication reports the synthesis and characterisation of two novel Intrinsic conducting polymer nano composites (ICPN s) with the formulae Ga (2x+2) N Fe 2(49-x) O3—PPY synthesized using Impregnation technique. The Gallium nitride ferrite nano particles were synthesized for x = 1 and x = 5 using the above stichiometric equation earlier by Sol—Gel route. The chemical composition in the assembly of the ICPNs were Ga4NFe96O3-3%,10%,30% Polypyrrole, Ga12NFe88O3-3%,10%,30% Polypyrrole by weight. The Sci-Finder software failed to trace any earlier articles or reviews related to these ICNPs synthesised by us in the literature. X-ray Diffractometric (Structural), Morphological, EDAX SAED, IR spectroscopic characterizations were done on the synthesized nanocomposites. Structural studies reveal the semi-crystalline nature of composites. The average crystallite size of nano composites is decreased when compared with nano ferrites. SEM findings reveal that the shape for higher percentage of PPY is nano rods; for lower percentage it is globular. TEM reveals good dispersion and average particle size from histograms are calculated. The FT- IR bands of PPY and GaNFe2O3 are observed which show strong interaction between PPY- GaNFe2O3. Also there is a shift of bands in GaNFe2O3-PPY nano composites when compared to the bands of PPY.

Synthesis and (spectro)electrochemistry of mixed-valent diferrocenyl-dihydrothiopyran derivatives.

PubMed

Kowalski, Konrad; Karpowicz, Rafał; Mlostoń, Grzegorz; Miesel, Dominique; Hildebrandt, Alexander; Lang, Heinrich; Czerwieniec, Rafał; Therrien, Bruno

2015-04-07

Three novel diferrocenyl complexes were prepared and characterised. 2,2-Diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran (1, sulphide) was accessible by the hetero-Diels-Alder reaction of diferrocenyl thioketone with 2,3-dimethyl-1,3-butadiene. Stepwise oxidation of 1 gave the respective oxides 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1-oxide (2, sulfoxide) and 2,2-diferrocenyl-4,5-dimethyl-3,6-dihydro-2H-thiopyran-1,1-dioxide (3, sulfone), respectively. The molecular structures of 1 and 3 in the solid state were determined by single crystal X-ray crystallography. The oxidation of sulphide 1 to sulfone 3, plays only a minor role on the overall structure of the two compounds. Electrochemical (cyclic voltammetry (= CV), square wave voltammetry (= SWV)) and spectroelectrochemical (in situ UV-Vis/NIR spectroscopy) studies were carried out. The CV and SWV measurements showed that an increase of the sulphur atom oxidation from -2 in 1 to +2 in 3 causes an anodic shift of the ferrocenyl-based oxidation potentials of about 100 mV. The electrochemical oxidation of 1-3 generates mixed-valent cations 1(+)-3(+). These monooxidised species display low-energy electronic absorption bands between 1000 and 3000 nm assigned to IVCT (= Inter-Valence Charge Transfer) electronic transitions. Accordingly, the mixed-valent cations 1(+)-3(+) are classified as weakly coupled class II systems according to Robin and Day.

Synthesis, Characterisation and 3D micro-structuring via 2-Photon Polymerisation of Poly(glycerol sebacate)-Methacrylate – an Elastomeric Degradable Polymer

NASA Astrophysics Data System (ADS)

Pashneh-Tala, Samand; Owen, Robert; Bahmaee, Hossein; Rekštytė, Sima; Malinauskas, Mangirdas; Claeyssens, Frederik

2018-05-01

Poly(glycerol sebacate) (PGS) has been utilised in numerous biomaterial applications over recent years. This elastomeric and rapidly degradable polymer is cytocompatible and suited to various applications in soft tissue engineering and drug delivery. Although PGS is simple to synthesise as an insoluble prepolymer, it requires the application of high temperatures for extended periods of time to produce an insoluble matrix. This places limitations on the processing capabilities of PGS and its possible applications. Here, we present a photocurable form of PGS with improved processing capabilities: PGS-methacrylate (PGS-M). By methacrylating the secondary hydroxyl groups of the glycerol units in the PGS prepolymer chains, the material was rendered photocurable and, in combination with a photoinitiator, crosslinked rapidly on exposure to UV light at ambient temperatures. The polymer's molecular weight and the degree of methacrylation could be controlled independently and the mechanical properties of the crosslinked material tailored. The polymer also displayed rapid degradation under physiological conditions and cytocompatibility with various primary cell types. As a demonstration of the processing capabilities of PGS-M, µm scale 3D scaffold structures were fabricated using 2-photon polymerisation and used for 3D cell culture. The tunable properties of PGS-M coupled with its enhanced processing capabilities make the polymer an attractive potential biomaterial for various future applications.

Flash microwave synthesis and sintering of nanosized La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}o{sub 3-{delta}} for fuel cell application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Combemale, L., E-mail: lionel.combemale@u-bourgogne.f; Caboche, G.; Stuerga, D.

2009-10-15

Perovskite-oxide nanocrystals of La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}O{sub 3-{delta}} with a mean size around 10 nm were prepared by microwave flash synthesis. This reaction was performed in alcoholic solution using metallic salts, sodium ethoxide and microwave autoclave. The obtained powder was characterised after purification by energy dispersive X-ray analysis (EDX), X-ray powder diffraction (XRD), BET adsorption technique, photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM). The results show that integrated perovskite-type phase and uniform particle size were obtained in the microwave treated samples. At last the synthesised powder was directly used in a sintering process. A porous solid, inmore » accordance with the expected applications, was then obtained at low sintering temperature (1000 deg. C) without use of pore forming agent. - Graphical abstract: TEM photograph of La{sub 0.75}Sr{sub 0.25}Cr{sub 0.93}Ru{sub 0.07}O{sub 3-{delta}} obtained by microwave flash synthesis. This picture confirms the nanometric size of the ceramic particles.« less

Lipoteichoic acid synthesis inhibition in combination with antibiotics abrogates growth of multidrug-resistant Enterococcus faecium.

PubMed

Paganelli, Fernanda L; van de Kamer, Tim; Brouwer, Ellen C; Leavis, Helen L; Woodford, Neil; Bonten, Marc J M; Willems, Rob J L; Hendrickx, Antoni P A

2017-03-01

Enterococcus faecium is a multidrug-resistant (MDR) nosocomial pathogen causing significant morbidity in debilitated patients. New antimicrobials are needed to treat antibiotic-resistant E. faecium infections in hospitalised patients. E. faecium incorporates lipoteichoic acid (LTA) (1,3-polyglycerol-phosphate linked to glycolipid) in its cell wall. The small-molecule inhibitor 1771 [2-oxo-2-(5-phenyl-1,3,4-oxadiazol-2-ylamino)ethyl 2-naphtho[2,1-b]furan-1-ylacetate] specifically blocks the activity of Staphylococcus aureus LtaS synthase, which polymerises 1,3-glycerolphosphate into LTA polymers. Here we characterised the effects of the small-molecule inhibitor 1771 on the growth of E. faecium isolates, alone (28 strains) or in combination with the antibiotics vancomycin, daptomycin, ampicillin, gentamicin or linezolid (15 strains), and on biofilm formation (16 strains). Inhibition of LTA synthesis at the surface of the cell by compound 1771 in combination with current antibiotic therapy abrogates enterococcal growth in vitro but does not affect mature E. faecium biofilms. Targeting LTA synthesis may provide new possibilities to treat MDR E. faecium infections. Copyright © 2017 Elsevier B.V. and International Society of Chemotherapy. All rights reserved.

Characterisation of Sol-Gel Synthesis of Phase Pure CaTiO3 Nano Powders after Drying

NASA Astrophysics Data System (ADS)

Mallik, P. K.; Biswal, G.; Patnaik, S. C.; Senapati, S. K.

2015-02-01

According to a few recent studies, calcium titanate (CT) is a material that is similar to hydroxyapatite in biological properties. However, calcium titanate is not currently being used in the biomedical applications as to hydroxyapatite. The objective is to prepare nano calcium titanate powders from the equimolar solution of calcium oxide, ethanol and Titanium (IV) isopropoxide via sol-gel synthesis. The phase analysis and morphology of powder particles were studied by X-ray diffraction (XRD), while the composition and size of powder particles were determined by Transmission electron microscope (TEM) attached with energy dispersive x-ray spectrometer (EDS). As results, XRD confirm the presence of phase pure crystalline CaTiO3 after drying at 100°C for 24 hours, while TEM analysis confirms about 13 nm sizes of CaTiO3 particles and some agglomerated particle of 20-30 nm. Moreover, EDS analysis indicates that the approximately stoichiometric Ca/Ti ratio 1:1 was obtained in the CaTiO3 powders. Finally, it can be concluded that described sol-gel synthesis could be novel method for the production of nano CaTiO3 particles at lower temperature compared to any other methods of production.

An antiviral protein from Bougainvillea spectabilis roots; purification and characterisation.

PubMed

Balasaraswathi, R; Sadasivam, S; Ward, M; Walker, J M

1998-04-01

An antiviral protein active against mechanical transmission of tomato spotted wilt virus was identified in the root tissues of Bougainvillea spectabilis Willd. Bougainvillea Antiviral Protein I (BAP I) was purified to apparent homogeneity from the roots of Bougainvillea by ammonium sulphate precipitation, CM- and DEAE-Sepharose chromatography and reverse phase HPLC. BAP I is a highly basic protein (pI value > 8.6) with an Mr of 28,000. The N-terminal sequence of BAP I showed homology with other plant antiviral proteins. Preliminary tests suggest that purified BAP I is capable of interfering with in vitro protein synthesis.

1-Methyl-5-Nitrotetrazole and 2-Methyl-5-Nitrotetrazole. Part 1. Synthesis, Characterisation and Detection, and Molecular Complex

DTIC Science & Technology

1980-06-01

sulfate pentahydrate (0.5 g) in water (120 cm3) was added dropwise, over a period of 90 minutes, to a stirred solution of sodium nitrite (42.4 g) in...nltrotetrazole (2) via Diazotlsation of 6 A solution of 6 (2.00 g), 98% sulfuric acid (4.0 cm3) and cupric sulfat . pentahydrate (0.4 g) in water (60...from 5 was much cleaner. A further intriguing observation is that the conversion of 5 to 1 is catalysed by copper ions whereas that of 6 to 2 is not

Design, Synthesis and Characterisation of New Chimeric Ruthenium(II)-Gold(I) Complexes as Improved Cytotoxic Agents

PubMed Central

Massai, Lara; Fernández-Gallardo, Jacob; Guerri, Annalisa; Arcangeli, Annarosa; Pillozzi, Serena

2015-01-01

Two heterobimetallic complexes, i.e. [RuCl2(p-cymene)(µ-dppm)AuC] (1) and [RuCl2(p-cymene)(µ-dppm)Au S(thiazoline)] (3), based on known cytotoxic [Ru(p-cymene)Cl2(PR3)] and [AuX(PR3)] (X = Cl, SR) molecular scaffolds, with the diphosphane linker 1,1-bis(diphenylphosphino) methane, dppm, were conveniently prepared and characterised. Remarkably, the new compounds manifested a more favourable in vitro pharmacological profile toward cancer cells than individual ruthenium and gold species being either more cytotoxic or more selective. The interactions of the study compounds with (pBR322) DNA and their inhibitory effects on cathepsin B were also assessed. In addition, their reactivity toward suitable models of protein targets was explored and clear evidence gained for disruption of the bimetallic motif and for protein binding of monometallic fragments. Overall, the data reported here strongly support the concept of multifunctional heterometallic compounds as “improved” candidate agents for cancer treatment. The mechanistic and pharmacological implications of the present findings are discussed. PMID:25996553

Proteomics in medical microbiology.

PubMed

Cash, P

2000-04-01

The techniques of proteomics (high resolution two-dimensional electrophoresis and protein characterisation) are widely used for microbiological research to analyse global protein synthesis as an indicator of gene expression. The rapid progress in microbial proteomics has been achieved through the wide availability of whole genome sequences for a number of bacterial groups. Beyond providing a basic understanding of microbial gene expression, proteomics has also played a role in medical areas of microbiology. Progress has been made in the use of the techniques for investigating the epidemiology and taxonomy of human microbial pathogens, the identification of novel pathogenic mechanisms and the analysis of drug resistance. In each of these areas, proteomics has provided new insights that complement genomic-based investigations. This review describes the current progress in these research fields and highlights some of the technical challenges existing for the application of proteomics in medical microbiology. The latter concern the analysis of genetically heterogeneous bacterial populations and the integration of the proteomic and genomic data for these bacteria. The characterisation of the proteomes of bacterial pathogens growing in their natural hosts remains a future challenge.

Construction and use of a Cupriavidus necator H16 soluble hydrogenase promoter (PSH) fusion to gfp (green fluorescent protein)

PubMed Central

Jugder, Bat-Erdene; Welch, Jeffrey; Braidy, Nady

2016-01-01

Hydrogenases are metalloenzymes that reversibly catalyse the oxidation or production of molecular hydrogen (H2). Amongst a number of promising candidates for application in the oxidation of H2 is a soluble [Ni–Fe] uptake hydrogenase (SH) produced by Cupriavidus necator H16. In the present study, molecular characterisation of the SH operon, responsible for functional SH synthesis, was investigated by developing a green fluorescent protein (GFP) reporter system to characterise PSH promoter activity using several gene cloning approaches. A PSH promoter-gfp fusion was successfully constructed and inducible GFP expression driven by the PSH promoter under de-repressing conditions in heterotrophic growth media was demonstrated in the recombinant C. necator H16 cells. Here we report the first successful fluorescent reporter system to study PSH promoter activity in C. necator H16. The fusion construct allowed for the design of a simple screening assay to evaluate PSH activity. Furthermore, the constructed reporter system can serve as a model to develop a rapid fluorescent based reporter for subsequent small-scale process optimisation experiments for SH expression. PMID:27547572

Design, synthesis and characterisation of new chimeric ruthenium(II)-gold(I) complexes as improved cytotoxic agents.

PubMed

Massai, Lara; Fernández-Gallardo, Jacob; Guerri, Annalisa; Arcangeli, Annarosa; Pillozzi, Serena; Contel, María; Messori, Luigi

2015-06-28

Two heterobimetallic complexes, i.e. [RuCl2(p-cymene)(μ-dppm)AuC] (1) and [RuCl2(p-cymene)(μ-dppm)Au(S-thiazoline)] (3), based on known cytotoxic [Ru(p-cymene)Cl2(PR3)] and [AuX(PR3)] (X = Cl, SR) molecular scaffolds, with the diphosphane linker 1,1-bis(diphenylphosphino)methane, dppm, were conveniently prepared and characterised. Remarkably, the new compounds manifested a more favourable in vitro pharmacological profile toward cancer cells than individual ruthenium and gold species being either more cytotoxic or more selective. The interactions of the studied compounds with (pBR322) DNA and their inhibitory effects on cathepsin B were also assessed. In addition, their reactivity toward suitable models of protein targets was explored and clear evidence gained for disruption of the bimetallic motif and for protein binding of monometallic fragments. Overall, the data reported here strongly support the concept of multifunctional heterometallic compounds as "improved" candidate agents for cancer treatment. The mechanistic and pharmacological implications of the present findings are discussed.

A Program Structure for Event-Based Speech Synthesis by Rules within a Flexible Segmental Framework.

ERIC Educational Resources Information Center

Hill, David R.

1978-01-01

A program structure based on recently developed techniques for operating system simulation has the required flexibility for use as a speech synthesis algorithm research framework. This program makes synthesis possible with less rigid time and frequency-component structure than simpler schemes. It also meets real-time operation and memory-size…

Application of X-ray and neutron small angle scattering techniques to study the hierarchical structure of plant cell walls: a review.

PubMed

Martínez-Sanz, Marta; Gidley, Michael J; Gilbert, Elliot P

2015-07-10

Plant cell walls present an extremely complex structure of hierarchically assembled cellulose microfibrils embedded in a multi-component matrix. The biosynthesis process determines the mechanism of cellulose crystallisation and assembly, as well as the interaction of cellulose with other cell wall components. Thus, a knowledge of cellulose microfibril and bundle architecture, and the structural role of matrix components, is crucial for understanding cell wall functional and technological roles. Small angle scattering techniques, combined with complementary methods, provide an efficient approach to characterise plant cell walls, covering a broad and relevant size range while minimising experimental artefacts derived from sample treatment. Given the system complexity, approaches such as component extraction and the use of plant cell wall analogues are typically employed to enable the interpretation of experimental results. This review summarises the current research status on the characterisation of the hierarchical structure of plant cell walls using small angle scattering techniques. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Dynamical properties of α-amylase in the folded and unfolded state: the role of thermal equilibrium fluctuations for conformational entropy and protein stabilisation

NASA Astrophysics Data System (ADS)

Fitter, J.; Herrmann, R.; Hauß, T.; Lechner, R. E.; Dencher, N. A.

2001-07-01

A comparative analysis of thermal equilibrium fluctuations occurring in a mesophilic and in a thermophilic α-amylase was performed to study the effect of structural fluctuations on thermostability. The thermal fluctuations determining the conformational entropy of both enzymes have been characterised for the folded (at 30°C and 60°C) and for the unfolded state by applying neutron spectroscopy (at 30°C). The folded state shows a higher structural flexibility for the thermophilic protein as compared to the mesophilic homologue. In contrast, the unfolded state of both enzymes is rather similar with respect to the structural fluctuations. On the basis of this result, a mechanism characterised by entropic stabilisation (i.e., smaller Δ S for the unfolding transition of thermophilic α-amylase) can be assumed to be responsible for the higher thermostability of the thermophilic enzyme.

Characterising the structural properties of polymer separators for lithium-ion batteries in 3D using phase contrast X-ray microscopy

NASA Astrophysics Data System (ADS)

Finegan, Donal P.; Cooper, Samuel J.; Tjaden, Bernhard; Taiwo, Oluwadamilola O.; Gelb, Jeff; Hinds, Gareth; Brett, Dan J. L.; Shearing, Paul R.

2016-11-01

Separators are an integral component for optimising performance and safety of lithium-ion batteries; therefore, a clear understanding of how their microstructure affects cell performance and safety is crucial. Phase contrast X-ray microscopy is used here to capture the microstructures of commercial monolayer, tri-layer, and ceramic-coated lithium-ion battery polymer separators. Spatial variations in key structural parameters, including porosity, tortuosity factor and pore size distribution, are determined through the application of 3D quantification techniques and stereology. The architectures of individual layers in multi-layer membranes are characterised, revealing anisotropy in porosity, tortuosity factor and mean pore size of the three types of separator. Detailed structural properties of the individual layers of multi-layered membranes are then related with their expected effect on safety and rate capability of cells.

Heterocyclic Salt Synthesis and Rational Properties Tailoring (PREPRINT)

DTIC Science & Technology

2009-06-23

performance behavior can be tailored in a controlled manner, defines the objective of a pertinent synthesis effort. Achieving this objective by...the structure of the anion. To illustrate this premise, four general synthesis methods to synthesize heterocyclic salts, including several new binary...manner, defines the objective of a pertinent synthesis effort. Achieving this objective by introducing structural alterations in a neutral covalent

Total Synthesis and Structural Revision of Antibiotic CJ-16,264.

PubMed

Nicolaou, K C; Shah, Akshay A; Korman, Henry; Khan, Tabrez; Shi, Lei; Worawalai, Wisuttaya; Theodorakis, Emmanuel A

2015-08-03

The total synthesis and structural revision of antibiotic CJ-16,264 is described. Starting with citronellal, the quest for the target molecule featured a novel bis-transannular Diels-Alder reaction that casted stereoselectively the decalin system and included the synthesis of six isomers before demystification of its true structure. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Throughput Synthesis and Structure of Zeolite ZSM-43 with Two-Directional 8-Ring Channels.

PubMed

Willhammar, Tom; Su, Jie; Yun, Yifeng; Zou, Xiaodong; Afeworki, Mobae; Weston, Simon C; Vroman, Hilda B; Lonergan, William W; Strohmaier, Karl G

2017-08-07

The aluminosilicate zeolite ZSM-43 (where ZSM = Zeolite Socony Mobil) was first synthesized more than 3 decades ago, but its chemical structure remained unsolved because of its poor crystallinity and small crystal size. Here we present optimization of the ZSM-43 synthesis using a high-throughput approach and subsequent structure determination by the combination of electron crystallographic methods and powder X-ray diffraction. The synthesis required the use of a combination of both inorganic (Cs + and K + ) and organic (choline) structure-directing agents. High-throughput synthesis enabled a screening of the synthesis conditions, which made it possible to optimize the synthesis, despite its complexity, in order to obtain a material with significantly improved crystallinity. When both rotation electron diffraction and high-resolution transmission electron microscopy imaging techniques are applied, the structure of ZSM-43 could be determined. The structure of ZSM-43 is a new zeolite framework type and possesses a unique two-dimensional channel system limited by 8-ring channels. ZSM-43 is stable upon calcination, and sorption measurements show that the material is suitable for adsorption of carbon dioxide as well as methane.

Synthesis of Chemiluminescent Esters: A Combinatorial Synthesis Experiment for Organic Chemistry Students

ERIC Educational Resources Information Center

Duarte, Robert; Nielson, Janne T.; Dragojlovic, Veljko

2004-01-01

A group of techniques aimed at synthesizing a large number of structurally diverse compounds is called combinatorial synthesis. Synthesis of chemiluminescence esters using parallel combinatorial synthesis and mix-and-split combinatorial synthesis is experimented.

One-pot synthesis of iniferter-bound polystyrene core nanoparticles for the controlled grafting of multilayer shells

NASA Astrophysics Data System (ADS)

Marchyk, Nataliya; Maximilien, Jacqueline; Beyazit, Selim; Haupt, Karsten; Sum Bui, Bernadette Tse

2014-02-01

A novel approach using one-pot synthesis for the production of uniform, iniferter-bound polystyrene core nanoparticles of size 30-40 nm is described. Conventional oil-in-water emulsion polymerisation of styrene and divinylbenzene, combining a hybrid initiation system (thermal and UV), triggered sequentially, was employed to form the surface-bound thiocarbamate iniferters in situ. The iniferter cores were then used as seeds for re-initiating further polymerisation by UV irradiation to produce water-compatible core-shell nanoparticles. Grafting of various shell-types is demonstrated: linear polymers of poly(N-isopropylacrylamide) brushes, crosslinked polymers bearing different surface charges and molecularly imprinted polymers. The shell thickness was readily tuned by varying the monomers' concentration and polymerisation time. Our method is straightforward and in addition, gives access to the preparation of fluorescent seeds and the possibility of grafting nanosized multiple shells. The core-shell nanoparticles were fully characterised by dynamic light scattering, transmission electron microscopy, Fourier transform infrared spectroscopy and microelemental analysis.A novel approach using one-pot synthesis for the production of uniform, iniferter-bound polystyrene core nanoparticles of size 30-40 nm is described. Conventional oil-in-water emulsion polymerisation of styrene and divinylbenzene, combining a hybrid initiation system (thermal and UV), triggered sequentially, was employed to form the surface-bound thiocarbamate iniferters in situ. The iniferter cores were then used as seeds for re-initiating further polymerisation by UV irradiation to produce water-compatible core-shell nanoparticles. Grafting of various shell-types is demonstrated: linear polymers of poly(N-isopropylacrylamide) brushes, crosslinked polymers bearing different surface charges and molecularly imprinted polymers. The shell thickness was readily tuned by varying the monomers' concentration and polymerisation time. Our method is straightforward and in addition, gives access to the preparation of fluorescent seeds and the possibility of grafting nanosized multiple shells. The core-shell nanoparticles were fully characterised by dynamic light scattering, transmission electron microscopy, Fourier transform infrared spectroscopy and microelemental analysis. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05295h

Hyperglycaemia and aberrated insulin signalling stimulate tumour progression via induction of the extracellular matrix component hyaluronan.

PubMed

Twarock, Sören; Reichert, Christina; Peters, Ulrike; Gorski, Daniel J; Röck, Katharina; Fischer, Jens W

2017-08-15

Epidemiological studies have detected a higher incidence of various tumour entities in diabetic patients. However, the underlying mechanisms remain insufficiently understood. Glucose-derived pericellular and extracellular hyaluronan (HA) promotes tumour progression and development. In our study, we tested the hypothesis that a diabetic metabolic state, characterised by hyperglycaemia and concomitant aberrant insulin signalling, stimulates tumour progression via the induction of HA synthesis. In a streptozotocin-induced diabetic nude mouse tumour xenograft model, hyperglycaemia and lack of insulin caused an increased formation of tumour-associated HA-matrix, which in turn accelerated tumour progression and neoangiogenesis. This process was effectively attenuated by treatment with 4-methylumbelliferone, a pharmacological inhibitor of HA-synthesis. To define the mechanisms behind these in vivo observations, we investigated the impact of hyperglycaemia and insulin on the glucose metabolism in oesophageal squamous cell cancer cells (ESCC). Hyperglycaemia induced HA synthesis while insulin diminished HA production by directing glucose metabolites to glycolysis. Vice versa, inhibition of glycolysis, either by knockdown of the glycolytic key enzyme phosphofructokinase or by an experimental abrogation of insulin signalling (knockdown of the insulin receptor and long-term treatment with insulin) augmented HA synthesis. Consequently, these processes induced invasion, anchorage-independent growth and adhesion of ESCC to endothelial cells in vitro. Thus, the cellular shift in glucose usage from catabolism of glucose to anabolism of HA driven by hyperglycaemia and insulin resistance may represent an important link between diabetes and cancer progression. Hence, therapeutical inhibition of HA synthesis may represent a promising approach for tumour treatment in diabetic patients. © 2017 UICC.

Nanostructured stannic oxide: Synthesis and characterisation for potential energy storage applications

NASA Astrophysics Data System (ADS)

Dodoo-Arhin, D.; Nuamah, R. A.; Jain, P. K.; Obada, D. O.; Yaya, A.

2018-06-01

SnO2 nanoparticles were synthesized using the hydrothermal technique. Well crystalline particles with different morphologies and crystallite size in the range of 2 nm-10 nm were obtained by using Urea and Soduim Borohydride as reducing agents, and deploying Dioctyl Sulfosuccinate Sodium Salt (AOT) and Cetyl Trimethyl ammonium bromide (CTAB) as the surfactants. Samples have been characterised by X-ray diffraction, Scanning Electron microscopy, Energy Dispersive X-ray spectroscopy, specific surface area, porosity, and Fourier Transform Infrared spectroscopy. Preliminary studies on the potential electrochemical properties of the as-produced nanoparticles were investigated using cyclic voltammetry, electrochemical impedance spectroscopy and potentiostatic charge-discharge in aqueous KOH electrolyte. The surfactant and reducing agents used in the synthesis procedure of SnO2 nanoparticles influenced the particle size and the morphology, which in turn influenced the capacitance of the SnO2 nanoparticles. The SnO2 electrode material showed pseudocapacitor properties with a maximum capacitance value of 1.6 Fg-1 at a scan rate of 5 mVs-1, an efficiency of 52% at a current of 1 mA and a maximum capacitance retention of about 40% after 10 cycles at a current of 1 mA. From the Nyquist plot, The ESR for the samples increase accordingly as SCA (31.5 Ω) < SAA (31.85 Ω) < SE (36.3 Ω) < SAT (36.92 Ω) < SCT (40.41 Ω) < SA < SC (53.97 Ω). These values are a confirmation of the low capacitance, efficiencies and capacitance retention recorded. The results obtained demonstrate the potential electrochemical storage applications of SnO2 nanoparticles without the addition of conductive materials.

Comparative Analysis and Distribution of Omega-3 lcPUFA Biosynthesis Genes in Marine Molluscs

PubMed Central

Surm, Joachim M.; Prentis, Peter J.; Pavasovic, Ana

2015-01-01

Recent research has identified marine molluscs as an excellent source of omega-3 long-chain polyunsaturated fatty acids (lcPUFAs), based on their potential for endogenous synthesis of lcPUFAs. In this study we generated a representative list of fatty acyl desaturase (Fad) and elongation of very long-chain fatty acid (Elovl) genes from major orders of Phylum Mollusca, through the interrogation of transcriptome and genome sequences, and various publicly available databases. We have identified novel and uncharacterised Fad and Elovl sequences in the following species: Anadara trapezia, Nerita albicilla, Nerita melanotragus, Crassostrea gigas, Lottia gigantea, Aplysia californica, Loligo pealeii and Chlamys farreri. Based on alignments of translated protein sequences of Fad and Elovl genes, the haeme binding motif and histidine boxes of Fad proteins, and the histidine box and seventeen important amino acids in Elovl proteins, were highly conserved. Phylogenetic analysis of aligned reference sequences was used to reconstruct the evolutionary relationships for Fad and Elovl genes separately. Multiple, well resolved clades for both the Fad and Elovl sequences were observed, suggesting that repeated rounds of gene duplication best explain the distribution of Fad and Elovl proteins across the major orders of molluscs. For Elovl sequences, one clade contained the functionally characterised Elovl5 proteins, while another clade contained proteins hypothesised to have Elovl4 function. Additional well resolved clades consisted only of uncharacterised Elovl sequences. One clade from the Fad phylogeny contained only uncharacterised proteins, while the other clade contained functionally characterised delta-5 desaturase proteins. The discovery of an uncharacterised Fad clade is particularly interesting as these divergent proteins may have novel functions. Overall, this paper presents a number of novel Fad and Elovl genes suggesting that many mollusc groups possess most of the required enzymes for the synthesis of lcPUFAs. PMID:26308548

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Cyclic β-glucans at the bacteria-host cells interphase: One sugar ring to rule them all.

PubMed

Guidolin, Leticia S; Arce-Gorvel, Vilma; Ciocchini, Andrés E; Comerci, Diego J; Gorvel, Jean-Pierre

2018-06-01

Cyclic β-1,2-D-glucans (CβG) are natural bionanopolymers present in the periplasmic space of many Proteobacteria. These molecules are sugar rings made of 17 to 25 D-glucose units linked exclusively by β-1,2-glycosidic bonds. CβG are important for environmental sensing and osmoadaptation in bacteria, but most importantly, they play key roles in complex host-cell interactions such as symbiosis, pathogenesis, and immunomodulation. In the last years, the identification and characterisation of the enzymes involved in the synthesis of CβG allowed to know in detail the steps necessary for the formation of these sugar rings. Due to its peculiar structure, CβG can complex large hydrophobic molecules, a feature possibly related to its function in the interaction with the host. The capabilities of the CβG to function as molecular boxes and to solubilise hydrophobic compounds are attractive for application in the development of drugs, in food industry, nanotechnology, and chemistry. More importantly, its excellent immunomodulatory properties led to the proposal of CβG as a new class of adjuvants for vaccine development. © 2018 John Wiley & Sons Ltd.

A solid-phase combinatorial approach for indoloquinolizidine-peptides with high affinity at D(1) and D(2) dopamine receptors.

PubMed

Molero, Anabel; Vendrell, Marc; Bonaventura, Jordi; Zachmann, Julian; López, Laura; Pardo, Leonardo; Lluis, Carme; Cortés, Antoni; Albericio, Fernando; Casadó, Vicent; Royo, Miriam

2015-06-05

Ligands acting at multiple dopamine receptors hold potential as therapeutic agents for a number of neurodegenerative disorders. Specifically, compounds able to bind at D1R and D2R with high affinity could restore the effects of dopamine depletion and enhance motor activation on degenerated nigrostriatal dopaminergic systems. We have directed our research towards the synthesis and characterisation of heterocycle-peptide hybrids based on the indolo[2,3-a]quinolizidine core. This privileged structure is a water-soluble and synthetically accessible scaffold with affinity for diverse GPCRs. Herein we have prepared a solid-phase combinatorial library of 80 indoloquinolizidine-peptides to identify compounds with enhanced binding affinity at D2R, a receptor that is crucial to re-establish activity on dopamine-depleted degenerated GABAergic neurons. We applied computational tools and high-throughput screening assays to identify 9a{1,3,3} as a ligand for dopamine receptors with nanomolar affinity and agonist activity at D2R. Our results validate the application of indoloquinolizidine-peptide combinatorial libraries to fine-tune the pharmacological profiles of multiple ligands at D1 and D2 dopamine receptors. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

The effect of milling time on the synthesis of Cu{sub 54}Mg{sub 22}Ti{sub 18}Ni{sub 6} alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kursun, C., E-mail: celalkursun@ksu.edu.tr; Gogebakan, M., E-mail: gogebakan@ksu.edu.tr

In the present work, nanocrystalline Cu{sub 54}Mg{sub 22}Ti{sub 18}Ni{sub 6} alloy was produced by mechanical alloying from mixtures of pure crystalline Cu, Mg, Ti and Ni powders using a Fritsch planetary ball mill with a ball to powder ratio of 10:1. Morphological changes, microstructural evolution and thermal behaviour of the Cu-Mg-Ti-Ni powders at different stages of milling were characterised by X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray detection (SEM/EDX) and differential thermal analysis (DTA). This alloy resulted in formation of single phase solid solution with FCC structure α-Cu (Mg, Ti, Ni) after 80 h of milling. In the initialmore » stage of milling different sized and shaped elemental powders became uniform during mechanical alloying. The homogeneity of the Cu{sub 54}Mg{sub 22}Ti{sub 18}Ni{sub 6} alloy increased with increasing milling time. The EDX result also confirmed the compositional homogeneity of the powder alloy. The crystallite size of alloy was calculated below 10 nm from XRD data.« less

Harmonised framework for ecological risk assessment of sediments from ports and estuarine zones of North and South Atlantic.

PubMed

Choueri, R B; Cesar, A; Abessa, D M S; Torres, R J; Riba, I; Pereira, C D S; Nascimento, M R L; Morais, R D; Mozeto, A A; DelValls, T A

2010-04-01

This paper presents a harmonised framework of sediment quality assessment and dredging material characterisation for estuaries and port zones of North and South Atlantic. This framework, based on the weight-of-evidence approach, provides a structure and a process for conducting sediment/dredging material assessment that leads to a decision. The main structure consists of "step 1" (examination of available data); "step 2" (chemical characterisation and toxicity assessment); "decision 1" (any chemical level higher than reference values? are sediments toxic?); "step 3" (assessment of benthic community structure); "step 4" (integration of the results); "decision 2" (are sediments toxic or benthic community impaired?); "step 5" (construction of the decision matrix) and "decision 3" (is there environmental risk?). The sequence of assessments may be interrupted when the information obtained is judged to be sufficient for a correct characterisation of the risk posed by the sediments/dredging material. This framework brought novel features compared to other sediment/dredging material risk assessment frameworks: data integration through multivariate analysis allows the identification of which samples are toxic and/or related to impaired benthic communities; it also discriminates the chemicals responsible for negative biological effects; and the framework dispenses the use of a reference area. We demonstrated the successful application of this framework in different port and estuarine zones of the North (Gulf of Cádiz) and South Atlantic (Santos and Paranaguá Estuarine Systems).

Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis

PubMed Central

van der Bij, Hendrik E.

2015-01-01

Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus–zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus–zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research. PMID:26051875

Phosphorus promotion and poisoning in zeolite-based materials: synthesis, characterisation and catalysis.

PubMed

van der Bij, Hendrik E; Weckhuysen, Bert M

2015-10-21

Phosphorus and microporous aluminosilicates, better known as zeolites, have a unique but poorly understood relationship. For example, phosphatation of the industrially important zeolite H-ZSM-5 is a well-known, relatively inexpensive and seemingly straightforward post-synthetic modification applied by the chemical industry not only to alter its hydrothermal stability and acidity, but also to increase its selectivity towards light olefins in hydrocarbon catalysis. On the other hand, phosphorus poisoning of zeolite-based catalysts, which are used for removing nitrogen oxides from exhaust fuels, poses a problem for their use in diesel engine catalysts. Despite the wide impact of phosphorus-zeolite chemistry, the exact physicochemical processes that take place require a more profound understanding. This review article provides the reader with a comprehensive and state-of-the-art overview of the academic literature, from the first reports in the late 1970s until the most recent studies. In the first part an in-depth analysis is undertaken, which will reveal universal physicochemical and structural effects of phosphorus-zeolite chemistry on the framework structure, accessibility, and strength of acid sites. The second part discusses the hydrothermal stability of zeolites and clarifies the promotional role that phosphorus plays. The third part of the review paper links the structural and physicochemical effects of phosphorus on zeolite materials with their catalytic performance in a variety of catalytic processes, including alkylation of aromatics, catalytic cracking, methanol-to-hydrocarbon processing, dehydration of bioalcohol, and ammonia selective catalytic reduction (SCR) of NOx. Based on these insights, we discuss potential applications and important directions for further research.

Green synthesis of silver nanoparticles using Terminalia chebula extract at room temperature and their antimicrobial studies

NASA Astrophysics Data System (ADS)

Mohan Kumar, Kesarla; Sinha, Madhulika; Mandal, Badal Kumar; Ghosh, Asit Ranjan; Siva Kumar, Koppala; Sreedhara Reddy, Pamanji

2012-06-01

A green rapid biogenic synthesis of silver nanoparticles (Ag NPs) using Terminalia chebula (T. chebula) aqueous extract was demonstrated in this present study. The formation of silver nanoparticles was confirmed by Surface Plasmon Resonance (SPR) at 452 nm using UV-visible spectrophotometer. The reduction of silver ions to silver nanoparticles by T. chebula extract was completed within 20 min which was evidenced potentiometrically. Synthesised nanoparticles were characterised using UV-vis spectroscopy, Fourier transformed infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The hydrolysable tannins such as di/tri-galloyl-glucose present in the extract were hydrolyzed to gallic acid and glucose that served as reductant while oxidised polyphenols acted as stabilizers. In addition, it showed good antimicrobial activity towards both Gram-positive bacteria (S. aureus ATCC 25923) and Gram-negative bacteria (E. coli ATCC 25922). Industrially it may be a smart option for the preparation of silver nanoparticles.

Screening of filamentous fungi for antimicrobial silver nanoparticles synthesis.

PubMed

Ottoni, Cristiane Angélica; Simões, Marta Filipa; Fernandes, Sara; Dos Santos, Jonas Gomes; da Silva, Elda Sabino; de Souza, Rodrigo Fernando Brambilla; Maiorano, Alfredo Eduardo

2017-12-01

The present work had the goal of screening a batch of 20 fungal strains, isolated from sugar cane plantation soil, in order to identify those capable of biosynthesis of silver nanoparticles. These nanoparticles are known to have a large and effective application in clinical microbiology. Four strains were found to be capable of biosynthesis of silver nanoparticles. The biosynthesised nanoparticles were characterised by UV-vis spectroscopy, scanning electron microscopy, EDX, and XRD. They were found to have an average size of 30-100 nm, a regular round shape, and potential antimicrobial activity against Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. The antimicrobial activity was found to be directly related to the nanoparticles concentration. Mycogenic synthesis of nanoparticles is a green biogenic process preferable to other alternatives. Because fungi are great producers of extracellular enzymes this process makes scaling-up an easier task with high importance for clinical microbiology on the fight against microbial resistance, as well as for other industrial applications.

Synthesis and coordination chemistry of 1,1,1-tris-(pyrid-2-yl)ethane.

PubMed

Santoro, Amedeo; Sambiagio, Carlo; McGowan, Patrick C; Halcrow, Malcolm A

2015-01-21

A new synthesis of 1,1,1-tris(pyrid-2-yl)ethane (L), and a survey of its coordination chemistry, are reported. The complexes [ML2](n+) (M(n+) = Fe(2+), Co(2+), Co(3+), Cu(2+) and Ag(+)), [PdCl2L] and [CuI(L)] have all been crystallographically characterised. Noteworthy results include an unusual square planar silver(i) complex [Ag(L)2]X (X(-) = NO3(-) and SbF6(-)); the oxidative fixation of aerobic CO2 by [CuI(L)] to yield [Cu2I(L)2(μ-CO3)]2[CuI3] and [Cu(CO3)(L)]; and, water/carbonato tape and water/iodo layer hydrogen bonding networks in hydrate crystals of two of the copper(ii) complexes. Cyclic voltammetric data on [Fe(L)2](2+) and [Co(L)2](2+/3+) imply that the peripheral methyl substituent has a weak influence on the ligand field exerted by L onto a coordinated metal ion.

How Learning Conditions and Program Structure Predict Burnout and Satisfaction in Teacher Education

ERIC Educational Resources Information Center

Zimmermann, Friederike; Rösler, Lena; Möller, Jens; Köller, Olaf

2018-01-01

To support prospective teachers' professional development, teacher education should be characterised by conditions that help to prevent burnout and facilitate satisfaction. This study investigates predictors of burnout and satisfaction in teacher education by drawing on universities with different teacher education programme structures and assumed…

Acoustic characterisation of liquid foams with an impedance tube.

PubMed

Pierre, Juliette; Guillermic, Reine-Marie; Elias, Florence; Drenckhan, Wiebke; Leroy, Valentin

2013-10-01

Acoustic measurements provide convenient non-invasive means for the characterisation of materials. We show here for the first time how a commercial impedance tube can be used to provide accurate measurements of the velocity and attenuation of acoustic waves in liquid foams, as well as their effective "acoustic" density, over the 0.5-6kHz frequency range. We demonstrate this using two types of liquid foams: a commercial shaving foam and "home-made" foams with well-controlled physico-chemical and structural properties. The sound velocity in the latter foams is found to be independent of the bubble size distribution and is very well described by Wood's law. This implies that the impedance technique may be a convenient way to measure in situ the density of liquid foams. Important questions remain concerning the acoustic attenuation, which is found to be influenced in a currently unpredictible manner by the physico-chemical composition and the bubble size distribution of the characterised foams. We confirm differences in sound velocities in the two types of foams (having the same structural properties) which suggests that the physico-chemical composition of liquid foams has a non-negligible effect on their acoustic properties.

High level expression, purification and physico- and immunochemical characterisation of recombinant Pen a 1: a major allergen of shrimp.

PubMed

Albrecht, Melanie; Alessandri, Stefano; Conti, Amedeo; Reuter, Andreas; Lauer, Iris; Vieths, Stefan; Reese, Gerald

2008-11-01

Well-characterised and immunologically active recombinant allergens are of eminent importance for improvement of diagnostic tools and immunotherapy of allergic diseases. The use of recombinant allergens has several advantages such as the more precise quantification of the active substance compared to allergen extracts and the reduced risk of contamination with other allergenic proteins compared to purified natural allergens. Optimised standard protocols for expression and purification and a detailed physico-chemical characterisation of such recombinant allergens are necessary to ensure consistent quality and comparability of results obtained with recombinant material. In this study the major allergen Pen a 1 of brown shrimp (Penaeus aztecus) was expressed in E. coli and purified in two steps by immobilised metal chelate-affinity chromatography (IMAC) and size-exclusion chromatography. Identity and purity were verified with N-terminal sequencing and peptide mass fingerprinting. Circular dichroism and NMR-spectroscopy indicated an alpha-helical flexible structure of rPen a 1 which is in accordance with the known structure of tropomyosins. Finally, the recombinant allergen proved to be immunologically reactive in IgE Western blot analysis and ELISA. This study provides a protocol for the preparation of recombinant shrimp tropomyosin in standardised quality.

Characterising the thermoforming behaviour of glass fibre textile reinforced thermoplastic composite materials

NASA Astrophysics Data System (ADS)

Kuhtz, M.; Maron, B.; Hornig, A.; Müller, M.; Langkamp, A.; Gude, M.

2018-05-01

Textile reinforced thermoplastic composites are predestined for highly automated medium- and high-volume production processes. The presented work focusses on experimental studies of different types of glass fibre reinforced polypropylene (GF-PP) semi-finished thermoplastic textiles to characterise the forming behaviour. The main deformation modes fabric shear, tension, thought-thickness compression and bending are investigated with special emphasis on the impact of the textile structure, the deformation temperature and rate dependency. The understanding of the fundamental forming behaviour is required to allow FEM based assessment and improvement of thermoforming process chains.

Quantification of micro-CT images of textile reinforcements

NASA Astrophysics Data System (ADS)

Straumit, Ilya; Lomov, Stepan V.; Wevers, Martine

2017-10-01

VoxTex software (KU Leuven) employs 3D image processing, which use the local directionality information, retrieved using analysis of local structure tensor. The processing results in a voxel 3D array, with each voxel carrying information on (1) material type (matrix; yarn/ply, with identification of the yarn/ply in the reinforcement architecture; void) and (2) fibre direction for fibrous yarns/plies. The knowledge of the material phase volume and known characterisation of the textile structure allows assigning to the voxels (3) fibre volume fraction. This basic voxel model can be further used for different type of the material analysis: Internal geometry and characterisation of defects; permeability; micromechanics; mesoFE voxel models. Apart from the voxel based analysis, approaches to reconstruction of the yarn paths are presented.

Uniqueness of the joint measurement and the structure of the set of compatible quantum measurements

NASA Astrophysics Data System (ADS)

Guerini, Leonardo; Terra Cunha, Marcelo

2018-04-01

We address the problem of characterising the compatible tuples of measurements that admit a unique joint measurement. We derive a uniqueness criterion based on the method of perturbations and apply it to show that extremal points of the set of compatible tuples admit a unique joint measurement, while all tuples that admit a unique joint measurement lie in the boundary of such a set. We also provide counter-examples showing that none of these properties are both necessary and sufficient, thus completely describing the relation between the joint measurement uniqueness and the structure of the compatible set. As a by-product of our investigations, we completely characterise the extremal and boundary points of the set of general tuples of measurements and of the subset of compatible tuples.

Fabrication and characterisation of a fully auxetic 3D lattice structure via selective electron beam melting

NASA Astrophysics Data System (ADS)

Warmuth, Franziska; Osmanlic, Fuad; Adler, Lucas; Lodes, Matthias A.; Körner, Carolin

2017-02-01

A three-dimensional fully auxetic cellular structure with negative Poisson’s ratio is presented. Samples are fabricated from Ti6Al4V powder via selective electron beam melting. The influence of the strut thickness and the amplitude of the strut on the mechanical properties and the deformation behaviour of cellular structures is studied.

A Multidimensional Diversity‐Oriented Synthesis Strategy for Structurally Diverse and Complex Macrocycles

PubMed Central

Nie, Feilin; Kunciw, Dominique L.; Wilcke, David; Stokes, Jamie E.; Galloway, Warren R. J. D.; Bartlett, Sean; Sore, Hannah F.

2016-01-01

Abstract Synthetic macrocycles are an attractive area in drug discovery. However, their use has been hindered by a lack of versatile platforms for the generation of structurally (and thus shape) diverse macrocycle libraries. Herein, we describe a new concept in library synthesis, termed multidimensional diversity‐oriented synthesis, and its application towards macrocycles. This enabled the step‐efficient generation of a library of 45 novel, structurally diverse, and highly‐functionalized macrocycles based around a broad range of scaffolds and incorporating a wide variety of biologically relevant structural motifs. The synthesis strategy exploited the diverse reactivity of aza‐ylides and imines, and featured eight different macrocyclization methods, two of which were novel. Computational analyses reveal a broad coverage of molecular shape space by the library and provides insight into how the various diversity‐generating steps of the synthesis strategy impact on molecular shape. PMID:27484830

Structural and optical properties of vanadium ion-implanted GaN

NASA Astrophysics Data System (ADS)

Macková, A.; Malinský, P.; Jagerová, A.; Sofer, Z.; Klímová, K.; Sedmidubský, D.; Mikulics, M.; Lorinčík, J.; Veselá, D.; Böttger, R.; Akhmadaliev, S.

2017-09-01

The field of advanced electronic and optical devices searches for a new generation of transistors and lasers. The practical development of these novel devices depends on the availability of materials with the appropriate magnetic and optical properties, which is strongly connected to the internal morphology and the structural properties of the prepared doped structures. In this contribution, we present the characterisation of V ion-doped GaN epitaxial layers. GaN layers, oriented along the (0 0 0 1) crystallographic direction, grown by low-pressure metal-organic vapour-phase epitaxy (MOVPE) on c-plane sapphire substrates were implanted with 400 keV V+ ions at fluences of 5 × 1015 and 5 × 1016 cm-2. Elemental depth profiling was accomplished by Rutherford Backscattering Spectrometry (RBS) and Secondary Ion Mass Spectrometry (SIMS) to obtain precise information about the dopant distribution. Structural investigations are needed to understand the influence of defect distribution on the crystal-matrix recovery and the desired structural and optical properties. The structural properties of the ion-implanted layers were characterised by RBS-channelling and Raman spectroscopy to get a comprehensive insight into the structural modification of implanted GaN and to study the influence of subsequent annealing on the crystalline matrix reconstruction. Photoluminescence measurement was carried out to check the optical properties of the prepared structures.

Mesoporous nickel oxide nanowires: hydrothermal synthesis, characterisation and applications for lithium-ion batteries and supercapacitors with superior performance.

PubMed

Su, Dawei; Kim, Hyun-Soo; Kim, Woo-Seong; Wang, Guoxiu

2012-06-25

Mesoporous nickel oxide nanowires were synthesized by a hydrothermal reaction and subsequent annealing at 400 °C. The porous one-dimensional nanostructures were analysed by field-emission SEM, high-resolution TEM and N(2) adsorption/desorption isotherm measurements. When applied as the anode material in lithium-ion batteries, the as-prepared mesoporous nickel oxide nanowires demonstrated outstanding electrochemical performance with high lithium storage capacity, satisfactory cyclability and an excellent rate capacity. They also exhibited a high specific capacitance of 348 F g(-1) as electrodes in supercapacitors. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of graphene quantum dots-silver nanocomposites

NASA Astrophysics Data System (ADS)

Vandana, M.; Ashokkumar, S. P.; Vijeth, H.; Niranjana, M.; Yesappa, L.; Devendrappa, H.

2018-04-01

A facile microwave assisted hydrothermal method is used to synthesise glucose derived water soluble crystalline graphene quantum dots (GQDs) andcitrate reduction method was used to synthesized silver nanoparticles (SNPs). The formation of graphene quantum dots-silver nanocomposites (GSC) was synthesized through a simple refluxing process and characterised using Fourier Transform Infrared (FT-IR) to study the chemical interaction, Surface morphology using FESEM, Optical properties were studied using UV-Visible spectroscopy. The absorption band shows at 249, 306 and 447 nm confirms the formation of GQDs and GSC. The electrochemical performance of GSC tested to determine the oxidation/reduction processes by cyclic voltammetry and linear sweep voltammetry.

A bio-psycho-social model of violence related to mental health problems.

PubMed

Steinert, Tilman; Whittington, Richard

2013-01-01

Psychiatry is characterised by bio-psycho-social approaches and therapies. Thus there should be an interest in comprehensive theoretical models for didactic purposes. A narrative synthesis of key themes in the current literature on psychiatric aspects of violence was conducted with the aim of integrating biological, psychological and sociological ideas in this area. Two didactical models are proposed for 1) individual disposition and for 2) acting in specific situations, each including available evidence-based knowledge. The proposed models may be helpful for a comprehensive understanding of all relevant influencing factors in violent mentally ill people and for didactical purposes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Regulation of Camphor Metabolism: Induction and Repression of Relevant Monooxygenases in Pseudomonas putida NCIMB 10007.

PubMed

Willetts, Andrew; Masters, Pamela; Steadman, Carol

2018-05-07

For the first time, the differential rates of synthesis of all the key monooxygenases involved in the catabolism by Pseudomonas putida NCIMB 10007 of bicyclic ( rac )-camphor to ∆ 2,5 -3,4,4-trimethylpimelyl-CoA, the first aliphatic pathway intermediate, have been determined to help establish the relevant induction profile of each of the oxygen-dependent enzymes. The efficacy of both relevant substrates and pathway metabolites as inducers has been established. Further, inhibitors with characterised functionality have been used to indicate that the pertinent regulatory controls operate at the level of transcription of the corresponding genes.

Surface and catalytic properties of acid metal carbons prepared by the sol gel method

NASA Astrophysics Data System (ADS)

Aguado-Serrano, J.; Rojas-Cervantes, M. L.; Martín-Aranda, R. M.; López-Peinado, A. J.; Gómez-Serrano, V.

2006-06-01

The sol-gel method has been applied for the synthesis of a series of acid metal-carbon xerogels (with M = V, Cr, Mo and Ni) by polymerisation of resorcinol with formaldehyde in the presence of metallic precursors. A blank sample was also prepared without any metal addition. The xerogels were heated in nitrogen at 1000 °C to obtain the pyrolysed products. The samples were characterised by different techniques such as thermal-mass spectrometry analysis, gas physisorption, and mercury porosimetry. In addition, the acid character of the pyrolysed products was tested by the Claisen-Schmidt condensation between benzaldehyde and acetophenone for the formation of chalcones.

Very High Performance High Nitrogen Energetic Ingredients and Energetic Polymers for Structural Components

DTIC Science & Technology

2011-12-31

have developed a vastly improved procedure for synthesis of the n- propyl ester that gives essentially quantitative yield and uses concentrated... Synthesis of n- propyl 4-aminofurazan-3-carboxylate. We next turned our attention to the synthesis of the amide. Again, the literature procedure is... synthesis and chemistry of 3-hydroxymethyl-4-amino[1,2,5]oxadiazole and 5) work on energetic polymers for structural components. 15. SUBJECT TERMS

Pathogenic mutations of the human mitochondrial citrate carrier SLC25A1 lead to impaired citrate export required for lipid, dolichol, ubiquinone and sterol synthesis.

PubMed

Majd, Homa; King, Martin S; Smith, Anthony C; Kunji, Edmund R S

2018-01-01

Missense mutations of the human mitochondrial citrate carrier, encoded by the SLC25A1 gene, lead to an autosomal recessive neurometabolic disorder characterised by neonatal-onset encephalopathy with severe muscular weakness, intractable seizures, respiratory distress, and lack of psychomotor development, often resulting in early death. Here, we have measured the effect of all twelve known pathogenic mutations on the transport activity. The results show that nine mutations abolish transport of citrate completely, whereas the other three reduce the transport rate by >70%, indicating that impaired citrate transport is the most likely primary cause of the disease. Some mutations may be detrimental to the structure of the carrier, whereas others may impair key functional elements, such as the substrate binding site and the salt bridge network on the matrix side of the carrier. To understand the consequences of impaired citrate transport on metabolism, the substrate specificity was also determined, showing that the human citrate carrier predominantly transports citrate, isocitrate, cis-aconitate, phosphoenolpyruvate and malate. Although D-2- and L-2 hydroxyglutaric aciduria is a metabolic hallmark of the disease, it is unlikely that the citrate carrier plays a significant role in the removal of hydroxyglutarate from the cytosol for oxidation to oxoglutarate in the mitochondrial matrix. In contrast, computer simulations of central metabolism predict that the export of citrate from the mitochondrion cannot be fully compensated by other pathways, restricting the cytosolic production of acetyl-CoA that is required for the synthesis of lipids, sterols, dolichols and ubiquinone, which in turn explains the severe disease phenotypes. Copyright © 2017. Published by Elsevier B.V.

Synthesis and Structure Property Studies of Toughened Epoxy Resins Via Functionalized Polysiloxanes.

DTIC Science & Technology

1987-09-30

34 87S N4 SYNTHESIS RNO STRUCTURE PROPERTY STUDIES OF OP NDD mEPOXY RESINS YIN FU.. (U) VIROINIR POLYTECHNIC INST OM STNTE UNIY RCKSBURG DEPT OF C.. J...Classification) Synthesis and Structure Property Studies of Toughened Epoxy Resins Via Functionalized Polysiloxanes 12. PERSONALAUTHOR(S) J. 5. HitTIe... Resins , Toughening 19. ABSTRACT (Continue on reverse if necessary and identify by block number) Epoxy resins chemically modified with functionally

Synthesis of Large Quantities of Single-Walled Aluminogermanante Nanotube

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levard,C.; Rose, J.; Mision, A.

2008-01-01

A simple aqueous synthesis yielded about 100 times more structurally well-organized single-walled aluminogermanate nanotubes than previously reported 'standard' procedures. The structure analyses using XRD, IRTF, TEM, and XAS were greatly facilitated by the high concentrations available, and they ascertained the imogolite-like structure of the nanotubes. Simplicity and yield of the synthesis protocol are likely to favor commercial applications of theses materials as well as simplified syntheses of other nanophases.

Synthesis of guanidinoacetate and creatine from amino acids by rat pancreas.

PubMed

da Silva, Robin P; Clow, Kathy; Brosnan, John T; Brosnan, Margaret E

2014-02-01

Creatine is an important molecule involved in cellular energy metabolism. Creatine is spontaneously converted to creatinine at a rate of 1·7% per d; creatinine is lost in the urine. Creatine can be obtained from the diet or synthesised from endogenous amino acids via the enzymes arginine:glycine amidinotransferase (AGAT) and guanidinoacetate N-methyltransferase (GAMT). The liver has high GAMT activity and the kidney has high AGAT activity. Although the pancreas has both AGAT and GAMT activities, its possible role in creatine synthesis has not been characterised. In the present study, we examined the enzymes involved in creatine synthesis in the pancreas as well as the synthesis of guanidinoacetate (GAA) and creatine by isolated pancreatic acini. We found significant AGAT activity and somewhat lower GAMT activity in the pancreas and that pancreatic acini had measurable activities of both AGAT and GAMT and the capacity to synthesise GAA and creatine from amino acids. Creatine supplementation led to a decrease in AGAT activity in the pancreas, though it did not affect its mRNA or protein abundance. This was in contrast with the reduction of AGAT activity and mRNA and protein abundance in the kidney, suggesting that the regulatory mechanisms that control the expression of this enzyme in the pancreas are different from those in the kidney. Dietary creatine increased the concentrations of GAA, creatine and phosphocreatine in the pancreas. Unexpectedly, creatine supplementation decreased the concentrations of S-adenosylmethionine, while those of S-adenosylhomocysteine were not altered significantly.

Rapid hydrothermal flow synthesis and characterisation of carbonate- and silicate-substituted calcium phosphates

PubMed Central

Knowles, Jonathan C; Rehman, Ihtesham; Darr, Jawwad A

2013-01-01

A range of crystalline and nano-sized carbonate- and silicate-substituted hydroxyapatite has been successfully produced by using continuous hydrothermal flow synthesis technology. Ion-substituted calcium phosphates are better candidates for bone replacement applications (due to improved bioactivity) as compared to phase-pure hydroxyapatite. Urea was used as a carbonate source for synthesising phase pure carbonated hydroxyapatite (CO3-HA) with ≈5 wt% substituted carbonate content (sample 7.5CO3-HA) and it was found that a further increase in urea concentration in solution resulted in biphasic mixtures of carbonate-substituted hydroxyapatite and calcium carbonate. Transmission electron microscopy images revealed that the particle size of hydroxyapatite decreased with increasing urea concentration. Energy-dispersive X-ray spectroscopy result revealed a calcium deficient apatite with Ca:P molar ratio of 1.45 (±0.04) in sample 7.5CO3-HA. For silicate-substituted hydroxyapatite (SiO4-HA) silicon acetate was used as a silicate ion source. It was observed that a substitution threshold of ∼1.1 wt% exists for synthesis of SiO4-HA in the continuous hydrothermal flow synthesis system, which could be due to the decreasing yields with progressive increase in silicon acetate concentration. All the as-precipitated powders (without any additional heat treatments) were analysed using techniques including Transmission electron microscopy, X-ray powder diffraction, Differential scanning calorimetry, Thermogravimetric analysis, Raman spectroscopy and Fourier transform infrared spectroscopy. PMID:22983020

Redirection of anthocyanin synthesis in Osteospermum hybrida by a two-enzyme manipulation strategy.

PubMed

Seitz, Christian; Vitten, Matthias; Steinbach, Peter; Hartl, Sabrina; Hirsche, Jörg; Rathje, Wiebke; Treutter, Dieter; Forkmann, Gert

2007-03-01

Modern biotechnology has developed powerful tools for genetic engineering and flower colours are an excellent object to study possibilities and limitations of engineering strategies. Osteospermum hybrida became a popular ornamental plant within the last 20 years. Many cultivars display rose to lilac flower colours mainly based on delphinidin-derived anthocyanins. The predominant synthesis of delphinidin derivatives is referred to a strong endogenous flavonoid 3',5'-hydroxylase (F3'5'H) activity. Furthermore, since dihydroflavonol 4-reductase (DFR) of Osteospermum does not convert dihydrokaempferol (DHK) to leucopelargonidin, synthesis of pelargonidin-based anthocyanins is naturally not realised. In order to redirect anthocyanin biosynthesis in Osteospermum towards pelargonidin derivatives, we introduced cDNAs coding for DFRs which efficiently convert DHK to LPg. But neither the expression of Gerbera hybrida DFR nor of Fragaria x ananassa DFR - the latter is characterised by an unusual high substrate preference for DHK - altered anthocyanin composition in flowers of transgenic plants. However, chemical inhibition of F3'5'H activity in ray florets of dfr transgenic plants resulted in the accumulation of pelargonidin derivatives. Accordingly, retransformation of a transgenic plant expressing Gerbera DFR with a construct for RNAi-mediated suppression of F3'5'H activity resulted in double transgenic plants accumulating predominantly pelargonidin derivatives in flowers.

Cultivation of Chlorella on brewery wastewater and nano-particle biosynthesis by its biomass.

PubMed

Subramaniyam, Vidhyasri; Subashchandrabose, Suresh Ramraj; Ganeshkumar, Vimalkumar; Thavamani, Palanisami; Chen, Zuliang; Naidu, Ravi; Megharaj, Mallavarapu

2016-07-01

This study investigated an integrated and sustainable approach for iron nanoparticles synthesis using Chlorella sp. MM3 biomass produced from the remediation of brewery wastewater. The algal growth characteristics, biomass production, nutrient removal, and nanoparticle synthesis including its characterisation were studied to prove the above approach. The growth curve of Chlorella depicted lag and exponential phase characteristics during the first 4days in a brewery wastewater collected from a single batch of brewing process (single water sample) indicating the growth of algae in brewery wastewater. The pollutants such as total nitrogen, total phosphorus and total organic carbon in single water sample were completely utilised by Chlorella for its growth. The X-ray photoelectron spectroscopy spectra showed peaks at 706.56eV, 727.02eV, 289.84eV and 535.73eV which corresponded to the zero-valent iron, iron oxides, carbon and oxygen respectively, confirming the formation of iron nanoparticle capped with algal biomolecules. Scanning electron microscopy and particle size analysis confirmed the presence of spherical shaped iron nanoparticles of size ranging from 5 to 50nm. To our knowledge, this is the first report on nanoparticle synthesis using the biomass generated from phycoremediation of brewery wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of a Hypersensitive Periodate-Cleavable Amino Acid that is Methionine- and Disulfide-Compatible and its Application in MHC Exchange Reagents for T Cell Characterisation

PubMed Central

Amore, Alessia; Wals, Kim; Koekoek, Evelyn; Hoppes, Rieuwert; Toebes, Mireille; Schumacher, Ton N M; Rodenko, Boris; Ovaa, Huib

2013-01-01

Incorporation of cleavable linkers into peptides and proteins is of particular value in the study of biological processes. Here we describe the synthesis of a cleavable linker that is hypersensitive to oxidative cleavage as the result of the periodate reactivity of a vicinal amino alcohol moiety. Two strategies directed towards the synthesis of a building block suitable for solid-phase peptide synthesis were developed: a chemoenzymatic route, involving l-threonine aldolase, and an enantioselective chemical route; these led to α,γ-diamino-β-hydroxybutanoic acids in diastereoisomerically mixed and enantiopure forms, respectively. Incorporation of the 1,2-amino alcohol linker into the backbone of a peptide generated a conditional peptide that was rapidly cleaved at very low concentrations of sodium periodate. This cleavable peptide ligand was applied in the generation of MHC exchange reagents for the detection of antigen-specific T cells in peripheral blood cells. The extremely low concentration of periodate required to trigger MHC peptide exchange allowed the co-oxidation of methionine and disulfide residues to be avoided. Conditional MHC reagents hypersensitive to periodate can now be applied without limitations when UV irradiation is undesired or less practical. PMID:23280887

Instability of an aromatic amine in fatty food and fatty food simulant: characterisation of reaction products and prediction of their toxicity.

PubMed

Paseiro-Cerrato, R; Rodríguez-Bernaldo de Quirós, A; Sendón, R; Bustos, J; Sánchez, J J; López-Hernández, J; Paseiro-Losada, P

2015-01-01

It is a well-known fact that amines are not stable in food of a fatty nature. In this study the synthesis and characterisation of the products obtained as a result of the reaction of amines in a fatty medium are reported. Based on the well-known reactions among amines and acid and esters groups, two novel compounds were synthesised using m-xylylenediamine (mXDA), a primary diamine widely used as monomer in the manufacture of food contact materials and two fatty acids, oleic acid and palmitic acid, which occur in most fats. The resulting compounds were two molecules belonging to the family of fatty acid amides, dioleamide and dipalmitamide. A complete characterisation of both products was carried out employing several techniques such as infrared spectroscopy, (1)H- and (13)C-NMR spectroscopy, electron ionisation mass spectrometry, LC-MS/MS and UV spectrometry. The results obtained by the different techniques were well correlated. In the second part of the work, the formation of these compounds in real samples was evaluated. For this purpose a certain volume of olive oil was spiked with a known amount of mXDA. Olive oil was selected as a fatty medium since it is a widely consumed food and additionally is used as a fatty food simulant in migration studies of food contact materials. A method was developed to extract the fatty acid amides from the fatty matrix, which were then identified by LC-MS/MS. The toxicity of the synthesised compounds was predicted using a toxicity estimation software tool.

Biochemical characterisation of an allantoate-degrading enzyme from French bean (Phaseolus vulgaris): the requirement of phenylhydrazine.

PubMed

Raso, María José; Muñoz, Alfonso; Pineda, Manuel; Piedras, Pedro

2007-10-01

In tropical legumes like French bean (Phaseolus vulgaris) or soybean (Glycine max), most of the atmospheric nitrogen fixed in nodules is used for synthesis of the ureides allantoin and allantoic acid, the major long distance transport forms of organic nitrogen in these species. The purpose of this investigation was to characterise the allantoate degradation step in Phaseolus vulgaris. The degradation of allantoin, allantoate and ureidoglycolate was determined "in vivo" using small pieces of chopped seedlings. With allantoate and ureidoglycolate as substrates, the determination of the reaction products required the addition of phenylhydrazine to the assay mixture. The protein associated with the allantoate degradation has been partially purified 22-fold by ultracentrifugation and batch separation with DEAE-Sephacel. This enzyme was specific for allantoate and could not use ureidoglycolate as substrate. The activity was completely dependent on phenylhydrazine, which acts as an activator at low concentrations and decreases the affinity of the enzyme for the substrate at higher concentrations. The optimal pH for the activity of the purified protein was 7.0 and the optimal temperature was 37 degrees C. The activity was completely inhibited by EDTA and only manganese partially restored the activity. The level of activity was lower in extracts obtained from leaves and fruits of French bean grown with nitrate than in plants actively fixing nitrogen and, therefore, relying on ureides as nitrogen supply. This is the first time that an allantoate-degrading activity has been partially purified and characterised from a plant extract. The allosteric regulation of the enzyme suggests a critical role in the regulation of ureide degradation.

Diversity-Oriented Synthesis as a Strategy for Fragment Evolution against GSK3β.

PubMed

Wang, Yikai; Wach, Jean-Yves; Sheehan, Patrick; Zhong, Cheng; Zhan, Chenyang; Harris, Richard; Almo, Steven C; Bishop, Joshua; Haggarty, Stephen J; Ramek, Alexander; Berry, Kayla N; O'Herin, Conor; Koehler, Angela N; Hung, Alvin W; Young, Damian W

2016-09-08

Traditional fragment-based drug discovery (FBDD) relies heavily on structural analysis of the hits bound to their targets. Herein, we present a complementary approach based on diversity-oriented synthesis (DOS). A DOS-based fragment collection was able to produce initial hit compounds against the target GSK3β, allow the systematic synthesis of related fragment analogues to explore fragment-level structure-activity relationship, and finally lead to the synthesis of a more potent compound.

Total synthesis of TMG-chitotriomycin based on an automated electrochemical assembly of a disaccharide building block.

PubMed

Isoda, Yuta; Sasaki, Norihiko; Kitamura, Kei; Takahashi, Shuji; Manmode, Sujit; Takeda-Okuda, Naoko; Tamura, Jun-Ichi; Nokami, Toshiki; Itoh, Toshiyuki

2017-01-01

The total synthesis of TMG-chitotriomycin using an automated electrochemical synthesizer for the assembly of carbohydrate building blocks is demonstrated. We have successfully prepared a precursor of TMG-chitotriomycin, which is a structurally-pure tetrasaccharide with typical protecting groups, through the methodology of automated electrochemical solution-phase synthesis developed by us. The synthesis of structurally well-defined TMG-chitotriomycin has been accomplished in 10-steps from a disaccharide building block.

An unusual stable mononuclear Mn(III) bis-terpyridine complex exhibiting Jahn-Teller compression: electrochemical synthesis, physical characterisation and theoretical study.

PubMed

Romain, Sophie; Duboc, Carole; Neese, Frank; Rivière, Eric; Hanton, Lyall R; Blackman, Allan G; Philouze, Christian; Leprêtre, Jean-Claude; Deronzier, Alain; Collomb, Marie-Noëlle

2009-01-01

The mononuclear manganese bis-terpyridine complex [Mn(tolyl-terpy)(2)](X)(3) (1(X)(3); X=BF(4), ClO(4), PF(6); tolyl-terpy=4'-(4-methylphenyl)-2,2':6',2"-terpyridine), containing Mn in the unusual +III oxidation state, has been isolated and characterised. The 1(3+) ion is a rare example of a mononuclear Mn(III) complex stabilised solely by neutral N ligands. Complex 1(3+) is obtained by electrochemical oxidation of the corresponding Mn(II) compound 1(2+) in anhydrous acetonitrile. Under these conditions the cyclic voltammogram of 1(2+) exhibits not only the well-known Mn(II)/Mn(III) oxidation at E(1/2)=+0.91 V versus Ag/Ag(+) (+1.21 V vs. SCE) but also a second metal-based oxidation process corresponding to Mn(III)/Mn(IV) at E(1/2)=+1.63 V (+1.93 V vs. SCE). Single crystals of 1(PF(6))(3)2 CH(3)CN were obtained by an electrocrystallisation procedure. X-ray analysis unambiguously revealed its tetragonally compressed octahedral geometry and high-spin character. The electronic properties of 1(3+) were investigated in detail by magnetic measurements and theoretical calculations, from which a D value of +4.82 cm(-1) was precisely determined. Density functional and complete active space self consistent field ab initio calculations both correctly predict a positive sign of D, in agreement with the compressed tetragonal distortion observed in the X-ray structure of 1(PF(6))(3)2 CH(3)CN. The different contributions to D were calculated, and the results show that 1) the spin-orbit coupling part (+2.593 cm(-1)) is predominant compared to the spin-spin interaction (+1.075 cm(-1)) and 2) the excited triplet states make the dominant contribution to the total D value.

Total Synthesis of Bryostatins. Development of Methodology for Atom-Economic and Stereoselective Synthesis of the C-ring Subunit

PubMed Central

Trost, Barry M.; Frontier, Alison J.; Thiel, Oliver R.; Yang, Hanbiao; Dong, Guangbin

2012-01-01

Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for stereoselective assembly of the C-ring subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the C-ring subunit of bryostatins. PMID:21793057

Correlating ultrasonic impulse and addition of ZnO promoter with CO2 conversion and methanol selectivity of CuO/ZrO2 catalysts.

PubMed

Ezeh, Collins I; Yang, Xiaogang; He, Jun; Snape, Colin; Cheng, Xiao Min

2018-04-01

The thermal characteristics of Cu-based catalysts for CO 2 utilization towards the synthesis of methanol were analysed and discussed in this study. The preparation process were varied by adopting ultrasonic irradiation at various impulses for the co-precipitation route and also, by introducing ZnO promoters using the solid-state reaction route. Prepared catalysts were characterised using XRD, TPR, TPD, SEM, BET and TG-DTA-DSC. In addition, the CO 2 conversion and CH 3 OH selectivity of these samples were assessed. Calcination of the catalysts facilitated the interaction of the Cu catalyst with the respective support bolstering the thermal stability of the catalysts. The characterisation analysis clearly reveals that the thermal performance of the catalysts was directly related to the sonication impulse and heating rate. Surface morphology and chemistry was enhanced with the aid of sonication and introduction of promoters. However, the impact of the promoter outweighs that of the sonication process. CO 2 conversion and methanol selectivity showed a significant improvement with a 270% increase in methanol yield. Copyright © 2017 Elsevier B.V. All rights reserved.

Copper resinate: preparation, characterisation and study of degradation.

PubMed

Colombini, M P; Lanterna, G; Mairani, A; Matteini, M; Modugno, F; Rizzi, M

2001-01-01

This paper describes a method for the synthesis of Copper Resinate, which disappeared from artists' palettes in the eighteenth century. This was carried out by interpreting ancient recipes following a scientific approach. Its characterisation using Fourier Transform-Infrared Spectrometry and Gas Chromatography-Mass Spectrometry demonstrated that it is a mixture containing copper and oxidised abietic acids, mainly dehydroabietic and 7-oxo-dehydroabietic acids, formed during the preparation of the pigment and the curing of the paint layer. The composition of copper resinate paint layers, artificially aged by U.V. irradiation at 365 nm (UV), heating (T), and exposed to atmospheric pollutants (NOX) in a climatic chamber, was investigated. The combination of irradiation and temperature produced a change in colour along with a significant increase in the recovered amount of 7-oxo-dehydroabietic acid. The identification of copper resinate in a sample from an old painting should be related to the presence of the following resin compounds which are stable in the ageing process: dehydroabietic and 7-oxo-dehydroabietic acid pimaradienic acids. Photo-oxidation of the resin acids co-ordinated with copper seem to be the most probable decay mechanism responsible for the colour change in the pigment.

Rhenium tetrazolato complexes coordinated to thioalkyl-functionalised phenanthroline ligands: synthesis, photophysical characterisation, and incubation in live HeLa cells.

PubMed

Werrett, Melissa V; Wright, Phillip J; Simpson, Peter V; Raiteri, Paolo; Skelton, Brian W; Stagni, Stefano; Buckley, Alysia G; Rigby, Paul J; Massi, Massimiliano

2015-12-21

Three new complexes of formulation fac-[Re(CO)3(diim)L], where diim is either 1,10-phenanthroline or 1,10-phenanthroline functionalised at position 5 by a thioalkyl chain, and L is either a chloro or aryltetrazolato ancillary ligand, were synthesised and photophysically characterised. The complexes exhibit phosphorescent emission with maxima around 600 nm, originating from triplet metal-to-ligand charge transfer states with partially mixed ligand-to-ligand charge transfer character. The emission is relatively long-lived, within the 200-400 ns range, and with quantum yields of 2-4%. The complexes were trialed as cellular markers in live HeLa cells, along with two previously reported rhenium tetrazolato complexes bound to unsubstituted 1,10-phenanthroline. All five complexes exhibit good cellular uptake and non-specific perinuclear localisation. Upon excitation at 405 nm, the emission from the rhenium complexes could be clearly distinguished from autofluorescence, as demonstrated by spectral detection within the live cells. Four of the complexes did not appear to be toxic, however prolonged excitation could result in membrane blebbing. No major sign of photobleaching was detected upon multiple imaging on the same cell sample.

Quasi physisorptive two dimensional tungsten oxide nanosheets with extraordinary sensitivity and selectivity to NO2.

PubMed

Khan, Hareem; Zavabeti, Ali; Wang, Yichao; Harrison, Christopher J; Carey, Benjamin J; Mohiuddin, Md; Chrimes, Adam F; De Castro, Isabela Alves; Zhang, Bao Yue; Sabri, Ylias M; Bhargava, Suresh K; Ou, Jian Zhen; Daeneke, Torben; Russo, Salvy P; Li, Yongxiang; Kalantar-Zadeh, Kourosh

2017-12-14

Attributing to their distinct thickness and surface dependent physicochemical properties, two dimensional (2D) nanostructures have become an area of increasing interest for interfacial interactions. Effectively, properties such as high surface-to-volume ratio, modulated surface activities and increased control of oxygen vacancies make these types of materials particularly suitable for gas-sensing applications. This work reports a facile wet-chemical synthesis of 2D tungsten oxide nanosheets by sonication of tungsten particles in an acidic environment and thermal annealing thereafter. The resultant product of large nanosheets with intrinsic substoichiometric properties is shown to be highly sensitive and selective to nitrogen dioxide (NO 2 ) gas, which is a major pollutant. The strong synergy between polar NO 2 molecules and tungsten oxide surface and also abundance of active surface sites on the nanosheets for molecule interactions contribute to the exceptionally sensitive and selective response. An extraordinary response factor of ∼30 is demonstrated to ultralow 40 parts per billion (ppb) NO 2 at a relatively low operating temperature of 150 °C, within the physisorption temperature band for tungsten oxide. Selectivity to NO 2 is demonstrated and the theory behind it is discussed. The structural, morphological and compositional characteristics of the synthesised and annealed materials are extensively characterised and electronic band structures are proposed. The demonstrated 2D tungsten oxide based sensing device holds the greatest promise for producing future commercial low-cost, sensitive and selective NO 2 gas sensors.

Uniaxial negative thermal expansion and metallophilicity in Cu3[Co(CN)6

NASA Astrophysics Data System (ADS)

Sapnik, A. F.; Liu, X.; Boström, H. L. B.; Coates, C. S.; Overy, A. R.; Reynolds, E. M.; Tkatchenko, A.; Goodwin, A. L.

2018-02-01

We report the synthesis and structural characterisation of the molecular framework copper(I) hexacyanocobaltate(III), Cu3[Co(CN)6], which we find to be isostructural to H3[Co(CN)6] and the colossal negative thermal expansion material Ag3[Co(CN)6]. Using synchrotron X-ray powder diffraction measurements, we find strong positive and negative thermal expansion behaviour respectively perpendicular and parallel to the trigonal crystal axis: αa = 25.4 (5)M K - 1 and αc = - 43.5 (8)M K - 1 . These opposing effects collectively result in a volume expansivity αV = 7.4 (11)M K - 1 that is remarkably small for an anisotropic molecular framework. This thermal response is discussed in the context of the behaviour of the analogous H- and Ag-containing systems. We make use of density-functional theory with many-body dispersion interactions (DFT + MBD) to demonstrate that Cu+…Cu+ metallophilic ('cuprophilic') interactions are significantly weaker in Cu3[Co(CN)6] than Ag+…Ag+ interactions in Ag3[Co(CN)6], but that this lowering of energy scale counterintuitively translates to a more moderate-rather than enhanced-degree of structural flexibility. The same conclusion is drawn from consideration of a simple GULP model, which we also present here. Our results demonstrate that strong interactions can actually be exploited in the design of ultra-responsive materials if those interactions are set up to act in tension.

Synthesis and characterisation of coating polyurethane cationomers containing fluorine built-in hard urethane segments

PubMed Central

Król, Bożena; Pikus, Stanisław; Chmielarz, Paweł; Skrzypiec, Krzysztof

2010-01-01

Polyurethane cationomers were synthesised in the reaction of 4,4’-methylenebis(phenyl isocyanate) with polyoxyethylene glycol (M = 2,000) or poly(tetrafluoroethyleneoxide-co-difluoromethylene oxide) α,ω-diisocyanate and N-methyl diethanolamine. Amine segments were built-in to the urethane-isocyanate prepolymer in the reaction with 1-bromobutane or formic acid, and then they were converted to alkylammonium cations. The obtained isocyanate prepolymers were then extended in the aqueous medium that yielded stable aqueous dispersions which were applied on the surfaces of test poly(tetrafluoroethylene) plates. After evaporation of water, the dispersions formed thin polymer coatings. 1H, 13C NMR and IR spectral methods were employed to confirm chemical structures of synthesised cationomers. Based on 1H NMR and IR spectra, the factors κ and α were calculated, which represented the polarity level of the obtained cationomers. The DSC, wide angle X-ray scattering and atom force microscopy methods were employed for the microstructural assessment of the obtained materials. Changes were discussed in the surface free energy and its components, as calculated independently according to the method suggested by van Oss–Good, in relation to chemical and physical structures of cationomers as well as morphology of coating surfaces obtained from those cationomers. Fluorine incorporated into cationomers (about 30%) contributed to lower surface free energy values, down to about 15 mJ/m2. That was caused by gradual weakening of long-range interactions within which the highest share is taken by dispersion interactions. PMID:20927181

Functional characterisation of ganglioside-induced differentiation-associated protein 1 as a glutathione transferase.

PubMed

Shield, Alison J; Murray, Tracy P; Board, Philip G

2006-09-08

Mutations in the ganglioside-induced differentiation-associated protein 1 (GDAP1) gene have been linked with Charcot-Marie-Tooth (CMT) disease. This protein, and its paralogue GDAP1L1, appear to be structurally related to the cytosolic glutathione S-transferases (GST) including an N-terminal thioredoxin fold domain with conserved active site residues. The specific function, of GDAP1 remains unknown. To further characterise their structure and function we purified recombinant human GDAP1 and GDAP1L1 proteins using bacterial expression and immobilised metal affinity chromatography. Like other cytosolic GSTs, GDAP1 protein has a dimeric structure. Although the full-length proteins were largely insoluble, the deletion of a proposed C-terminal transmembrane domain allowed the preparation of soluble protein. The purified proteins were assayed for glutathione-dependent activity against a library of 'prototypic' GST substrates. No evidence of glutathione-dependent activity or an ability to bind glutathione immobilised on agarose was found.

Simultaneous NMR characterisation of multiple minima in the free energy landscape of an RNA UUCG tetraloop.

PubMed

Borkar, Aditi N; Vallurupalli, Pramodh; Camilloni, Carlo; Kay, Lewis E; Vendruscolo, Michele

2017-01-25

RNA molecules in solution tend to undergo structural fluctuations of relatively large amplitude and to populate a range of different conformations some of which with low populations. It is still very challenging, however, to characterise the structures of these low populated states and to understand their functional roles. In the present study, we address this problem by using NMR residual dipolar couplings (RDCs) as structural restraints in replica-averaged metadynamics (RAM) simulations. By applying this approach to a 14-mer RNA hairpin containing the prototypical UUCG tetraloop motif, we show that it is possible to construct the free energy landscape of this RNA molecule. This free energy landscapes reveals the surprisingly rich dynamics of the UUCG tetraloop and identifies the multiple substates that exist in equilibrium owing to thermal fluctuations. The approach that we present is general and can be applied to the study of the free energy landscapes of other RNA or RNA-protein systems.

Infrared and infrared emission spectroscopic study of typical Chinese kaolinite and halloysite.

PubMed

Cheng, Hongfei; Frost, Ray L; Yang, Jing; Liu, Qinfu; He, Junkai

2010-12-01

The structure and thermal stability between typical Chinese kaolinite and halloysite were analysed by X-ray diffraction (XRD), infrared spectroscopy, infrared emission spectroscopy (IES) and Raman spectroscopy. Infrared emission spectroscopy over the temperature range of 300-700°C has been used to characterise the thermal decomposition of both kaolinite and halloysite. Halloysite is characterised by two bands in the water bending region at 1629 and 1648 cm(-1), attributed to structural water and coordinated water in the interlayer. Well defined hydroxyl stretching bands at around 3695, 3679, 3652 and 3625 cm(-1) are observed for both kaolinite and halloysite. The 550°C infrared emission spectrum of halloysite is similar to that of kaolinite in 650-1350 cm(-1) spectral region. The infrared emission spectra of halloysite were found to be considerably different to that of kaolinite at lower temperatures. These differences are attributed to the fundamental difference in the structure of the two minerals. Copyright © 2010 Elsevier B.V. All rights reserved.

Genetics Home Reference: TRNT1 deficiency

MedlinePlus

... in the production (synthesis) of other proteins. During protein synthesis, a molecule called transfer RNA (tRNA) helps assemble ... thought to be less able to participate in protein synthesis. Researchers suspect that protein synthesis in cellular structures ...

Fourier transform Raman spectroscopic characterisation of cells of the plant-associated soil bacterium Azospirillum brasilense Sp7

NASA Astrophysics Data System (ADS)

Kamnev, A. A.; Tarantilis, P. A.; Antonyuk, L. P.; Bespalova, L. A.; Polissiou, M. G.; Colina, M.; Gardiner, P. H. E.; Ignatov, V. V.

2001-05-01

Structural and compositional features of bacterial cell samples and of lipopolysaccharide-protein complex isolated from the cell surface of the plant-growth-promoting rhizobacterium Azospirillum brasilense (wild-type strain Sp7) were characterised using Fourier transform (FT) Raman spectroscopy. The structural spectroscopic information obtained is analysed and considered together with analytical data on the content of metal cations (Co 2+, Cu 2+ and Zn 2+) in the bacterial cells grown in a standard medium as well as in the presence of each of the cations (0.2 mM). The latter, being taken up by bacterial cells from the culture medium in significant amounts, were shown to induce certain metabolic changes in the bacterium revealed in FT-Raman spectra, which is discussed from the viewpoint of bacterial response to environmental stresses.

Production and Structural Investigation of Polyethylene Composites with Modified Kaolin

NASA Astrophysics Data System (ADS)

Domka, L.; Malicka, A.; Stachowiak, N.

2008-08-01

The study was undertaken to evaluate the effect of the filler (kaolin) modification with silane coupling agents on the properties of the polyethylene (HDPE Hostalen ACP 5831) composites. Powder mineral fillers are added to polymers to modify the properties of the latter and to reduce the cost of their production. A very important factor is the filler dispersion in the polymer matrix. Kaolin modified with 3-methacryloxypropyltrimethoxysilane and pure kaolin were characterised by surface area, pore size, water absorbing capacity, paraffin oil absorbing capacity, bulk density, scanning electron microscopy observations and X-ray diffraction measurements. Their performance was characterised by determination of the mechanical resistance upon static stretching and tearing, and their structure was observed in scanning electron microscopy images. The results were compared to those obtained for the composites with unmodified filler and pure HDPE.

Infaunal Benthic Communities from the Inner Shelf off Southwestern Africa Are Characterised by Generalist Species

PubMed Central

Steffani, Nina; Sedick, Safiyya; Rogers, John; Gibbons, Mark John

2015-01-01

Infaunal communities of benthic macro-organisms (≥ 1mm length) were studied from 81 samples collected across nine sites to the north and south of the Orange River in the Benguela upwelling ecosystem in 2003, with a view to describing communities and understanding the drivers of regional community structure, as well as to document diversity and to examine geographic affinities. Although the fauna was dominated by polychaetes and peracarid crustaceans, patterns in community structure could only weakly be explained by the measured environment (~35%). This is attributed to the generalist nature of the species recovered, which were widely distributed amongst different sediments, water-depths and latitudes. The fauna is dominated by species that enjoy a widespread regional and global distribution and is characterised by relatively low diversity, which is discussed. PMID:26618477

Total synthesis of TMG-chitotriomycin based on an automated electrochemical assembly of a disaccharide building block

PubMed Central

Isoda, Yuta; Sasaki, Norihiko; Kitamura, Kei; Takahashi, Shuji; Manmode, Sujit; Takeda-Okuda, Naoko; Tamura, Jun-ichi

2017-01-01

The total synthesis of TMG-chitotriomycin using an automated electrochemical synthesizer for the assembly of carbohydrate building blocks is demonstrated. We have successfully prepared a precursor of TMG-chitotriomycin, which is a structurally-pure tetrasaccharide with typical protecting groups, through the methodology of automated electrochemical solution-phase synthesis developed by us. The synthesis of structurally well-defined TMG-chitotriomycin has been accomplished in 10-steps from a disaccharide building block. PMID:28684973

Networked dynamical systems with linear coupling: synchronisation patterns, coherence and other behaviours.

PubMed

Judd, Kevin

2013-12-01

Many physical and biochemical systems are well modelled as a network of identical non-linear dynamical elements with linear coupling between them. An important question is how network structure affects chaotic dynamics, for example, by patterns of synchronisation and coherence. It is shown that small networks can be characterised precisely into patterns of exact synchronisation and large networks characterised by partial synchronisation at the local and global scale. Exact synchronisation modes are explained using tools of symmetry groups and invariance, and partial synchronisation is explained by finite-time shadowing of exact synchronisation modes.

Schistosoma comparative genomics: integrating genome structure, parasite biology and anthelmintic discovery

PubMed Central

Swain, Martin T.; Larkin, Denis M.; Caffrey, Conor R.; Davies, Stephen J.; Loukas, Alex; Skelly, Patrick J.; Hoffmann, Karl F.

2011-01-01

Schistosoma genomes provide a comprehensive resource for identifying the molecular processes that shape parasite evolution and for discovering novel chemotherapeutic or immunoprophylactic targets. Here, we demonstrate how intra- and intergenus comparative genomics can be used to drive these investigations forward, illustrate the advantages and limitations of these approaches and review how post genomic technologies offer complementary strategies for genome characterisation. While sequencing and functional characterisation of other schistosome/platyhelminth genomes continues to expedite anthelmintic discovery, we contend that future priorities should equally focus on improving assembly quality, and chromosomal assignment, of existing schistosome/platyhelminth genomes. PMID:22024648

Total synthesis of the proposed structure of trichodermatide A.

PubMed

Myers, Eddie; Herrero-Gómez, Elena; Albrecht, Irina; Lachs, Jennifer; Mayer, Peter; Hanni, Matti; Ochsenfeld, Christian; Trauner, Dirk

2014-10-17

A short total synthesis of the published structure of racemic trichodermatide A is reported. Our synthesis involves a Knoevenagel condensation/Michael addition sequence, followed by the formation of tricyclic hexahydroxanthene-dione and a diastereoselective bis-hydroxylation. The final product, the structure of which was confirmed by X-ray crystallography, has NMR spectra that are very similar, but not identical, to those of the isolated natural product. Quantum chemically computed (13)C shifts agree well with the present NMR measurements.

Structure and functional dynamics of the mitochondrial Fe/S cluster synthesis complex.

PubMed

Boniecki, Michal T; Freibert, Sven A; Mühlenhoff, Ulrich; Lill, Roland; Cygler, Miroslaw

2017-11-03

Iron-sulfur (Fe/S) clusters are essential protein cofactors crucial for many cellular functions including DNA maintenance, protein translation, and energy conversion. De novo Fe/S cluster synthesis occurs on the mitochondrial scaffold protein ISCU and requires cysteine desulfurase NFS1, ferredoxin, frataxin, and the small factors ISD11 and ACP (acyl carrier protein). Both the mechanism of Fe/S cluster synthesis and function of ISD11-ACP are poorly understood. Here, we present crystal structures of three different NFS1-ISD11-ACP complexes with and without ISCU, and we use SAXS analyses to define the 3D architecture of the complete mitochondrial Fe/S cluster biosynthetic complex. Our structural and biochemical studies provide mechanistic insights into Fe/S cluster synthesis at the catalytic center defined by the active-site Cys of NFS1 and conserved Cys, Asp, and His residues of ISCU. We assign specific regulatory rather than catalytic roles to ISD11-ACP that link Fe/S cluster synthesis with mitochondrial lipid synthesis and cellular energy status.

Programmable Triplet Formation and Decay in Metal-Organic Chromophores

DTIC Science & Technology

2011-12-13

potential applications in optical limiting molecules has resulted in the synthesis and characterization of many new classes of chromophores in...Castellano, F.N. Inorg. Chem. 2006, 45, 4304-4306. Inorganic Chemistry Cover May 29, 2006. The synthesis , structural characterization, and...The synthesis , photophysics, electronic structure, and electrochemical characterization of 4′-tert- butylacetylene-2,2′:6′,2″-terpyridineplatinum(II

Morphological Characterisation of Unstained and Intact Tissue Micro-architecture by X-ray Computed Micro- and Nano-Tomography

NASA Astrophysics Data System (ADS)

Walton, Lucy A.; Bradley, Robert S.; Withers, Philip J.; Newton, Victoria L.; Watson, Rachel E. B.; Austin, Clare; Sherratt, Michael J.

2015-05-01

Characterisation and quantification of tissue structures is limited by sectioning-induced artefacts and by the difficulties of visualising and segmenting 3D volumes. Here we demonstrate that, even in the absence of X-ray contrast agents, X-ray computed microtomography (microCT) and nanotomography (nanoCT) can circumvent these problems by rapidly resolving compositionally discrete 3D tissue regions (such as the collagen-rich adventitia and elastin-rich lamellae in intact rat arteries) which in turn can be segmented due to their different X-ray opacities and morphologies. We then establish, using X-ray tomograms of both unpressurised and pressurised arteries that intra-luminal pressure not only increases lumen cross-sectional area and straightens medial elastic lamellae but also induces profound remodelling of the adventitial layer. Finally we apply microCT to another human organ (skin) to visualise the cell-rich epidermis and extracellular matrix-rich dermis and to show that conventional histological and immunohistochemical staining protocols are compatible with prior X-ray exposure. As a consequence we suggest that microCT could be combined with optical microscopy to characterise the 3D structure and composition of archival paraffin embedded biological materials and of mechanically stressed dynamic tissues such as the heart, lungs and tendons.

Morphological Characterisation of Unstained and Intact Tissue Micro-architecture by X-ray Computed Micro- and Nano-Tomography

PubMed Central

Walton, Lucy A.; Bradley, Robert S.; Withers, Philip J.; Newton, Victoria L.; Watson, Rachel E. B.; Austin, Clare; Sherratt, Michael J.

2015-01-01

Characterisation and quantification of tissue structures is limited by sectioning-induced artefacts and by the difficulties of visualising and segmenting 3D volumes. Here we demonstrate that, even in the absence of X-ray contrast agents, X-ray computed microtomography (microCT) and nanotomography (nanoCT) can circumvent these problems by rapidly resolving compositionally discrete 3D tissue regions (such as the collagen-rich adventitia and elastin-rich lamellae in intact rat arteries) which in turn can be segmented due to their different X-ray opacities and morphologies. We then establish, using X-ray tomograms of both unpressurised and pressurised arteries that intra-luminal pressure not only increases lumen cross-sectional area and straightens medial elastic lamellae but also induces profound remodelling of the adventitial layer. Finally we apply microCT to another human organ (skin) to visualise the cell-rich epidermis and extracellular matrix-rich dermis and to show that conventional histological and immunohistochemical staining protocols are compatible with prior X-ray exposure. As a consequence we suggest that microCT could be combined with optical microscopy to characterise the 3D structure and composition of archival paraffin embedded biological materials and of mechanically stressed dynamic tissues such as the heart, lungs and tendons. PMID:25975937

Discovery and structural characterisation of new fold type IV-transaminases exemplify the diversity of this enzyme fold

PubMed Central

Pavkov-Keller, Tea; Strohmeier, Gernot A.; Diepold, Matthias; Peeters, Wilco; Smeets, Natascha; Schürmann, Martin; Gruber, Karl; Schwab, Helmut; Steiner, Kerstin

2016-01-01

Transaminases are useful biocatalysts for the production of amino acids and chiral amines as intermediates for a broad range of drugs and fine chemicals. Here, we describe the discovery and characterisation of new transaminases from microorganisms which were enriched in selective media containing (R)-amines as sole nitrogen source. While most of the candidate proteins were clearly assigned to known subgroups of the fold IV family of PLP-dependent enzymes by sequence analysis and characterisation of their substrate specificity, some of them did not fit to any of these groups. The structure of one of these enzymes from Curtobacterium pusillum, which can convert d-amino acids and various (R)-amines with high enantioselectivity, was solved at a resolution of 2.4 Å. It shows significant differences especially in the active site compared to other transaminases of the fold IV family and thus indicates the existence of a new subgroup within this family. Although the discovered transaminases were not able to convert ketones in a reasonable time frame, overall, the enrichment-based approach was successful, as we identified two amine transaminases, which convert (R)-amines with high enantioselectivity, and can be used for a kinetic resolution of 1-phenylethylamine and analogues to obtain the (S)-amines with e.e.s >99%. PMID:27905516

Testing new methodologies and assessing their potential for reservoir characterisation: Geoelectrical studies in the Northwest Carboniferous Basin (Ireland).

NASA Astrophysics Data System (ADS)

Ogaya, Xènia; Campanyà, Joan; Rath, Volker; Jones, Alan G.; Reay, Derek; Raine, Rob; McConnell, Brian; Ledo, Juanjo

2016-04-01

The overarching objective of this study is to improve our methods of characterising saline aquifers by integrating newly acquired electromagnetic data with existing geophysical and geological data. The work presented here is part of an ongoing project to evaluate Ireland's potential for onshore carbon sequestration (IRECCSEM; funded by Science Foundation Ireland). The methodology presented in this characterisation work is not only relevant for studying the potential for onshore carbon sequestration, but is generally applicable for aquifer characterisation, particularly for the evaluation of geothermal resources in appropriate geological settings. We present first results of the three-dimensional (3D) modelling and inversion of the magnetotelluric (MT) data acquired in the Northwest Carboniferous Basin (Ireland) in summer 2015. The electrical resistivity distribution beneath the survey area is constrained using a joint inversion of three different types of electromagnetic data: MT impedance tensor responses (Z), geomagnetic transfer functions (GTF) and inter-station horizontal magnetic transfer-functions (HMT). The preliminary 3D resistivity model obtained reveals the geoelectrical structure of the subsurface, which is translated into parameters relevant to fluid flow. The electromagnetic data were acquired along profiles linking four wells drilled in the area and the available well log data from those wells are used to evaluate some of the existing petrophysical relationships and calibrate them for the study area. This allows us to interpolate the rock physical properties from one well to another well, using the computed geoelectrical model as a reference. The obtained results are compared to available independent geological and geophysical data in order to analyse the validity of this technique, to characterise the uncertainties inherent to our approach, and to assess the potential of this methodology for reservoir characterisation.

Phellilane L, Sesquiterpene Metabolite of Phellinus linteus: Isolation, Structure Elucidation, and Asymmetric Total Synthesis.

PubMed

Ota, Koichiro; Yamazaki, Ikuma; Saigoku, Takahiro; Fukui, Mei; Miyata, Tomoki; Kamaike, Kazuo; Shirahata, Tatsuya; Mizuno, Fumi; Asada, Yoshihisa; Hirotani, Masao; Ino, Chieko; Yoshikawa, Takafumi; Kobayashi, Yoshinori; Miyaoka, Hiroaki

2017-12-01

A new cyclopropane-containing sesquiterpenoid, phellilane L (1), was isolated from the medicinal mushroom Phellinus linteus ("Meshimakobu" in Japanese), a member of the Hymenochaetaceae family and a well-known fungus that is widely used in East Asia. The planar structure of 1 was determined on the basis of spectroscopic analysis. The authors achieved the first total synthesis of 1. Our protecting group-free synthesis features a highly stereoselective one-pot synthesis involving an intermolecular alkylation/cyclization/lactonization strategy for construction of the key cyclopropane-γ-lactone intermediate. Additionally, our synthesis determined the absolute configuration of phellilane L (1).

Characterisation of cuticular nanostructures on surfaces of insects by atomic force microscopy: mining evolution for smart structures

NASA Astrophysics Data System (ADS)

Watson, Gregory S.; Blach, Jolanta A.

2002-11-01

The optical properties of insect nano-structures have been extensively studied. In particular, nano-scale ordered arrays have been reported from studies of the corneal surfaces of some insects and of insect wings showing anti-reflective properties. These arrays have been ascribed to evolutionary adaptation and survival value arising from increased visual capacity and better camouflage against predators. In this study we show that the Atomic Force Microscope (AFM) can effectively reveal and quantify the three dimensional structures of nano-arrays on moth eyes and cicada wings. It is also shown that the arrays present an ideal surface for in situ characterisation of the AFM probe/tip. In addition, a new structure is presented which has been discovered on a termite wing. The structure is similar to that found on the cicada wing, but has a much larger 'lattice parameter' for the ordered array. The function(s) of the array is unknown at present. It could be effective as an anti-reflective coating, but would then be active in the infra-red region of the light spectrum. Alternatively, it may confer evolutionary advantage by virtue of its mechanical strength, or it may improve the aerodynamics of flying. The study demonstrates that natural selection may be a rich source of 'smart' structures.

Protic ammonium carboxylate ionic liquids: insight into structure, dynamics and thermophysical properties by alkyl group functionalization.

PubMed

Reddy, Th Dhileep N; Mallik, Bhabani S

2017-04-19

This study is aimed at characterising the structure, dynamics and thermophysical properties of five alkylammonium carboxylate ionic liquids (ILs) from classical molecular dynamics simulations. The structural features of these ILs were characterised by calculating the site-site radial distribution functions, g(r), spatial distribution functions and structure factors. The structural properties demonstrate that ILs show greater interaction between cations and anions when alkyl chain length increases on the cation or anion. In all ILs, spatial distribution functions show that the anion is close to the acidic hydrogen atoms of the ammonium cation. We determined the role of alkyl group functionalization of the charged entities, cations and anions, in the dynamical behavior and the transport coefficients of this family of ionic liquids. The dynamics of ILs are described by studying the mean square displacement (MSD) of the centres of mass of the ions, diffusion coefficients, ionic conductivities and hydrogen bonds as well as residence dynamics. The diffusion coefficients and ionic conductivity decrease with an increase in the size of the cation or anion. The effect of alkyl chain length on ionic conductivity calculated in this article is consistent with the findings of other experimental studies. Hydrogen bond lifetimes and residence times along with structure factors were also calculated, and are related to alkyl chain length.

Barriers, facilitators, strategies and outcomes to engaging policymakers, healthcare managers and policy analysts in knowledge synthesis: a scoping review protocol

PubMed Central

Tricco, Andrea C; Zarin, Wasifa; Rios, Patricia; Pham, Ba’; Straus, Sharon E; Langlois, Etienne V

2016-01-01

Introduction Engaging policymakers, healthcare managers and policy analysts in the conduct of knowledge synthesis can help increase its impact. This is particularly important for knowledge synthesis studies commissioned by decision-makers with limited timelines, as well as reviews of health policy and systems research. A scoping review will be conducted to assess barriers, facilitators, strategies and outcomes of engaging these individuals in the knowledge synthesis process. Methods and analysis We will follow the Joanna Briggs Institute guidance for scoping reviews. Literature searches of electronic databases (eg, MEDLINE, EMBASE, Cochrane Library, ERIC, PsycINFO) will be conducted from inception onwards. The electronic search will be supplemented by searching for sources that index unpublished/difficult to locate studies (eg, GreyNet International database), as well as through scanning of reference lists of reviews on related topics. All study designs using either qualitative or quantitative methodologies will be eligible if there is a description of the strategies, barriers or facilitators, and outcomes of engaging policymakers, healthcare managers and policy analysts in the knowledge synthesis process. Screening and data abstraction will be conducted by 2 team members independently after a calibration exercise across the team. A third team member will resolve all discrepancies. We will conduct frequency analysis and thematic analysis to chart and characterise the literature, identifying data gaps and opportunities for future research, as well as implications for policy. Ethics and dissemination This project was commissioned by the Alliance for Health Policy and Systems Research, WHO. The results will be used by Alliance Review Centers of health policy and systems research in low-income and middle-income countries that are conducting knowledge synthesis to inform health policymaking and decision-making. Our results will also be disseminated through conference presentations, train-the-trainer events, peer-reviewed publication and a 1-page policy brief that will be posted on the authors' websites. PMID:28011815

Synthesis and optimization of four bar mechanism with six design parameters

NASA Astrophysics Data System (ADS)

Jaiswal, Ankur; Jawale, H. P.

2018-04-01

Function generation is synthesis of mechanism for specific task, involves complexity for specially synthesis above five precision of coupler points. Thus pertains to large structural error. The methodology for arriving to better precision solution is to use the optimization technique. Work presented herein considers methods of optimization of structural error in closed kinematic chain with single degree of freedom, for generating functions like log(x), ex, tan(x), sin(x) with five precision points. The equation in Freudenstein-Chebyshev method is used to develop five point synthesis of mechanism. The extended formulation is proposed and results are obtained to verify existing results in literature. Optimization of structural error is carried out using least square approach. Comparative structural error analysis is presented on optimized error through least square method and extended Freudenstein-Chebyshev method.

Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keates, Adam C.; Wang, Qianlong; Weller, Mark T., E-mail: m.t.weller@bath.ac.uk

2014-02-15

Single crystal and bulk polycrystalline forms of K{sub 2}MP{sub 2}O{sub 7} (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42{sub 1}m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP{sub 2}O{sub 7}]{sup 2−} with potassium cations situated between the layers. The MO{sub 4} tetrahedra share oxygen atoms with [P{sub 2}O{sub 7}]{sup 4−} diphosphate groups and the potassium ions have KO{sub 8} square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen,more » as a result of the Jahn–Teller (JT) effect for the high spin d{sup 6} Fe(II) and p-orbital mixing or a second order JT effect for d{sup 9} Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K{sub 2}MP{sub 2}O{sub 7}, M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP{sub 2}O{sub 7}]{sup 2−}, formed from linked pyrophosphate groups and MO{sub 4} tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d{sup 6} Fe(II) and p-orbital mixing and second-order JT effects for d{sup 9} Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d{sup 10} distorted coordinations.« less

Synthesis, characterisation and thermoelectric properties of the oxytelluride Bi{sub 2}O{sub 2}Te

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luu, Son D.N.; Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD; Vaqueiro, Paz, E-mail: p.vaqueiro@reading.ac.uk

2015-03-15

Bi{sub 2}O{sub 2}Te was synthesised from a stoichiometric mixture of Bi, Bi{sub 2}O{sub 3} and Te by a solid state reaction. Analysis of powder X-ray diffraction data indicates that this material crystallises in the anti-ThCr{sub 2}Si{sub 2} structure type (space group I4/mmm), with lattice parameters a=3.98025(4) and c=12.70391(16) Å. The electrical and thermal transport properties of Bi{sub 2}O{sub 2}Te were investigated as a function of temperature over the temperature range 300≤T (K)≤665. These measurements indicate that Bi{sub 2}O{sub 2}Te is an n-type semiconductor, with a band gap of 0.23 eV. The thermal conductivity of Bi{sub 2}O{sub 2}Te is remarkably lowmore » for a crystalline material, with a value of only 0.91 W m{sup −1} K{sup −1} at room temperature. - Graphical abstract: Bi{sub 2}O{sub 2}Te, which crystallises in the anti-ThCr{sub 2}Si{sub 2} structure type, is an n-type semiconductor with a remarkably low thermal conductivity. - Highlights: • Bi{sub 2}O{sub 2}Te crystallises in the anti-ThCr{sub 2}Si{sub 2} structure type. • Bi{sub 2}O{sub 2}Te is an n-type semiconductor, with a band gap of 0.23 eV. • The thermal conductivity of Bi{sub 2}O{sub 2}Te approaches values found for amorphous solids. • The thermoelectric figure of merit of undoped Bi{sub 2}O{sub 2}Te reaches 0.13 at 573 K.« less

Flaws in foldamers: conformational uniformity and signal decay in achiral helical peptide oligomers† †Electronic supplementary information (ESI) available: Synthesis and characterisation of all new compounds. See DOI: 10.1039/c4sc03944k Click here for additional data file.

PubMed Central

Le Bailly, Bryden A. F.; Byrne, Liam; Diemer, Vincent; Foroozandeh, Mohammadali; Morris, Gareth A.

2015-01-01

Although foldamers, by definition, are extended molecular structures with a well-defined conformation, minor conformers must be populated at least to some extent in solution. We present a quantitative analysis of these minor conformers for a series of helical oligomers built from achiral but helicogenic α-amino acids. By measuring the chain length dependence or chain position dependence of NMR or CD quantities that measure screw-sense preference in a helical oligomer, we quantify values for the decay constant of a conformational signal as it passes through the molecular structure. This conformational signal is a perturbation of the racemic mixture of M and P helices that such oligomers typically adopt by the inclusion of an N or C terminal chiral inducer. We show that decay constants may be very low (<1% signal loss per residue) in non-polar solvents, and we evaluate the increase in decay constant that results in polar solvents, at higher temperatures, and with more conformationally flexible residues such as Gly. Decay constants are independent of whether the signal originates from the N or the C terminus. By interpreting the decay constant in terms of the probability with which conformations containing a screw-sense reversal are populated, we quantify the populations of these alternative minor conformers within the overall ensemble of secondary structures adopted by the foldamer. We deduce helical persistence lengths for Aib polymers that allow us to show that in a non-polar solvent a peptide helix, even in the absence of chiral residues, may continue with the same screw sense for approximately 200 residues. PMID:29308146

Structural, thermal, dielectric and phonon properties of perovskite-like imidazolium magnesium formate.

PubMed

Mączka, Mirosław; Marinho Costa, Nathalia Leal; Gągor, Anna; Paraguassu, Waldeci; Sieradzki, Adam; Hanuza, Jerzy

2016-05-18

We report the synthesis and characterisation of a magnesium formate framework templated by protonated imidazole. Single-crystal X-ray diffraction data showed that this compound crystallizes in the monoclinic structure in the P21/n space group with lattice parameters a = 12.1246(4) Å, b = 12.2087(5) Å, c = 12.4991(4) Å and β = 91.39(1)°. The antiparallel arrangement of the dipole moments associated with imidazolium cations suggests the antiferroelectric character of the room-temperature phase. The studied compound undergoes a structural phase transition at 451 K associated with a halving of the c lattice parameter and the disappearance of the antiferroelectric order. The monoclinic symmetry is preserved and the new metrics are a = 12.261(7) Å, b = 12.290(4) Å, c = 6.280(4) Å, and β = 90.62(5)°. Raman and IR data are consistent with the X-ray diffraction data. They also indicate that the disorder of imidazolium cations plays a significant role in the mechanism of the phase transition. Dielectric data show that the phase transition is associated with a relaxor nature of electric ordering. We also report high-pressure Raman scattering studies of this compound that revealed the presence of two pressure-induced phase transitions near 3 and 7 GPa. The first transition is most likely associated with a rearrangement of the imidazolium cations without any significant distortion of these cations and the magnesium formate framework, whereas the second transition leads to strong distortion of both the framework and imidazolium cations. High-pressure data also show that imidazolium magnesium formate does not show any signs of amorphization up to 11.4 GPa.

Synthesis of phosphinoferrocene amides and thioamides from carbamoyl chlorides and the structural chemistry of Group 11 metal complexes with these mixed-donor ligands.

PubMed

Fernandes, Tiago A; Solařová, Hana; Císařová, Ivana; Uhlík, Filip; Štícha, Martin; Štěpnička, Petr

2015-02-21

The reaction of in situ generated 1'-(diphenylphosphino)-1-lithioferrocene with carbamoyl chlorides, ClC(E)NMe2, affords the corresponding (thio)amides, Ph2PfcC(E)NMe2 (E = O (), S (); fc = ferrocene-1,1'-diyl). These compounds as well as their analogues, Ph2PfcC(O)NHMe () and Ph2PfcC(O)NH2 (), prepared from 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) were studied as ligands for the Group 11 metal ions. In the reactions with [Cu(MeCN)4][BF4], the amides give rise to bis-chelate complexes of the type [Cu(L-κ(2)O,P)2][BF4]. Similar products, [Ag(L-κ(2)O,P)2]ClO4, are obtained from silver(i) perchlorate and , or . In contrast, the reaction of AgClO4 with produces a unique molecular dimer [Ag()(ClO4-κO)]2, where the metal centres are bridged by the sulfur atoms of the P,S-chelating thioamides. The reactions of with [AuCl(tht)] (tht = tetrahydrothiophene) afford the expected gold(i)-phosphine complexes, [AuCl(L-κP)], containing uncoordinated (thio)amide moieties. Hemilabile coordination of the phosphinoamide ligands in complexes with the soft Group 11 metal ions is established by the crystal structure of a solvento complex, [Cu(-κ(2)O,P)(-κP)(CHCl3-κCl)][BF4], which was isolated serendipitously during an attempted crystallisation of [Cu(-κ(2)O,P)2][BF4]. All of the compounds are characterised by spectroscopic methods, and the structures of several representatives of both the free phosphinoamides and their complexes are determined by X-ray diffraction analysis and further studied by DFT calculations and cyclic voltammetry.

Genomic characterisation of Wongabel virus reveals novel genes within the Rhabdoviridae.

PubMed

Gubala, Aneta J; Proll, David F; Barnard, Ross T; Cowled, Chris J; Crameri, Sandra G; Hyatt, Alex D; Boyle, David B

2008-06-20

Viruses belonging to the family Rhabdoviridae infect a variety of different hosts, including insects, vertebrates and plants. Currently, there are approximately 200 ICTV-recognised rhabdoviruses isolated around the world. However, the majority remain poorly characterised and only a fraction have been definitively assigned to genera. The genomic and transcriptional complexity displayed by several of the characterised rhabdoviruses indicates large diversity and complexity within this family. To enable an improved taxonomic understanding of this family, it is necessary to gain further information about the poorly characterised members of this family. Here we present the complete genome sequence and predicted transcription strategy of Wongabel virus (WONV), a previously uncharacterised rhabdovirus isolated from biting midges (Culicoides austropalpalis) collected in northern Queensland, Australia. The 13,196 nucleotide genome of WONV encodes five typical rhabdovirus genes N, P, M, G and L. In addition, the WONV genome contains three genes located between the P and M genes (U1, U2, U3) and two open reading frames overlapping with the N and G genes (U4, U5). These five additional genes and their putative protein products appear to be novel, and their functions are unknown. Predictive analysis of the U5 gene product revealed characteristics typical of viroporins, and indicated structural similarities with the alpha-1 protein (putative viroporin) of viruses in the genus Ephemerovirus. Phylogenetic analyses of the N and G proteins of WONV indicated closest similarity with the avian-associated Flanders virus; however, the genomes of these two viruses are significantly diverged. WONV displays a novel and unique genome structure that has not previously been described for any animal rhabdovirus.

Controlled Synthesis of Ultralong Carbon Nanotubes with Perfect Structures and Extraordinary Properties.

PubMed

Zhang, Rufan; Zhang, Yingying; Wei, Fei

2017-02-21

Carbon nanotubes (CNTs) have drawn intensive research interest in the past 25 years due to their excellent properties and wide applications. Ultralong CNTs refers to the horizontally aligned CNT arrays which are usually grown on flat substrates, parallel with each other with large intertube distances. They usually have perfect structures, excellent properties, and lengths up to centimeters, even decimeters. Ultralong CNTs are promising candidates as building blocks for transparent displays, nanoelectronics, superstrong tethers, aeronautics and aerospace materials, etc. The controlled synthesis of ultralong CNTs with perfect structures is the key to fully exploit the extraordinary properties of CNTs. CNTs are typical one-dimensional single-crystal nanomaterials. It has always been a great challenge how to grow macroscale single-crystals with no defects. Thus, the synthesis of ultralong CNTs with no defect is of significant importance from both fundamental and industrial aspects. In this Account, we focus on our progress on the controlled synthesis of ultralong CNTs with perfect structures and excellent properties. A deep understanding of the CNT growth mechanism is the first step for the controlled synthesis of ultralong CNTs with high quality. We first introduce the growth mechanism for ultralong CNTs and the main factor affecting their structures. We then discuss the strategies to control the defects in the as-grown ultralong CNTs. With these approaches, ultralong high-quality CNTs with different structures can be obtained. By completely eliminating the factors which may induce defects in the CNT walls, ultralong CNTs with perfect structures can be obtained. Their chiral indices keep unchanged for several centimeters long along the axial direction of the CNTs. The defect-free structures render the ultralong CNTs with excellent electrical, mechanical and thermal properties. The as-grown ultralong CNTs exhibit superhigh mechanical strength (>100 GPa) and their breaking strain (>17.5%) reach the theoretical limits. They also show excellent electrical and thermal properties. In addition, centimeters long CNTs showed macroscale interwall superlubricious properties due to their defect-free structures. Ultralong, defect-free CNTs with controlled structures are highly desirable for many high-end applications. We hope that this Account will shed light on the controlled synthesis of ultralong CNTs with perfect structures and excellent properties. Moreover, the growth mechanism and controlled synthesis of ultralong CNTs with perfect structures also offers a good model for other one-dimensional nanomaterials.

Characterisation and modelling of defect formation in direct-chill cast AZ80 alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mackie, D.; Robson, J.D.; Withers, P.J.

2015-06-15

Wrought magnesium alloys for demanding structural applications require high quality defect free cast feedstock. The aim of this study was to first identify and characterise typical defects in direct chill cast magnesium–aluminium–zinc (AZ) alloy billet and then use modelling to understand the origins of these defects so they can be prevented. Defects were first located using ultrasonic inspection and were then characterised using X-ray computed tomography (XCT) and serial sectioning, establishing the presence of oxide films and intermetallic particles Al{sub 8}Mn{sub 5} in all defects. A model was developed to predict the flow patterns and growth kinetics of the intermetallicmore » phases during casting, which influence the formation of defects. Simulation of the growth of the intermetallic particles demonstrated that precipitation from the liquid occurs in the mould. The combination of the entrained oxide films and intermetallic particles recirculates in the liquid metal and continues to grow, until large enough to settle, which is predicted to occur at the centre of the mould where the flow is the slowest. Based on these predictions, strategies to reduce the susceptibility to defect formation are suggested. - Highlights: • Casting defects in magnesium direct chill casting have been imaged and characterised in 3-dimensions. • The occurrences of co-located clusters of particles and oxide films have been characterised and explained. • A coupled model has been developed to help interpret the observed trend for defects located towards the centre of billets.« less

Dermoscopy of accessory nipples in authors’ own study

PubMed Central

Szymszal, Jan; Silny, Wojciech

2014-01-01

Introduction The accessory nipple (AN) is characterised by its network-like structures, which may suggest the diagnosis of a melanocytic lesion. The knowledge about additional dermoscopic features of AN may greatly minimise the risk of unnecessary surgical excisions. Aim To analyse and present different clinical and dermoscopic forms, in which the AN may appear. Material and methods Ninety AN with dermoscopic features were evaluated in the study, detected in 14 patients between the years 2008 and 2014. Results The most common dermoscopic features of the AN were central, scar-like areas (15/19) and peripheral network-like structures (12/19). A number of cleft-like appearances (8/19) and central network-like structures (7/19) had also been observed. Moreover, among the dermoscopic features, white cobblestone-like structures (7/19), a central round dimpling with a plug (6/19) and fisheye-like structures resembling comedo-like openings (9/19) have all also been noted. There is a statistical significance in the occurrence of white cobblestone-like structures with central network-like structures (Fisher's exact test p = 0.0449). The presence of peripheral network-like structures with the occurrence of central scar-like areas was statistically highly significant (p = 0.0091). The central round dimpling was never observed alongside any central network-like structures in any of the lesions (p = 0.0436). Conclusions Accessory nipples are most commonly characterised by the occurrence of a peripheral network-like structure accompanied by the presence of a scar-like area. PMID:25097482

Energy dissipation in slipping biological pumps.

PubMed

Kjelstrup, Signe; Rubi, J Miguel; Bedeaux, Dick

2005-12-07

We describe active transport in slipping biological pumps, using mesoscopic nonequilibrium thermodynamics. The pump operation is characterised by its stochastic nature and energy dissipation. We show how heating as well as cooling effects can be associated with pump operation. We use as an example the well studied active transport of Ca2+ across a biological membrane by means of its ATPase, and use published data to find values for the transport coefficients of the pump under various conditions. Most of the transport coefficients of the pump, including those that relate ATP hydrolysis or synthesis to thermal effects, are estimated. This can give a quantitative description of thermogenesis. We show by calculation that all of these coupling coefficients are significant.

Microwave-assisted synthesis and electrochemical evaluation of VO 2 (B) nanostructures

DOE PAGES

Ashton, Thomas E.; Borras, David Hevia; Iadecola, Antonella; ...

2015-12-01

Understanding how intercalation materials change during electrochemical operation is paramount to optimising their behaviour and function and in situ characterisation methods allow us to observe these changes without sample destruction. Here, we first report the improved intercalation properties of bronze phase vanadium dioxide VO2 (B) prepared by a microwave assisted route which exhibits a larger electrochemical capacity (232 mAh g -1) compared to VO 2 (B) prepared by a solvothermal route (197 mAh g -1). These electrochemical differences have also been followed using in situ X-ray absorption spectroscopy allowing us to follow oxidation state changes as they occur during batterymore » operation.« less

Data for the synthesis of resorcinol-formaldehyde aerogels in acidic and basic media.

PubMed

Molina-Campos, Daniel F; Fonseca-Correa, Rafael A; Vargas-Delgadillo, Diana P; Giraldo, Liliana; Moreno-Piraján, Juan Carlos

2017-06-01

The aim of this research is to synthesise carbon aerogels and to compare the differences in their textural, morphological and chemical properties when synthesised in basic and acidic media, and with two different types of pretreatment carbonization and activation with CO 2 . Four samples are prepared and characterised using TGA-DTA, SEM, DRX, isotherm determination of N 2 adsorption-desorption at -196 °C and immersion calorimetry. The data for pore distribution are reported using non-local density functional theory and quenched solid density functional theory. Finally, with the immersion calorimetry data, the consistency between the results using this technique and those obtained using the nitrogen isotherms is analysed.

Acute complications of sickle cell disease in children.

PubMed

2001-05-01

Sickle cell disease is a recessively inherited condition in which synthesis of haemoglobin is abnormal. The disease, which occurs mainly in people of African, African-Caribbean, Indian, Mediterranean and Middle Eastern descent, is characterised by chronic anaemia, susceptibility to infection, bouts of severe pain and organ dysfunction. While the life expectancy for patients has improved, from a median survival age of 14 years in the 1970s among those homozygous for the sickle haemoglobin gene to survival into the mid-40s, childhood remains a period of peak mortality and morbidity. Here, we discuss the acute complications of sickle cell disease in children, concentrating on the management of the acutely unwell child.

Synthesis of deuterium-labelled substrates for the study of oleuropein biosynthesis in Olea europaea callus cultures.

PubMed

Serrilli, Anna Maria; Maggi, Agnese; Casagrande, Valentina; Bianco, Armandodoriano

2016-01-01

We propose the cell culture approach to investigate oleuropein (1) biogenesis in Olea europaea L. We suggest employing olive callus cultures to identify the iridoidic precursor of oleuropein. In fact, we confirmed that callus cells from olive shoot explants are able to produce key secoiridoid as 1. To enable this approach, we synthesised and characterised deuterium-labelled iridoidic precursors belonging both to the loganin and the 8-epiloganin series. These iridoids are [7,8-(2)H2]-7-deoxy-8-epi-loganin (2(D)), [8,10-(2)H2]-8-epi-loganin (4(D)) and [7,8-(2)H2]-7-deoxy-loganin (3(D)).

Concepts in Biochemistry: Chemical Synthesis of DNA.

ERIC Educational Resources Information Center

Caruthers, Marvin H.

1989-01-01

Outlines the chemistry of the rapid synthesis of relatively large DNA fragments (100-200 monomers each) with yields exceeding 99 percent per coupling. DNA synthesis methodologies are outlined and a polymer-supported synthesis of DNA using deoxynucleoside phosphoramidites is described with structural formulas. (YP)

A transmission Kikuchi diffraction study of cementite in a quenched and tempered steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saleh, Ahmed A., E-mail: asaleh@uow.edu.au; Casillas, Gilberto; Pereloma, Elena V.

2016-04-15

This is the first transmission Kikuchi diffraction (TKD) study to report the indexing of nano-sized cementite as distinct structures and its orientation relationship with the body-centered cubic matrix in a quenched and tempered steel. Crystallographic analysis via TKD and selected area diffraction returned the well-known Bagaryatskii and Isaichev orientation relationships. However, the indexing of nano-sized cementite via TKD was sensitive to the thickness of the electron transparent region such that TEM remains the most precise method to characterise such precipitates. - Highlights: • Nano-sized cementite in a QT steel has been investigated by TKD and TEM. • Cementite has beenmore » indexed as distinct structures via TKD. • Crystallographic analysis returned the Bagaryatskii and Isaichev ORs. • Success of TKD is sensitive to the thickness of the electron transparent region. • TEM remains the most precise technique to characterise nano-sized precipitates.« less

Total synthesis of bryostatins: the development of methodology for the atom-economic and stereoselective synthesis of the ring C subunit.

PubMed

Trost, Barry M; Frontier, Alison J; Thiel, Oliver R; Yang, Hanbiao; Dong, Guangbin

2011-08-22

Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for the stereoselective assembly of the ring C subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the ring C subunit of bryostatins. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sugar analog synthesis by in vitro biocatalytic cascade: A comparison of alternative enzyme complements for dihydroxyacetone phosphate production as a precursor to rare chiral sugar synthesis

PubMed Central

French, Nigel G.; Scoble, Judith A.; Williams, Charlotte C.; Churches, Quentin I.; Frazer, Andrew R.; Taylor, Matthew C.; Coia, Greg; Simpson, Gregory; Turner, Nicholas J.; Scott, Colin

2017-01-01

Carbon-carbon bond formation is one of the most challenging reactions in synthetic organic chemistry, and aldol reactions catalysed by dihydroxyacetone phosphate-dependent aldolases provide a powerful biocatalytic tool for combining C-C bond formation with the generation of two new stereo-centres, with access to all four possible stereoisomers of a compound. Dihydroxyacetone phosphate (DHAP) is unstable so the provision of DHAP for DHAP-dependent aldolases in biocatalytic processes remains complicated. Our research has investigated the efficiency of several different enzymatic cascades for the conversion of glycerol to DHAP, including characterising new candidate enzymes for some of the reaction steps. The most efficient cascade for DHAP production, comprising a one-pot four-enzyme reaction with glycerol kinase, acetate kinase, glycerophosphate oxidase and catalase, was coupled with a DHAP-dependent fructose-1,6-biphosphate aldolase enzyme to demonstrate the production of several rare chiral sugars. The limitation of batch biocatalysis for these reactions and the potential for improvement using kinetic modelling and flow biocatalysis systems is discussed. PMID:29112947

Sugar analog synthesis by in vitro biocatalytic cascade: A comparison of alternative enzyme complements for dihydroxyacetone phosphate production as a precursor to rare chiral sugar synthesis.

PubMed

Hartley, Carol J; French, Nigel G; Scoble, Judith A; Williams, Charlotte C; Churches, Quentin I; Frazer, Andrew R; Taylor, Matthew C; Coia, Greg; Simpson, Gregory; Turner, Nicholas J; Scott, Colin

2017-01-01

Carbon-carbon bond formation is one of the most challenging reactions in synthetic organic chemistry, and aldol reactions catalysed by dihydroxyacetone phosphate-dependent aldolases provide a powerful biocatalytic tool for combining C-C bond formation with the generation of two new stereo-centres, with access to all four possible stereoisomers of a compound. Dihydroxyacetone phosphate (DHAP) is unstable so the provision of DHAP for DHAP-dependent aldolases in biocatalytic processes remains complicated. Our research has investigated the efficiency of several different enzymatic cascades for the conversion of glycerol to DHAP, including characterising new candidate enzymes for some of the reaction steps. The most efficient cascade for DHAP production, comprising a one-pot four-enzyme reaction with glycerol kinase, acetate kinase, glycerophosphate oxidase and catalase, was coupled with a DHAP-dependent fructose-1,6-biphosphate aldolase enzyme to demonstrate the production of several rare chiral sugars. The limitation of batch biocatalysis for these reactions and the potential for improvement using kinetic modelling and flow biocatalysis systems is discussed.

Synthesis of flexirubin-mediated silver nanoparticles using Chryseobacterium artocarpi CECT 8497 and investigation of its anticancer activity.

PubMed

Venil, Chidambaram Kulandaisamy; Sathishkumar, Palanivel; Malathi, Mahalingam; Usha, Rajamanickam; Jayakumar, Rajarajeswaran; Yusoff, Abdull Rahim Mohd; Ahmad, Wan Azlina

2016-02-01

In this work, the synthesis of silver nanoparticles from a pigment produced by a recently-discovered bacterium, Chryseobacterium artocarpi CECT 8497, was achieved, followed by an investigation of its anticancer properties. The bacterial pigment was identified as flexirubin following NMR ((1)H NMR and (13)C NMR), UV-Vis, and LC-MS analysis. An aqueous silver nitrate solution was treated with isolated flexirubin to produce silver nanoparticles. The synthesised silver nanoparticles were subsequently characterised by UV-Vis spectroscopy, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), X-Ray Diffraction (XRD), and Fourier Transform Infrared (FTIR) Spectroscopy methodologies. Furthermore, the anticancer effects of synthesised silver nanoparticles in a human breast cancer cell line (MCF-7) were evaluated. The tests showed significant cytotoxicity activity of the silver nanoparticles in the cultured cells, with an IC50 value of 36μgmL(-1). This study demonstrates that silver nanoparticles, synthesised from flexirubin from C. artocarpi CECT 8497, may have potential as a novel chemotherapeutic agent. Copyright © 2015 Elsevier B.V. All rights reserved.

Chitosan supramolecularly cross linked with trimesic acid - Facile synthesis, characterization and evaluation of adsorption potential for chromium(VI).

PubMed

Bhatt, Ronak; Sreedhar, B; Padmaja, P

2017-11-01

A facile synthesis of Chitosan Supramolecularly cross-linked with Trimesic Acid (CTMA) is reported in this work. The adsorption potential of CTMA for removal of hexavalent chromium was evaluated and the influence of pH, temperature, contact time and adsorbent dose on the adsorption process was investigated. The experimental results showed that CTMA could efficiently adsorb Cr 6+ and partially reduce it to the less toxic Cr 3+ state. The maximum adsorption capacity of CTMA for Cr 6+ was found to be 129.53mg/g at pH 2.0. CTMA and chromium loaded CTMA were characterised by FT-IR, Raman, TGA-DSC, SEM-EDX, XRD, ESR and XPS spectroscopic techniques. Chitosan was observed to be cross- linked with TMA via ionic, hydrogen bonding and pi-pi supramolecular interactions while adsorption of chromium onto CTMA was by electrostatic forces and hydrogen bonding. From the observed results it was evident that CTMA was successfully applied for simultaneous removal of chromium, lead and iron from chrome plating effluent. Copyright © 2017 Elsevier B.V. All rights reserved.

Improving the 'tool box' for robust industrial enzymes.

PubMed

Littlechild, J A

2017-05-01

The speed of sequencing of microbial genomes and metagenomes is providing an ever increasing resource for the identification of new robust biocatalysts with industrial applications for many different aspects of industrial biotechnology. Using 'natures catalysts' provides a sustainable approach to chemical synthesis of fine chemicals, general chemicals such as surfactants and new consumer-based materials such as biodegradable plastics. This provides a sustainable and 'green chemistry' route to chemical synthesis which generates no toxic waste and is environmentally friendly. In addition, enzymes can play important roles in other applications such as carbon dioxide capture, breakdown of food and other waste streams to provide a route to the concept of a 'circular economy' where nothing is wasted. The use of improved bioinformatic approaches and the development of new rapid enzyme activity screening methodology can provide an endless resource for new robust industrial biocatalysts.This mini-review will discuss several recent case studies where industrial enzymes of 'high priority' have been identified and characterised. It will highlight specific hydrolase enzymes and recent case studies which have been carried out within our group in Exeter.

Gold nanoparticles: novel catalyst for the preparation of direct methanol fuel cell.

PubMed

Kuralkar, Mayuri; Ingle, Avinash; Gaikwad, Swapnil; Gade, Aniket; Rai, Mahendra

2015-04-01

The authors report the biosynthesis of gold nanoparticles (Au-NPs) using plant pathogenic Phoma glomerata (MTCC 2210). The synthesis of nanoparticles was characterised by visual observation followed UV-visible spectrophotometric analysis, Fourier transform infrared spectroscopy and nanoparticle tracking analysis. Later, direct methanol fuel cell (DMFC) was constructed using two chambers (anodic chamber and cathodic chamber). These Au-NPs as catalysts have various advantages over the other catalysts that are used in the DMFC. Most importantly, it is cheaper as compared with other catalysts like platinum, and showed higher catalytic activity because of its effective surface structure. Being nano in size, it provides more surface area for the attachment of reactant molecules (methanol molecules). The DMFC catalysed by Au-NPs are found to be suitable to replace lithium ion battery technology in consumer electronics like cell phones, laptops and so on due to the fact that they can produce a high amount of energy in a small space. As long as fuel and air are supplied to the DMFC, it will continue to produce power, so it does not need to be recharged. The use of Au-NPs as catalyst in DMFC has not been reported in the past; it is reported here the first time.

Analysis of new growth promoting black market products.

PubMed

Krug, Oliver; Thomas, Andreas; Malerød-Fjeld, Helle; Dehnes, Yvette; Laussmann, Tim; Feldmann, Ingo; Sickmann, Albert; Thevis, Mario

2018-05-19

Detecting agents allegedly or evidently promoting growth such as human growth hormone (GH) or growth hormone releasing peptides (GHRP) in doping controls has represented a pressing issue for sports drug testing laboratories. While GH is a recombinant protein with a molecular weight of 22 kDa, the GHRPs are short (3-6 amino acids long) peptides with GH releasing properties. The endogenously produced GH (22 kDa isoform) consists of 191 amino acids and has a monoisotopic molecular mass of 22,124 Da. Within this study, a slightly modified form of GH was discovered consisting of 192 amino acids carrying an additional alanine at the N-terminus, leading to a monoisotopic mass of 22,195 Da. This was confirmed by top-down and bottom-up experiments using liquid chromatography coupled to high resolution/high accuracy mass spectrometry. Additionally, three analogues of GHRPs were identified as Gly-GHRP-6, Gly-GHRP-2 and Gly-Ipamorelin, representing the corresponding GHRP extended by a N-terminal glycine residue. The structure of these peptides was characterised by means of high resolution (tandem) mass spectrometry, and for Gly-Ipamorelin and Gly-GHRP-2 their identity was additionally confirmed by custom synthesis. Further, established in-vitro experiments provided preliminary information considering the potential metabolism after administration. Copyright © 2018. Published by Elsevier Ltd.

Novel bimetallic thiocyanate-bridged Cu(II)-Hg(II) compounds—synthesis, X-Ray studies and magnetic properties

NASA Astrophysics Data System (ADS)

Machura, B.; Świtlicka, A.; Zwoliński, P.; Mroziński, J.; Kalińska, B.; Kruszynski, R.

2013-01-01

Seven novel heterobimetallic Cu/Hg polymers based on thiocyanate bridges have been synthesised and characterised by means of IR, EPR, magnetic measurements and single crystal X-Ray. Three of them, [Cu(pzH)4Hg(SCN)4]n (1) [Cu(indH)4Hg(SCN)4]n (2) and [Cu(ampy)2Hg(SCN)4]n (3), have one-dimensional coordination structure. Two compounds [Cu(pzH)2Hg(SCN)4]n (4) and [Cu(abzimH)Hg(SCN)4]n (5) form two-dimensional nets, whereas the complexes [Cu(pyCN)2Hg(SCN)4]n (6) and [Cu(pyCH(OH)(OMe))2Hg(SCN)4]n (7) are three-dimensional coordination polymers. The chains of 1 are connected by the intermolecular N-H•••N hydrogen bonds to the three dimensional net. In 2 the N-H•••S hydrogen bonds link the polymeric chains to the two dimensional layer extending along crystallographic (0 0 1) plane. The polymeric chains of compound 3 are joined by the intermolecular N-H•••N and N-H•••S hydrogen bonds to the three dimensional net. The polymeric layers of 4 are connected by the intermolecular N-H•••N hydrogen bonds to the three dimensional net.

Optimised synthesis of ZnO-nano-fertiliser through green chemistry: boosted growth dynamics of economically important L. esculentum.

PubMed

Jabeen, Nyla; Maqbool, Qaisar; Bibi, Tahira; Nazar, Mudassar; Hussain, Syed Z; Hussain, Talib; Jan, Tariq; Ahmad, Ishaq; Maaza, Malik; Anwaar, Sadaf

2018-06-01

Mounting-up economic losses to annual crops yield due to micronutrient deficiency, fertiliser inefficiency and increasing microbial invasions (e.g. Xanthomonas cempestri attack on tomatoes) are needed to be solved via nano-biotechnology. So keeping this in view, the authors' current study presents the new horizon in the field of nano-fertiliser with highly nutritive and preservative effect of green fabricated zinc oxide-nanostructures (ZnO-NSs) during Lycopersicum esculentum (tomato) growth dynamics. ZnO-NS prepared via green chemistry possesses highly homogenous crystalline structures well-characterised through ultraviolet and visible spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscope. The ZnO-NS average size was found as small as 18 nm having a crystallite size of 5 nm. L. esculentum were grown in different concentrations of ZnO-NS to examine the different morphological parameters includes time of seed germination, germination percentage, the number of plant leaves, the height of the plant, average number of branches, days count for flowering and fruiting time period along with fruit quantity. Promising results clearly predict that bio-fabricated ZnO-NS at optimum concentration resulted as growth booster and dramatically triggered the plant yield.

Polymethylated [Fe(η6-arene)2]2+ dications: methyl-group rearrangements and application of the EINS mechanism.

PubMed

Štíbr, Bohumil; Bakardjiev, Mario; Hájková, Zuzana; Holub, Josef; Padělková, Zdenka; Růžička, Aleš; Kennedy, John D

2011-06-14

Reactions between the methylated arenes ArMe(n) [where ArMe(n) = C(6)Me(n)H((6-n)), and n = 1-6] and FeCl(2) in heptane at 90 °C in the presence of anhydrous AlCl(3) give, for the arenes with n = 1-5, extensive isomerisations and disproportionations involving the methyl groups on the arene rings, and the formation of mixtures of [Fe(ArMe(n))(2)](2+) dications that defy separation into pure species. GC-MS studies of AlCl(3)/mesitylene and AlCl(3)/durene reactions in the absence of FeCl(2) (90 °C, 2 h) allow quantitative assessments of the rearrangements, and the EINS mechanism (electrophile-induced nucleophilic substitution) is applied to rationalise the phenomena. By contrast, ArMe(n) / FeCl(2) /AlCl(3) reactions in heptane for 24-36 h at room-temperature proceed with no rearrangements, allowing the synthesis of the complete series of pure [Fe(ArMen)](2+) cations in yields of 48-71%. The pure compounds are characterised by (1)H NMR spectroscopy and electrospray-ionization mass-spectrometry (ESI-MS), and the structures of [Fe(m-xylene)(2)][PF(6)](2) and [Fe(durene)(2)][PF(6)](2) are established by single-crystal X-ray diffraction analyses.

Approximation concepts for efficient structural synthesis

NASA Technical Reports Server (NTRS)

Schmit, L. A., Jr.; Miura, H.

1976-01-01

It is shown that efficient structural synthesis capabilities can be created by using approximation concepts to mesh finite element structural analysis methods with nonlinear mathematical programming techniques. The history of the application of mathematical programming techniques to structural design optimization problems is reviewed. Several rather general approximation concepts are described along with the technical foundations of the ACCESS 1 computer program, which implements several approximation concepts. A substantial collection of structural design problems involving truss and idealized wing structures is presented. It is concluded that since the basic ideas employed in creating the ACCESS 1 program are rather general, its successful development supports the contention that the introduction of approximation concepts will lead to the emergence of a new generation of practical and efficient, large scale, structural synthesis capabilities in which finite element analysis methods and mathematical programming algorithms will play a central role.

Clinical review: Exogenous surfactant therapy for acute lung injury/acute respiratory distress syndrome - where do we go from here?

PubMed Central

2012-01-01

Acute lung injury and acute respiratory distress syndrome (ARDS) are characterised by severe hypoxemic respiratory failure and poor lung compliance. Despite advances in clinical management, morbidity and mortality remains high. Supportive measures including protective lung ventilation confer a survival advantage in patients with ARDS, but management is otherwise limited by the lack of effective pharmacological therapies. Surfactant dysfunction with quantitative and qualitative abnormalities of both phospholipids and proteins are characteristic of patients with ARDS. Exogenous surfactant replacement in animal models of ARDS and neonatal respiratory distress syndrome shows consistent improvements in gas exchange and survival. However, whilst some adult studies have shown improved oxygenation, no survival benefit has been demonstrated to date. This lack of clinical efficacy may be related to disease heterogeneity (where treatment responders may be obscured by nonresponders), limited understanding of surfactant biology in patients or an absence of therapeutic effect in this population. Crucially, the mechanism of lung injury in neonates is different from that in ARDS: surfactant inhibition by plasma constituents is a typical feature of ARDS, whereas the primary pathology in neonates is the deficiency of surfactant material due to reduced synthesis. Absence of phenotypic characterisation of patients, the lack of an ideal natural surfactant material with adequate surfactant proteins, coupled with uncertainty about optimal timing, dosing and delivery method are some of the limitations of published surfactant replacement clinical trials. Recent advances in stable isotope labelling of surfactant phospholipids coupled with analytical methods using electrospray ionisation mass spectrometry enable highly specific molecular assessment of phospholipid subclasses and synthetic rates that can be utilised for phenotypic characterisation and individualisation of exogenous surfactant replacement therapy. Exploring the clinical benefit of such an approach should be a priority for future ARDS research. PMID:23171712

Convergent Synthesis and Structural Confirmation of Phellodonin and Sarcodonin ε

PubMed Central

Usui, Ippei; Lin, David W.; Masuda, Takeshi

2013-01-01

The first synthesis of members of the sarcodonin family, phellodonin and sarcodonin ε, is reported herein. This verifies that the unprecedented and seemingly unstable N,N-dioxide-containing benzodioxazine framework can be constructed in the laboratory, and lends further support to the proposed structures. The key step in the synthesis involves a biomimetic hetero-Diels–Alder reaction between a pyrazine N-oxide and an ortho-quinone. PMID:23577748

Chemistry of Peptidoglycan in Mycobacterium tuberculosis Life Cycle: An off-the-wall Balance of Synthesis and Degradation.

PubMed

Squeglia, Flavia; Ruggiero, Alessia; Berisio, Rita

2018-02-21

The cell wall envelope of mycobacteria is structurally distinct from that of both Gram-positive and Gram-negative bacteria. In Mycobacterium tuberculosis, this cell wall has unique structural features and plays a crucial role in drug resistance and macrophage survival under stress conditions. Peptidoglycan is the major constituent of this cell wall, with an important structural role, giving structural strength, and counteracting the osmotic pressure of the cytoplasm. Synthesis of this complex polymer takes place in three stages that occur at three different locations in the cell, from the cytoplasm to the external side of the cell membrane, where polymerization occurs. A fine balance of peptidoglycan synthesis and degradation is responsible for a plethora of molecular mechanisms which are key to the pathogenicity of M. tuberculosis. Enlargement of mycobacterial cells can occur through the synthesis of new peptidoglycan, autolysis of old peptidoglycan, or a combination of both processes. Here, we discuss the chemical aspects of peptidoglycan synthesis and degradation, in relation to metabolic stages of M. tuberculosis. Going from inside the mycobacterial cytoplasm to outside its membrane, we describe the assembly line of peptidoglycan synthesis and polymerization, and continue with its depolymerization events and their consequences on mycobacterial life and resuscitation from dormancy. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurement of airborne ultrasonic slow waves in calcaneal cancellous bone.

PubMed

Strelitzki, R; Paech, V; Nicholson, P H

1999-05-01

Measurements of an airborne ultrasonic wave were made in defatted cancellous bone from the human calcaneus using standard ultrasonic equipment. The wave propagating under these conditions was consistent with a decoupled Biot slow wave travelling in the air alone, as previously reported in gas-saturated foams. Reproducible measurements of phase velocity and attenuation coefficient were possible, and an estimate of the tortuosity of the trabecular framework was derived from the high frequency limit of the phase velocity. Thus the method offers a new approach to the acoustic characterisation of bone in vitro which, in contrast to existing techniques, has the potential to yield information directly characterising the trabecular structure.

High-throughput SRCD using multi-well plates and its applications

NASA Astrophysics Data System (ADS)

Hussain, Rohanah; Jávorfi, Tamás; Rudd, Timothy R.; Siligardi, Giuliano

2016-12-01

The sample compartment for high-throughput synchrotron radiation circular dichroism (HT-SRCD) has been developed to satisfy an increased demand of protein characterisation in terms of folding and binding interaction properties not only in the traditional field of structural biology but also in the growing research area of material science with the potential to save time by 80%. As the understanding of protein behaviour in different solvent environments has increased dramatically the development of novel functions such as recombinant proteins modified to have different functions from harvesting solar energy to metabolonics for cleaning heavy and metal and organic molecule pollutions, there is a need to characterise speedily these system.

Ultra fine grained Ti prepared by severe plastic deformation

NASA Astrophysics Data System (ADS)

Lukáč, F.; Čížek, J.; Knapp, J.; Procházka, I.; Zháňal, P.; Islamgaliev, R. K.

2016-01-01

The positron annihilation spectroscopy was employed for characterisation of defects in pure Ti with ultra fine grained (UFG) structure. UFG Ti samples were prepared by two techniques based on severe plastic deformation (SPD): (i) high pressure torsion (HPT) and (ii) equal channel angular pressing (ECAP). Although HPT is the most efficient technique for grain refinement, the size of HPT-deformed specimens is limited. On the other hand, ECAP is less efficient in grain refinement but enables to produce larger samples more suitable for industrial applications. Characterisation of defects by positron annihilation spectroscopy was accompanied by hardness testing in order to monitor the development of mechanical properties of UFG Ti.

Evaluating the roles of detailed endocardial structures on right ventricular haemodynamics by means of CFD simulations.

PubMed

Sacco, Federica; Paun, Bruno; Lehmkuhl, Oriol; Iles, Tinen L; Iaizzo, Paul A; Houzeaux, Guillaume; Vázquez, Mariano; Butakoff, Constantine; Aguado-Sierra, Jazmin

2018-06-11

Computational modelling plays an important role in right ventricular (RV) haemodynamic analysis. However, current approaches employ smoothed ventricular anatomies. The aim of this study is to characterise RV haemodynamics including detailed endocardial structures like trabeculae, moderator band and papillary muscles (PMs). Four paired detailed and smoothed RV endocardium models (two male and two female) were reconstructed from ex-vivo human hearts high-resolution magnetic resonance images (MRI). Detailed models include structures with ≥1 mm 2 cross-sectional area. Haemodynamic characterisation was done by computational fluid dynamics (CFD) simulations with steady and transient inflows, using high performance computing (HPC). The differences between the flows in smoothed and detailed models were assessed using Q-criterion for vorticity quantification, the pressure drop between inlet and outlet, and the wall shear stress (WSS). Results demonstrated that detailed endocardial structures increase the degree of intra-ventricular pressure drop, decrease the WSS and disrupt the dominant vortex creating secondary small vortices. Increasingly turbulent blood flow was observed in the detailed RVs. Female RVs were less trabeculated and presented lower pressure drops than the males. In conclusion, neglecting endocardial structures in RV haemodynamic models may lead to inaccurate conclusions about the pressures, stresses, and blood flow behaviour in the cavity. This article is protected by copyright. All rights reserved.

Influence of Synthesis Mode of Supplement Based on Calcium Hydrosylicates on the Structure and Properties of Lime Compositions

NASA Astrophysics Data System (ADS)

Loganina, V. I.; Pyshkina, I. S.

2017-11-01

It was proposed to use synthesized calcium hydrosilicates in finishing lime dry mixes as a modifying supplement. The effect of substances containing amorphous silica which are used for synthesis on the activity of the modifying supplement was established. The effect of the synthesis mode of supplement on the structure formation of lime compositions was illustrated. It was found that the injection of supplements of hydrosilicates accelerates the increase of mechanical strength. The efficiency of the modifying supplements of amorphous silica, such as diatomite, in the synthesis was shown.

Stereoselective heterocycle synthesis through oxidative carbon-hydrogen bond activation.

PubMed

Liu, Lei; Floreancig, Paul E

2010-01-01

Heterocycles are ubiquitous structures in both drugs and natural products, and efficient methods for their construction are being pursued constantly. Carbon-hydrogen bond activation offers numerous advantages for the synthesis of heterocycles with respect to minimizing the length of synthetic routes and reducing waste. As interest in chiral medicinal leads increases, stereoselective methods for heterocycle synthesis must be developed. The use of carbon-hydrogen bond activation reactions for stereoselective heterocycle synthesis has produced a range of creative transformations that provide a wide array of structural motifs, selected examples of which are described in this review.

Kinematical synthesis of an inversion of the double linked fourbar for morphing wing applications

NASA Astrophysics Data System (ADS)

Aguirrebeitia, J.; Avilés, R.; Fernández, I.; Abasolo, M.

2013-03-01

This paper presents the kinematical features of an inversion of the double linked fourbar for morphing wing purposes. The structure of the mechanism is obtained using structural synthesis concepts, from an initial conceptual schematic. Then, kinematic characteristics as instant center of rotation, lock positions, dead point positions and uncertainty positions are derived for this mechanism in order to face the last step, the dimensional synthesis; in this sense, two kinds of dimensional synthesis are arranged to guide the wing along two positions, and to fulfill with the second one some aerodynamic and minimum actuation energy related issues.

Geophysical characterisation of the groundwater-surface water interface

NASA Astrophysics Data System (ADS)

McLachlan, P. J.; Chambers, J. E.; Uhlemann, S. S.; Binley, A.

2017-11-01

Interactions between groundwater (GW) and surface water (SW) have important implications for water quantity, water quality, and ecological health. The subsurface region proximal to SW bodies, the GW-SW interface, is crucial as it actively regulates the transfer of nutrients, contaminants, and water between GW systems and SW environments. However, geological, hydrological, and biogeochemical heterogeneity in the GW-SW interface makes it difficult to characterise with direct observations. Over the past two decades geophysics has been increasingly used to characterise spatial and temporal variability throughout the GW-SW interface. Geophysics is a powerful tool in evaluating structural heterogeneity, revealing zones of GW discharge, and monitoring hydrological processes. Geophysics should be used alongside traditional hydrological and biogeochemical methods to provide additional information about the subsurface. Further integration of commonly used geophysical techniques, and adoption of emerging techniques, has the potential to improve understanding of the properties and processes of the GW-SW interface, and ultimately the implications for water quality and environmental health.

An infrared and Raman spectroscopic study of natural zinc phosphates.

PubMed

Frost, Ray L

2004-06-01

Zinc phosphates are important in the study of the phosphatisation of metals. Raman spectroscopy in combination with infrared spectroscopy has been used to characterise the zinc phosphate minerals. The minerals may be characterised by the patterns of the hydroxyl stretching vibrations in both the Raman and infrared spectra. Spencerite is characterised by a sharp Raman band at 3516 cm(-1) and tarbuttite by a single band at 3446 cm(-1). The patterns of the Raman spectra of the hydroxyl stretching region of hopeite and parahopeite are different in line with their differing crystal structures. The Raman spectrum of the PO4 stretching region shows better band separated peaks than the infrared spectra which consist of a complex set of overlapping bands. The position of the PO4 symmetric stretching mode can be used to identify the zinc phosphate mineral. It is apparent that Raman spectroscopy lends itself to the fundamental study of the evolution of zinc phosphate films.

Detection, breakpoint identification and detailed characterisation of a CNV at the FRA16D site using SNP assays.

PubMed

Winchester, L; Newbury, D F; Monaco, A P; Ragoussis, J

2008-01-01

Copy Number Variants (CNV) and other submicroscopic structural changes are now recognised to be widespread across the human genome. We show that SNP data generated for association study can be utilised for the identification of deletion CNVs. During analysis of data for an SNP association study for Specific Language Impairment (SLI) a deletion was identified. SLI adversely affects the language development of children in the absence of any obvious cause. Previous studies have found linkage to a region on chromosome 16. The deletion was located in a known fragile site FRA16D in intron 5-6 of the WWOX gene (also known as FOR). Changes in the FRA16D site have been previously linked to cancer and are often characterised in cell lines. A long-range PCR assay was used to confirm the existence of the deletion. We also show the breakpoint identification and large-scale characterisation of this CNV in a normal human sample set. Copyright 2009 S. Karger AG, Basel.

Mapping of Ligand-Binding Cavities in Proteins

PubMed Central

Andersson, C. David; Chen, Brian Y.; Linusson, Anna

2010-01-01

The complex interactions between proteins and small organic molecules (ligands) are intensively studied because they play key roles in biological processes and drug activities. Here, we present a novel approach to characterise and map the ligand-binding cavities of proteins without direct geometric comparison of structures, based on Principal Component Analysis of cavity properties (related mainly to size, polarity and charge). This approach can provide valuable information on the similarities, and dissimilarities, of binding cavities due to mutations, between-species differences and flexibility upon ligand-binding. The presented results show that information on ligand-binding cavity variations can complement information on protein similarity obtained from sequence comparisons. The predictive aspect of the method is exemplified by successful predictions of serine proteases that were not included in the model construction. The presented strategy to compare ligand-binding cavities of related and unrelated proteins has many potential applications within protein and medicinal chemistry, for example in the characterisation and mapping of “orphan structures”, selection of protein structures for docking studies in structure-based design and identification of proteins for selectivity screens in drug design programs. PMID:20034113

Liquid structure of dibutyl sulfoxide

DOE PAGES

Lo Celso, Fabrizio; Aoun, Bachir; Triolo, Alessandro; ...

2016-05-16

We present experimental (x-ray diffraction) data on the structure of liquid dibutyl sulfoxide at 320 K and rationalize them by means of Molecular Dynamics simulations. Not unexpectedly, DBSO bearing a strong dipolar moiety and two medium length, apolar, butyl chains, this compound turns out to be characterised by a distinct degree of polar-vs-apolar structural differentiation at the nm spatial scale that is fingerprinted in a low Q peak in its x-ray diffraction pattern. Similarly to, but to a larger extent than its shorter chain family members (such as DMSO), DBSO is also characterised by an enhanced dipole-dipole correlation that ismore » responsible for the moderate Kirkwood correlation factor as well as for the self-association detected in this compound. In conclusion, we show however that the supposedly relevant hydrogen bonding correlations between oxygen and butyl chain hydrogens are of limited extent and only in the case of α-hydrogens appreciable indication of the existence of such an interaction is found, but it turns out to be a mere consequence of the strong dipole-dipole correlation.« less

Rheological and structural characterisation of film-forming solutions and biodegradable edible film made from kefiran as affected by various plasticizer types.

PubMed

Ghasemlou, Mehran; Khodaiyan, Faramarz; Oromiehie, Abdulrasoul

2011-11-01

The rheological properties of kefiran film-forming solutions, as well as the structural characterisation of the resulting films, were investigated as a function of various plasticizer types. The behaviours of the storage (G') and loss (G″) moduli as a function of frequency were typical of gel-like material, with the G' higher than the G″. Kefiran-based films, which may find application as edible films, were prepared by a casting and solvent-evaporation method. Possible interaction between the adjacent chains in the kefiran polymer and various plasticizers was proven by Fourier-transform infrared spectroscopy (FT-IR). The crystallinity of plasticized kefiran film was also analysed using X-ray diffraction (XRD); this revealed an amorphous-crystalline structure. These results were explained by the film's microstructure, which was analysed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The present study has helped determine possible interactions of kefiran, plasticizer and water molecules in determining film properties. Copyright © 2011 Elsevier B.V. All rights reserved.

Zebavidin - An Avidin-Like Protein from Zebrafish

PubMed Central

Taskinen, Barbara; Zmurko, Joanna; Ojanen, Markus; Kukkurainen, Sampo; Parthiban, Marimuthu; Määttä, Juha A. E.; Leppiniemi, Jenni; Jänis, Janne; Parikka, Mataleena; Turpeinen, Hannu; Rämet, Mika; Pesu, Marko; Johnson, Mark S.; Kulomaa, Markku S.; Airenne, Tomi T.; Hytönen, Vesa P.

2013-01-01

The avidin protein family members are well known for their high affinity towards D-biotin and high structural stability. These properties make avidins valuable tools for a wide range of biotechnology applications. We have identified a new member of the avidin family in the zebrafish (Danio rerio) genome, hereafter called zebavidin. The protein is highly expressed in the gonads of both male and female zebrafish and in the gills of male fish, but our data suggest that zebavidin is not crucial for the developing embryo. Biophysical and structural characterisation of zebavidin revealed distinct properties not found in any previously characterised avidins. Gel filtration chromatography and native mass spectrometry suggest that the protein forms dimers in the absence of biotin at low ionic strength, but assembles into tetramers upon binding biotin. Ligand binding was analysed using radioactive and fluorescently labelled biotin and isothermal titration calorimetry. Moreover, the crystal structure of zebavidin in complex with biotin was solved at 2.4 Å resolution and unveiled unique ligand binding and subunit interface architectures; the atomic-level details support our physicochemical observations. PMID:24204770

An improved divergent synthesis of comb-type branched oligodeoxyribonucleotides (bDNA) containing multiple secondary sequences.

PubMed

Horn, T; Chang, C A; Urdea, M S

1997-12-01

The divergent synthesis of branched DNA (bDNA) comb structures is described. This new type of bDNA contains one unique oligonucleotide, the primary sequence, covalently attached through a comb-like branch network to many identical copies of a different oligonucleotide, the secondary sequence. The bDNA comb structures were assembled on a solid support and several synthesis parameters were investigated and optimized. The bDNA comb molecules were characterized by polyacrylamide gel electrophoretic methods and by controlled cleavage at periodate-cleavable moieties incorporated during synthesis. The developed chemistry allows synthesis of bDNA comb molecules containing multiple secondary sequences. In the accompanying article we describe the synthesis and characterization of large bDNA combs containing all four deoxynucleotides for use as signal amplifiers in nucleic acid quantification assays.

An improved divergent synthesis of comb-type branched oligodeoxyribonucleotides (bDNA) containing multiple secondary sequences.

PubMed Central

Horn, T; Chang, C A; Urdea, M S

1997-01-01

The divergent synthesis of branched DNA (bDNA) comb structures is described. This new type of bDNA contains one unique oligonucleotide, the primary sequence, covalently attached through a comb-like branch network to many identical copies of a different oligonucleotide, the secondary sequence. The bDNA comb structures were assembled on a solid support and several synthesis parameters were investigated and optimized. The bDNA comb molecules were characterized by polyacrylamide gel electrophoretic methods and by controlled cleavage at periodate-cleavable moieties incorporated during synthesis. The developed chemistry allows synthesis of bDNA comb molecules containing multiple secondary sequences. In the accompanying article we describe the synthesis and characterization of large bDNA combs containing all four deoxynucleotides for use as signal amplifiers in nucleic acid quantification assays. PMID:9365265

An Investigation of Porous Structure of TiNi-Based SHS-Materials Produced at Different Initial Synthesis Temperatures

NASA Astrophysics Data System (ADS)

Khodorenko, V. N.; Anikeev, S. G.; Kokorev, O. V.; Yasenchuk, Yu. F.; Gunther, V. É.

2018-02-01

An investigation of structural characteristics and behavior of TiNi-based pore-permeable materials manufactured by the methods of selfpropagating high-temperature synthesis (SHS) at the initial synthesis temperatures T = 400 and 600°C is performed. It is shown that depending on the temperature regime, the resulting structure and properties of the material can differ. It is found out that the SHS-material produced at the initial synthesis temperature T = 400°C possesses the largest number of micropores in the pore wall surface structure due to a high phase inhomogeneity of the alloy. The regime of structure optimization of the resulting materials is described and the main stages of formation of the pore wall microporous surfaces are revealed. It is demonstrated that after optimization of the surface structure of a TiNi-based fine-pore alloy by its chemical etching, the fraction of micropores measuring in size less than 50 nm increased from 59 to 68%, while the number of pores larger than 1 μm increased twofold from 11 to 22%. In addition, peculiar features of interaction between certain cell cultures with the surface of the SHS-material manufactured at different initial synthesis temperatures are revealed. It is found out that the dynamics of the cell material integration depends on the pore wall surface morphology and dimensions of macropores.

Component mode synthesis and large deflection vibrations of complex structures. [beams and trusses

NASA Technical Reports Server (NTRS)

Mei, C.

1984-01-01

The accuracy of the NASTRAN modal synthesis analysis was assessed by comparing it with full structure NASTRAN and nine other modal synthesis results using a nine-bay truss. A NASTRAN component mode transient response analysis was also performed on the free-free truss structure. A finite element method was developed for nonlinear vibration of beam structures subjected to harmonic excitation. Longitudinal deformation and inertia are both included in the formula. Tables show the finite element free vibration results with and without considering the effects of longitudinal deformation and inertia as well as the frequency ratios for a simply supported and a clamped beam subjected to a uniform harmonic force.

Mechanical, thermal and morphological characterisation of 3D porous Pennisetum purpureum/PLA biocomposites scaffold.

PubMed

Revati, R; Abdul Majid, M S; Ridzuan, M J M; Normahira, M; Mohd Nasir, N F; Rahman Y, M N; Gibson, A G

2017-06-01

The mechanical, thermal, and morphological properties of a 3D porous Pennisetum purpureum (PP)/polylactic acid (PLA) based scaffold were investigated. In this study, a scaffold containing P. purpureum and PLA was produced using the solvent casting and particulate leaching method. P. purpureum fibre, also locally known as Napier grass, is composed of 46% cellulose, 34% hemicellulose, and 20% lignin. PLA composites with various P. purpureum contents (10%, 20%, and 30%) were prepared and subsequently characterised. The morphologies, structures and thermal behaviours of the prepared composite scaffolds were characterised using field-emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The morphology was studied using FESEM; the scaffold possessed 70-200μm-sized pores with a high level of interconnectivity. The moisture content and mechanical properties of the developed porous scaffolds were further characterised. The P. purpureum/PLA scaffold had a greater porosity factor (99%) and compression modulus (5.25MPa) than those of the pure PLA scaffold (1.73MPa). From the results, it can be concluded that the properties of the highly porous P. purpureum/PLA scaffold developed in this study can be controlled and optimised. This can be used to facilitate the construction of implantable tissue-engineered cartilage. Copyright © 2017 Elsevier B.V. All rights reserved.

Time Dependent Structural Evolution of Porous Organic Cage CC3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lucero, Jolie; Elsaidi, Sameh; Anderson, Ryther

Porous organic cage compounds are emerged with remarkable structural diversity and functionality that have applications in gas separation, catalysis and energy storage. Fundamental understanding of nucleation and growth of such materials have significant implications for understanding molecularly directed self-assembly phenomena. Herein we followed the structural evolution of a prototypical type of porous organic cage, CC3 as a function of synthesis time. Three distinctive crystal formation stages were identified: at short synthesis times, a rapid crystal growth stage in which amorphous agglomerates transformed into larger irregular particles was observed. At intermediate synthesis times, a decrease in crystal size over time wasmore » observed presumably due to crystal fragmentation, redissolution and/or homogeneous nucleation led. Finally, at longer synthesis times, a regrowth process was observed in which particles coalesced through Ostwald ripening leading to a continuous increase in crystal size. Molecular simulation studies, based on the construction of in silico CC3 models and simulation of XRD patterns and nitrogen isotherms, confirm the samples at different synthesis times to be a mixture of CC3α and CC3 amorphous phases. The CC3α phase is found to contract at different synthesis times, and the amorphous phase is found to essentially disappear at the longest synthesis time. Nitrogen and carbon dioxide adsorption properties of these CC3 phases were evaluated, and were highly dependent on synthesis time.« less

Synthesis and structural study of N-isopropenylbenzimidazolone

NASA Astrophysics Data System (ADS)

Mondieig, D.; Negrier, Ph.; Leger, J. M.; Lakhrissi, L.; El Assyry, A.; Lakhrissi, B.; Essassi, E. M.; Benali, B.; Boucetta, A.

2015-05-01

The synthesis and the crystal structure of the N-isopropenylbenzimidazolone (C10H10N2O) are presented. The synthesis was performed by Meth-Cohen method by reaction of o-phenylenediamine with ethyl acetoacetate in refluxed xylene. The single crystal structure was determined at room temperature by means of X-rays diffraction. The crystal system is monoclinic, with space group C2/c and eight molecules per unit cell. The unit cell dimensions are: a = 15.978(1) Å, b = 6.100(2) Å, c = 18.222(2) Å, β = 90.16(1)° and V = 1776.0(6) Å3.

Robust control synthesis for uncertain dynamical systems

NASA Technical Reports Server (NTRS)

Byun, Kuk-Whan; Wie, Bong; Sunkel, John

1989-01-01

This paper presents robust control synthesis techniques for uncertain dynamical systems subject to structured parameter perturbation. Both QFT (quantitative feedback theory) and H-infinity control synthesis techniques are investigated. Although most H-infinity-related control techniques are not concerned with the structured parameter perturbation, a new way of incorporating the parameter uncertainty in the robust H-infinity control design is presented. A generic model of uncertain dynamical systems is used to illustrate the design methodologies investigated in this paper. It is shown that, for a certain noncolocated structural control problem, use of both techniques results in nonminimum phase compensation.

Experimental and simulation characterisation of flexural vibration modes in unimorph ultrasound transducers.

PubMed

Eriksson, T J R; Ramadas, S N; Dixon, S M

2016-02-01

A unimorph flexural transducer design is proposed and tested with regard to mode shapes and frequencies. The transducers consist of a passive metal cap structure, and a thin piezoelectric disc, rigidly bonded to the inside. Extensive finite element (FE) modelling, and experimental 2D, time-resolved displacement measurements were done to characterise the transducers flexural properties, and to compare them to the analytical solutions of thin vibrating plates. Emphasis was put on characterising the passive layer of the unimorph structure, before bonding the piezoelectric element, to understand how the active element affects the behaviour of the flexing plate. A high power Nd:YAG laser was used to actuate the metal plate (non-contact), and the frequency content of the resulting displacement signal was analysed to identify the flexural modes. The non-axisymmetric modes, which are conventionally disregarded because of their unfavourable acoustic properties, were also taken into account. There was excellent agreement between the experimental results and the FE simulation data. There was good agreement with the analytical edge clamped plate model, but with some notable deviations, which have not previously been identified or commented upon. Specifically, the second axisymmetric mode is split into three separate modes, which is not explained by the traditional theory of vibrating plates. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Understanding the role of hydrogen bonding in the aggregation of fumed silica particles in triglyceride solvents.

PubMed

Whitby, Catherine P; Krebsz, Melinda; Booty, Samuel J

2018-10-01

Fumed silica particles are thought to thicken organic solvents into gels by aggregating to form networks. Hydrogen bonding between silanol groups on different particle surfaces causes the aggregation. The gel structure and hence flow behaviour is altered by varying the proportion of silanol groups on the particle surfaces. However, characterising the gel using rheology measurements alone is not sufficient to optimise the aggregation. We have used confocal microscopy to characterise the changes in the network microstructure caused by altering the particle surface chemistry. Organogels were formed by dispersing fumed silica nanoparticles in a triglyceride solvent. The particle surface chemistry was systematically varied from oleophobic to oleophilic by functionalisation with hydrocarbons. We directly visualised the particle networks using confocal scanning laser microscopy and investigated the correlations between the network structure and the shear response of the organogels. Our key finding is that the sizes of the pore spaces in the networks depend on the fraction of silanol groups available to form hydrogen bonds. The reduction in the network elasticity of gels formed by methylated particles can be accounted for by the increasing pore size and tenuous nature of the networks. This is the first report that characterises the changes in the microstructure of fumed silica particle networks in non-polar solvents caused by manipulating the particle surface chemistry. Copyright © 2018 Elsevier Inc. All rights reserved.

Tissue engineering and regenerative medicine: manufacturing challenges.

PubMed

Williams, D J; Sebastine, I M

2005-12-01

Tissue engineering and regenerative medicine are interdisciplinary fields that apply principles of engineering and life sciences to develop biological substitutes, typically composed of biological and synthetic components, that restore, maintain or improve tissue function. Many tissue engineering technologies are still at a laboratory or pre-commercial scale. The short review paper describes the most significant manufacturing and bio-process challenges inherent in the commercialisation and exploitation of the exciting results emerging from the biological and clinical laboratories exploring tissue engineering and regenerative medicine. A three-generation road map of the industry has been used to structure a view of these challenges and to define where the manufacturing community can contribute to the commercial success of the products from these emerging fields. The first-generation industry is characterised by its demonstrated clinical applications and products in the marketplace, the second is characterised by emerging clinical applications, and the third generation is characterised by aspirational clinical applications. The paper focuses on the cost reduction requirement of the first generation of the industry to allow more market penetration and consequent patient impact. It indicates the technological requirements, for instance the creation of three-dimensional tissue structures, and value chain issues in the second generation of the industry. The third-generation industry challenges lie in fundamental biological and clinical science. The paper sets out a road map of these generations to identify areas for research.

Non-destructive testing of satellite nozzles made of carbon fibre ceramic matrix composite, C/SiC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rebelo Kornmeier, J.; Hofmann, M.; Schmidt, S.

Carbon fibre ceramic matrix composite materials, C/SiC, are excellent candidates as lightweight structural materials for high performance hot structures such as in aerospace applications. Satellite nozzles are manufactured from C/SiC, using, for instance, the Liquid Polymer Infiltration (LPI) process. In this article the applicability of different non-destructive analysis methods for the characterisation of C/SiC components will be discussed. By using synchrotron and neutron tomography it is possible to characterise the C/SiC material in each desired location or orientation. Synchrotron radiation using tomography on small samples with a resolution of 1.4 {mu}m, i.e. the fibre scale, was used to characterise threemore » dimensionally fibre orientation and integrity, matrix homogeneity and dimensions and distributions of micro pores. Neutron radiation tomography with a resolution of about 300 {mu}m was used to analyse the over-all C/SiC satellite nozzle component with respect to the fibre content. The special solder connection of a C/SiC satellite nozzle to a metallic ring was also successfully analysed by neutron tomography. In addition, the residual stress state of a temperature tested satellite nozzle was analysed non-destructively in depth by neutron diffraction. The results revealed almost zero stress for the principal directions, radial, axial and tangential, which can be considered to be the principal directions.« less

Fabrication and characterisation of a novel biomimetic anisotropic ceramic/polymer-infiltrated composite material.

PubMed

Al-Jawoosh, Sara; Ireland, Anthony; Su, Bo

2018-04-10

To fabricate and characterise a novel biomimetic composite material consisting of aligned porous ceramic preforms infiltrated with polymer. Freeze-casting was used to fabricate and control the microstructure and porosity of ceramic preforms, which were subsequently infiltrated with 40-50% by volume UDMA-TEGDMA polymer. The composite materials were then subjected to characterisation, namely density, compression, three-point bend, hardness and fracture toughness testing. Samples were also subjected to scanning electron microscopy and computerised tomography (Micro-CT). Three-dimensional aligned honeycomb-like ceramic structures were produced and full interpenetration of the polymer phase was observed using micro-CT. Depending on the volume fraction of the ceramic preform, the density of the final composite ranged from 2.92 to 3.36g/cm 3 , compressive strength ranged from 206.26 to 253.97MPa, flexural strength from 97.73 to 145.65MPa, hardness ranged from 1.46 to 1.62GPa, and fracture toughness from 3.91 to 4.86MPam 1/2 . Freeze-casting provides a novel method to engineer composite materials with a unique aligned honeycomb-like interpenetrating structure, consisting of two continuous phases, inorganic and organic. There was a correlation between the ceramic fraction and the subsequent, density, strength, hardness and fracture toughness of the composite material. Copyright © 2018 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.

Functional characterisation of Burkholderia pseudomallei biotin protein ligase: A toolkit for anti-melioidosis drug development.

PubMed

Bond, Thomas E H; Sorenson, Alanna E; Schaeffer, Patrick M

2017-06-01

Burkholderia pseudomallei (Bp) is the causative agent of melioidosis. The bacterium is responsible for 20% of community-acquired sepsis cases and 40% of sepsis-related mortalities in northeast Thailand, and is intrinsically resistant to aminoglycosides, macrolides, rifamycins, cephalosporins, and nonureidopenicillins. There is no vaccine and its diagnosis is problematic. Biotin protein ligase (BirA) which is essential for fatty acid synthesis has been proposed as a drug target in bacteria. Very few bacterial BirA have been characterized, and a better understanding of these enzymes is necessary to further assess their value as drug targets. BirA within the Burkholderia genus have not yet been investigated. We present for the first time the cloning, expression, purification and functional characterisation of the putative Bp BirA and orthologous B. thailandensis (Bt) biotin carboxyl carrier protein (BCCP) substrate. A GFP-tagged Bp BirA was produced and applied for the development of a high-throughput (HT) assay based on our differential scanning fluorimetry of GFP-tagged proteins (DSF-GTP) principle as well as an electrophoretic mobility shift assay. Our biochemical data in combination with the new HT DSF-GTP and biotinylation activity assay could facilitate future drug screening efforts against this drug-resistant organism. Copyright © 2017 Elsevier GmbH. All rights reserved.

Synthesis, characterisation and physicochemical properties of hydrophobically modified inulin using long-chain fatty acyl chlorides.

PubMed

Han, Lingyu; Ratcliffe, I; Williams, P A

2017-12-15

A series of inulin derivatives were synthesized in aqueous solution using acyl chlorides with varying alkyl chain length (C10-C16). They were characterised using a number of techniques including MALDI TOF-MS, 1 H NMR and FTIR and their degree of substitution determined. The solution properties of the hydrophobically modified inulins were investigated using dye solubilisation and surface tension and it was confirmed that the molecules aggregated in solution above a critical concentration (critical aggregation concentration, CAC). The value of the CAC was found to be reasonably consistent between the different techniques and was shown to decrease with increasing hydrophobe chain length. It was found that the C10, C12 and C14 derivatives formed stable oil-in-water emulsions and the emulsion droplet size decreased with increasing alkyl chain length. The C16 derivative was not able to produce stable oil-in-water emulsions; however, it was able to form stable water-in-oil emulsions. The fact that the derivatives are able to form micellar-like aggregates and stabilise emulsions makes them suitable candidates for the encapsulation and delivery of active compounds with potential application in food, cosmetic, personal care and pharmaceutical formulations. Copyright © 2017 Elsevier Ltd. All rights reserved.

African hydroclimatic variability during the last 2000 years

NASA Astrophysics Data System (ADS)

Nash, David J.; De Cort, Gijs; Chase, Brian M.; Verschuren, Dirk; Nicholson, Sharon E.; Shanahan, Timothy M.; Asrat, Asfawossen; Lézine, Anne-Marie; Grab, Stefan W.

2016-12-01

The African continent is characterised by a wide range of hydroclimate regimes, ranging from humid equatorial West Africa to the arid deserts in the northern and southern subtropics. The livelihoods of much of its population are also vulnerable to future climate change, mainly through variability in rainfall affecting water resource availability. A growing number of data sources indicate that such hydroclimatic variability is an intrinsic component of Africa's natural environment. This paper, co-authored by members of the PAGES Africa 2k Working Group, presents an extensive assessment and discussion of proxy, historical and instrumental evidence for hydroclimatic variability across the African continent, spanning the last two millennia. While the African palaeoenvironmental record is characterised by spatially disjunctive datasets, with often less-than-optimal temporal resolution and chronological control, the available evidence allows the assessment of prominent spatial patterns of palaeomoisture variability through time. In this study, we focus sequentially on data for six major time windows: the first millennium CE, the Medieval Climate Anomaly (900-1250 CE), the Little Ice Age (1250-1750 CE), the end of the LIA (1750-1850 CE), the Early Modern Period (1850-1950), and the period of recent warming (1950 onwards). This results in a continent-wide synthesis of regional moisture-balance trends through history, allowing consideration of possible driving mechanisms, and suggestions for future research.

Increased gene dosage for β- and κ-casein in transgenic cattle improves milk composition through complex effects

PubMed Central

Laible, Götz; Smolenski, Grant; Wheeler, Thomas; Brophy, Brigid

2016-01-01

We have previously generated transgenic cattle with additional copies of bovine β- and κ casein genes. An initial characterisation of milk produced with a hormonally induced lactation from these transgenic cows showed an altered milk composition with elevated β-casein levels and twofold increased κ-casein content. Here we report the first in-depth characterisation of the composition of the enriched casein milk that was produced through a natural lactation. We have analyzed milk from the high expressing transgenic line TG3 for milk composition at early, peak, mid and late lactation. The introduction of additional β- and κ-casein genes resulted in the expected expression of the transgene derived proteins and an associated reduction in the size of the casein micelles. Expression of the transgenes was associated with complex changes in the expression levels of other milk proteins. Two other major milk components were affected, namely fat and micronutrients. In addition, the sialic acid content of the milk was increased. In contrast, the level of lactose remained unchanged. This novel milk with its substantially altered composition will provide insights into the regulatory processes synchronizing the synthesis and assembly of milk components, as well as production of potentially healthier milk with improved dairy processing characteristics. PMID:27876865

Biofilm responses to ageing and to a high phosphate load in a bench-scale drinking water system.

PubMed

Batté, Magali; Koudjonou, Boniface; Laurent, Patrick; Mathieu, Laurence; Coallier, Josée; Prévost, Michèle

2003-03-01

The effects of ageing and of phosphate load on drinking water biofilms developed on a polycarbonate substratum in the pseudo-equilibrium state have been evaluated. Phosphate was added in an amount higher than the stochiometric nutrient requirements of bacteria, at concentrations commonly applied in a drinking water distribution system for corrosion control. Multiple parameters were monitored: heterotrophic plate counts (HPCs), total direct counts (TDCs) and potential exoproteolytic activity (PEPA) in order to characterise changes in bacterial biofilms. The total carbohydrate, amino acid and phosphate contents of biofilms were analysed to characterise and monitor the biochemical composition of the biofilm.The three enumeration methods showed that a pseudo-equilibrium state was reached after 7 weeks of colonisation after which, the bacterial growth rate in the biofilm was 0.1 log per week on average. Bulk phosphate addition doubled the phosphate in the biofilm, but did not affect the other biological, physiological or chemical parameters measured. Polysaccharides increased in the biofilm with ageing and the dynamics of individual carbohydrate synthesis also varied with the age of the biofilm. Once pseudo-equilibrium, it was found that the total proteins were globally constant, whereas the spectra of some individual amino acids of the proteins had significantly changed.

An Innovative Electrolysis Approach for the Synthesis of Metal Matrix Bulk Nanocomposites: A Case Study on Copper-Niobium System

NASA Astrophysics Data System (ADS)

Shokrvash, Hussein; Rad, Rahim Yazdani; Massoudi, Abouzar

2018-04-01

Design and synthesis of a prototype Cu-Nb nanocomposite are presented. Oxygen-free Cu-Nb nanocomposites were prepared using an electrolysis facility with special emphasis on the cathodic deoxidation of Cu and nanometric Nb2O5 blends in a molten NaCl-CaCl2 electrolyte. The as-prepared nanocomposites were characterized by X-ray diffraction and energy-dispersive X-ray spectroscopy. The elemental analysis of the Cu matrix and Nb phase revealed the high solubility of Nb in the Cu structure (0.85 at. pct) and Cu in the Nb structure (10.59 at. pct) over short synthesis times (4-5 hours). Furthermore, precise analysis using field emission scanning electron microscopy and transmission electron microscopy confirmed the unique structure and nanocomposite morphology of the Cu-Nb nanocomposite. The successful synthesis of Cu-Nb nanocomposites offers a new conceptual and empirical outlook on the generation of bulk nanostructures of immiscible bimetals using electro-synthesis.

Divergent Synthesis of Heparan Sulfate Oligosaccharides

PubMed Central

2015-01-01

Heparan sulfates are implicated in a wide range of biological processes. A major challenge in deciphering their structure and activity relationship is the synthetic difficulties to access diverse heparan sulfate oligosaccharides with well-defined sulfation patterns. In order to expedite the synthesis, a divergent synthetic strategy was developed. By integrating chemical synthesis and two types of O-sulfo transferases, seven different hexasaccharides were obtained from a single hexasaccharide precursor. This approach combined the flexibility of chemical synthesis with the selectivity of enzyme-catalyzed sulfations, thus simplifying the overall synthetic operations. In an attempt to establish structure activity relationships of heparan sulfate binding with its receptor, the synthesized oligosaccharides were incorporated onto a glycan microarray, and their bindings with a growth factor FGF-2 were examined. The unique combination of chemical and enzymatic approaches expanded the capability of oligosaccharide synthesis. In addition, the well-defined heparan sulfate structures helped shine light on the fine substrate specificities of biosynthetic enzymes and confirm the potential sequence of enzymatic reactions in biosynthesis. PMID:26574650

A New Triterpenoidal from Vernonia cinerea.

PubMed

Misra, T N; Singh, R S; Srivastava, R; Pandey, H S; Prasad, C; Singh, S

1993-10-01

From the roots of VERNONIA CINEREA Less. (Compositae) a new triterpenoid has been isolated and characterised as 3beta-acetoxyurs-19-ene ( 1). A further constituent has been identified as lupeol acetate. Structure elucidation has been made with the help of spectral analyses.

Bioinspired total synthesis and structural revision of yuremamine, an alkaloid from the entheogenic plant Mimosa tenuiflora.

PubMed

Calvert, Matthew B; Sperry, Jonathan

2015-04-11

Guided by a biosynthetic hypothesis, a serendipitous total synthesis of yuremamine has resulted in its structural revision from the putative pyrroloindole (1) to the flavonoidal indole (2), which was initially proposed as a biosynthetic intermediate.

Synthesis of 1-O-methylchlorogenic acid: reassignment of structure for MCGA3 isolated from bamboo (Phyllostachys edulis) leaves

USDA-ARS?s Scientific Manuscript database

The first synthesis of 1-O-methylchlorogenic acid is described. The short and efficient synthesis of this compound provides laboratory-scale quantities of the material to investigate its biological properties. The synthesis involved C-1 alkylation of the known (-)-4,5-cyclohexylidenequinic acid lact...

Synthesis of Large-Area 2D Layered Materials and Their Heterostacking Structures

DTIC Science & Technology

2017-10-13

Volume: 6 Pages: 7666 Published: JUL 2015 4. Title: Atomically Thin Heterostructures Based on Single- Layer Tungsten Diselenide and DISTRIBUTION A...AFRL-AFOSR-JP-TR-2017-0070 Synthesis of Large-Area 2D layered Materials and Their Heterostacking Structures Chih-Wei Chu Academia Sinica Final Report...TYPE Final 3. DATES COVERED (From - To) 20 Nov 2014 to 19 Nov 2016 4. TITLE AND SUBTITLE Synthesis of Large-Area 2D layered Materials and Their

Stereoselective Total Synthesis of (±)-5- epi-Cyanthiwigin I via an Intramolecular Pauson-Khand Reaction as the Key Step.

PubMed

Chang, Yuanyuan; Shi, Linlin; Huang, Jun; Shi, Lili; Zhang, Zichun; Hao, Hong-Dong; Gong, Jianxian; Yang, Zhen

2018-05-09

A convenient approach to the construction of the 5-6-7 tricarbocyclic fused core structure of cyanthiwigins via a Co-mediated Pauson-Khand reaction as a key step has been developed. The cyathane core intermediate obtained by this strategy was used in the concise synthesis of (±)-5- epi-cyanthiwigin I. The developed chemistry paves the way for the total synthesis of structurally diverse cyanthiwigins.

NMR Studies of Peroxidases.

NASA Astrophysics Data System (ADS)

Veitch, Nigel Charles

Available from UMI in association with The British Library. Requires signed TDF. Peroxidases are a haem-containing group of enzymes with a wide diversity of function within biological systems. While a common characteristic is the ability to catalyse the conversion of hydrogen peroxide to water, it is the accompanying processes of hormone synthesis and degradation which have generated such a high level of interest. However, information at the molecular level is limited to a single well-resolved crystal structure, that of yeast cytochrome c peroxidase. This thesis presents a strategy for the investigation of peroxidase structure and function based on proton nuclear magnetic resonance spectroscopy, a technique which has the ability to address aspects of both protein structure and protein dynamics in solution. The application of one- and two-dimensional NMR techniques has been developed in the context of plant peroxidases, notably the isoenzyme HRP-C derived from the horseradish root. Characterisation of the proton NMR spectra of HRP -C in resting and ligated states provided new information enabling the structure of the binding site for aromatic donor molecules, such as indole-3-propionic, ferulic and benzhydroxamic acids, to be resolved. In order to overcome difficulties encountered with a protein of the complexity of peroxidase, additional information was obtained from chemical shift parameters and the use of peroxidase variants produced by site-directed mutagenesis. A comparative study using NMR spectroscopy was undertaken for wild-type recombinant HRP-C expressed in Escherichia coli, and two protein variants with substitutions made to residues located on the distal side of the haem pocket, Phe41 to Val and Arg38 to Lys. NMR analyses of a plant peroxidase from barley grains and the fungal peroxidase from Coprinus cinereus were also successful using methods conceived with HRP-C. Examination of three specifically constructed recombinant protein variants of C. cinereus peroxidase was essential in confirming the identity of residues participating in the aromatic donor molecule binding site of peroxidases.

Synthesis, Characterization, and Secondary Structure Determination of a Silk-Inspired, Self-Assembling Peptide: A Laboratory Exercise for Organic and Biochemistry Courses

ERIC Educational Resources Information Center

Albin, Tyler J.; Fry, Melany M.; Murphy, Amanda R.

2014-01-01

This laboratory experiment gives upper-division organic or biochemistry undergraduate students a comprehensive look at the synthesis, chemical characterization, self-assembly, and secondary structure determination of small, N-acylated peptides inspired by the protein structure of silkworm silk. All experiments can be completed in one 4 h lab…

Effects of Gold Salt Speciation and Structure of Human and Bovine Serum Albumins on the Synthesis and Stability of Gold Nanostructures

PubMed Central

Miranda, Érica G. A.; Tofanello, Aryane; Brito, Adrianne M. M.; Lopes, David M.; Albuquerque, Lindomar J. C.; de Castro, Carlos E.; Costa, Fanny N.; Giacomelli, Fernando C.; Ferreira, Fabio F.; Araújo-Chaves, Juliana C.; Nantes, Iseli L.

2016-01-01

The present study aimed to investigate the influence of albumin structure and gold speciation on the synthesis of gold nanoparticles (GNPs). The strategy of synthesis was the addition of HAuCl4 solutions at different pH values (3–12) to solutions of human and bovine serum albumins (HSA and BSA) at the same corresponding pH values. Different pH values influence the GNP synthesis due to gold speciation. Besides the inherent effect of pH on the native structure of albumins, the use N-ethylmaleimide (NEM)-treated and heat-denaturated forms of HSA and BSA provided additional insights about the influence of protein structure, net charge, and thiol group approachability on the GNP synthesis. NEM treatment, heating, and the extreme values of pH promoted loss of the native albumin structure. The formation of GNPs indicated by the appearance of surface plasmon resonance (SPR) bands became detectable from 15 days of the synthesis processes that were carried out with native, NEM-treated and heat-denaturated forms of HSA and BSA, exclusively at pH 6 and 7. After 2 months of incubation, SPR band was also detected for all synthesis carried out at pH 8.0. The mean values of the hydrodynamic radius (RH) were 24 and 34 nm for GNPs synthesized with native HSA and BSA, respectively. X-ray diffraction (XRD) revealed crystallites of 13 nm. RH, XRD, and zeta potential values were consistent with GNP capping by the albumins. However, the GNPs produced with NEM-treated and heat-denaturated albumins exhibited loss of protein capping by lowering the ionic strength. This result suggests a significant contribution of non-electrostatic interactions of albumins with the GNP surface, in these conditions. The denaturation of proteins exposes hydrophobic groups to the solvent, and these groups could interact with the gold surface. In these conditions, the thiol blockage or oxidation, the latter probably favored upon heating, impaired the formation of a stable capping by thiol coordination with the gold surface. Therefore, the cysteine side chain of albumins is important for the colloidal stabilization of GNPs rather than as the reducing agent for the synthesis. Despite the presence of more reactive gold species at more acidic pH values, i.e., below 6.0, in these conditions the loss of native albumin structure impaired GNP synthesis. Alkaline pH values (9–12) combined the unfavorable conditions of denaturated protein structure with less reactive gold species. Therefore, an optimal condition for the synthesis of GNPs using serum albumins involves more reactive gold salt species combined with a reducing and negatively charged form of the protein, all favored at pH 6–7. PMID:27066476

Effect of synthesis method on structure, band gap and surface morphology of delafossite oxides, CuAlO2 and CuFeO2

NASA Astrophysics Data System (ADS)

Shah, Aadil Abass; Azam, Ameer

2018-04-01

In this research work we have reported the synthesis of two different delafossites, CuAlO2 and CuFeO2 by two different synthesis methods viz hydrothermal method and the combustion method. The effect of synthesis on structure, band gap and morphology of the synthesized delafossites was carried out using various techniques. The phase and structure of the synthesized delafossites were studied and confirmed using X-ray diffraction and the crystallite size was calculated. FTIR measurements showed the presence of different stretching modes and functional groups in the synthesized oxides. The surface morphology was studied using the scanning electron microscopy. The band gap of the synthesized delafossite oxides was found to be in the range of 2.8 and 3.3 eV.

Synthesis and biological evaluation of manzamine analogues.

PubMed

Winkler, Jeffrey D; Londregan, Allyn T; Ragains, Justin R; Hamann, Mark T

2006-07-20

[Structure: see text] The synthesis and biological evaluation of a series of analogues of manzamine A, representing partial structures of the pentacyclic ABCDE diamine core, is described. All new compounds were screened against Plasmodium falciparum and demonstrated attenuated antimalarial activity relative to that of manzamine A.

Accessibility of selenomethionine proteins by total chemical synthesis: structural studies of human herpesvirus-8 MIP-II.

PubMed

Shao, W; Fernandez, E; Wilken, J; Thompson, D A; Siani, M A; West, J; Lolis, E; Schweitzer, B I

1998-12-11

The determination of high resolution three-dimensional structures by X-ray crystallography or nuclear magnetic resonance (NMR) is a time-consuming process. Here we describe an approach to circumvent the cloning and expression of a recombinant protein as well as screening for heavy atom derivatives. The selenomethionine-modified chemokine macrophage inflammatory protein-II (MIP-II) from human herpesvirus-8 has been produced by total chemical synthesis, crystallized, and characterized by NMR. The protein has a secondary structure typical of other chemokines and forms a monomer in solution. These results indicate that total chemical synthesis can be used to accelerate the determination of three-dimensional structures of new proteins identified in genome programs.

Optimal Full Information Synthesis for Flexible Structures Implemented on Cray Supercomputers

NASA Technical Reports Server (NTRS)

Lind, Rick; Balas, Gary J.

1995-01-01

This paper considers an algorithm for synthesis of optimal controllers for full information feedback. The synthesis procedure reduces to a single linear matrix inequality which may be solved via established convex optimization algorithms. The computational cost of the optimization is investigated. It is demonstrated the problem dimension and corresponding matrices can become large for practical engineering problems. This algorithm represents a process that is impractical for standard workstations for large order systems. A flexible structure is presented as a design example. Control synthesis requires several days on a workstation but may be solved in a reasonable amount of time using a Cray supercomputer.

Room-temperature Electrochemical Synthesis of Carbide-derived Carbons and Related Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gogotsi, Yury

2015-02-28

This project addresses room-temperature electrochemical etching as an energy-efficient route to synthesis of 3D nanoporous carbon networks and layered 2D carbons and related structures, as well as provides fundamental understanding of structure and properties of materials produced by this method. Carbide-derived-carbons (CDCs) are a growing class of nanostructured carbon materials with properties that are desirable for many applications, such as electrical energy and gas storage. The structure of these functional materials is tunable by the choice of the starting carbide precursor, synthesis method, and process parameters. Moving from high-temperature synthesis of CDCs through vacuum decomposition above 1400°C and chlorination abovemore » 400°C, our studies under the previous DOE BES support led to identification of precursor materials and processing conditions for CDC synthesis at temperatures as low as 200°C, resulting in amorphous and highly reactive porous carbons. We also investigated synthesis of monolithic CDC films from carbide films at 250-1200°C. The results of our early studies provided new insights into CDC formation, led to development of materials for capacitive energy storage, and enabled fundamental understanding of the electrolyte ions confinement in nanoporous carbons.« less

Corporatised Leadership in English Schools

ERIC Educational Resources Information Center

Courtney, Steven J.

2015-01-01

Corporatised leadership in schools in England is being promoted through new actors and new types of school, these latter with corporate structures, values, regulatory freedoms and contractual arrangements with staff. Corporatised leadership is characterised "inter alia" by the promotion of the interests of business through the…

Schooling in Times of Acceleration

ERIC Educational Resources Information Center

Buddeberg, Magdalena; Hornberg, Sabine

2017-01-01

Modern societies are characterised by forms of acceleration, which influence social processes. Sociologist Hartmut Rosa has systematised temporal structures by focusing on three categories of social acceleration: technical acceleration, acceleration of social change, and acceleration of the pace of life. All three processes of acceleration are…

Synthesis and synchrotron characterisation of novel dual-template of hydroxyapatite scaffolds with controlled size porous distribution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lima, Thiago A. R. M.; Ilavsky, Jan; Hammons, Joshua

Hydroxyapatite (HAP) scaffolds with a hierarchical porous architecture were prepared by a new dual-template (corn starch and cetyltrimethylammonium bromide (CTAB) surfactant) used to cast HAP nanoparticles and development scaffolds with size hierarchical porous distribution. The Powder X-Ray diffraction (XRD) results showed that only the HAP crystalline phase is present in the samples after calcination; the Scanning Electron Microscopy (SEM) combined with Small Angle (SAXS) and Ultra-Small Angle X-ray Scattering (USAXS) techniques showed that the porous arrangement is promoted by needle-like HAP nanoparticles, and that the pore size distributions depend on the drip-order of the calcium and the phosphate solutions duringmore » the template preparation stage.« less

Consensus for multi-agent systems with time-varying input delays

NASA Astrophysics Data System (ADS)

Yuan, Chengzhi; Wu, Fen

2017-10-01

This paper addresses the consensus control problem for linear multi-agent systems subject to uniform time-varying input delays and external disturbance. A novel state-feedback consensus protocol is proposed under the integral quadratic constraint (IQC) framework, which utilises not only the relative state information from neighbouring agents but also the real-time information of delays by means of the dynamic IQC system states for feedback control. Based on this new consensus protocol, the associated IQC-based control synthesis conditions are established and fully characterised as linear matrix inequalities (LMIs), such that the consensus control solution with optimal ? disturbance attenuation performance can be synthesised efficiently via convex optimisation. A numerical example is used to demonstrate the proposed approach.

Volcano-tectonic structures, gravity and helium in geothermal areas of Tuscany and Latium (Vulsini volcanic district), Italy

USGS Publications Warehouse

Di, Filippo M.; Lombardi, S.; Nappi, G.; Reimer, G.M.; Renzulli, A.; Toro, B.

1999-01-01

Since the early 1980s, geological and structural mapping, gravity, and helium soil-gas studies have been performed in the eastern sector of the Vulsini Volcanic District (Roman Magmatic Province) in an attempt to locate potential geothermal reservoirs. This area is characterised by an anomalous geothermal gradient of > 100??C/km, and by widespread hydrothermal mineralization, thermal springs, high gas fluxes, and fossil and current travertine deposits. The results of these surveys indicate the existence of a number of fault systems, with N-S and E-W structures that appear to be superimposed on older NW-SE and NE-SW features. Comparison of the results of the various studies also reveals differences in permeability and potential reservoir structures at depth.Since the early 1980s, geological and structural mapping, gravity, and helium soil-gas studies have been performed in the eastern sector of the Vulsini Volcanic District (Roman Magmatic Province) in an attempt to locate potential geothermal reservoirs. This area is characterised by an anomalous geothermal gradient of > 100??C/km, and by widespread hydrothermal mineralization, thermal springs, high gas fluxes, and fossil and current travertine deposits. The results of these surveys indicate the existence of a number of fault systems, with N-S and E-W structures that appear to be superimposed on older NW-SE and NE-SW features. Comparison of the results of the various studies also reveals differences in permeability and potential reservoir structures at depth.

Enantioselective synthesis of pactamycin, a complex antitumor antibiotic.

PubMed

Malinowski, Justin T; Sharpe, Robert J; Johnson, Jeffrey S

2013-04-12

Medicinal application of many complex natural products is precluded by the impracticality of their chemical synthesis. Pactamycin, the most structurally intricate aminocyclopentitol antibiotic, displays potent antiproliferative properties across multiple phylogenetic domains, but it is highly cytotoxic. A limited number of analogs produced by genetic engineering technologies show reduced cytotoxicity against mammalian cells, renewing promise for therapeutic applications. For decades, an efficient synthesis of pactamycin amenable to analog derivatizations has eluded researchers. Here, we present a short asymmetric total synthesis of pactamycin. An enantioselective Mannich reaction and symmetry-breaking reduction sequence was designed to enable assembly of the entire carbon core skeleton in under five steps and control critical three-dimensional (stereochemical) functional group relationships. This modular route totals 15 steps and is immediately amenable for structural analog synthesis.

Peloruside B, a Potent Antitumor Macrolide from the New Zealand Marine Sponge Mycale hentscheli: Isolation, Structure, Total Synthesis and Bioactivity

PubMed Central

Singh, A. Jonathan; Xu, Chun-Xiao; Xu, Xiaoming; West, Lyndon M.; Wilmes, Anja; Chan, Ariane; Hamel, Ernest; Miller, John H.; Northcote, Peter T.; Ghosh, Arun K.

2009-01-01

Peloruside B (2), a natural congener of peloruside A (1), was isolated in sub-milligram quantities from the New Zealand marine sponge Mycale hentscheli. Peloruside B promotes microtubule polymerization and arrests cells in the G2M phase of mitosis similar to paclitaxel, and its bioactivity was comparable to that of peloruside A. NMR-directed isolation, structure elucidation, structure confirmation by total synthesis and bioactivity of peloruside B are described in this article. The synthesis features Sharpless dihydroxylation, Brown's asymmetric allylboration reaction, reductive aldol coupling, Yamaguchi macrolactonization and selective methylation. PMID:19957922

Electrically induced microflows probed by fluorescence correlation spectroscopy.

PubMed

Ybert, C; Nadal, F; Salomé, R; Argoul, F; Bourdieu, L

2005-03-01

We report on the experimental characterisation of electrically induced flows at the micrometer scale through Fluorescence Correlation Spectroscopy (FCS) measurements. We stress the potential of FCS as a useful characterisation technique in microfluidics devices for transport properties cartography. The experimental results obtained in a model situation are in agreement with previous calculations (F. Nadal, F. Argoul, P. Kestener, B. Pouligny, C. Ybert, A. Ajdari, Eur. Phys. J. E 9, 387 (2002)) predicting the structure and electric-field dependency of the induced flow. Additionally, the present study evidences a complex behaviour of the probe nanobeads under electric field whose precise understanding might prove relevant for situations where nano-objects interact with an external electric field.

Relationships between electron transport system (ETS) activity and particulate organic matter features in three areas of the Ross Sea (Antarctica)

NASA Astrophysics Data System (ADS)

Misic, C.; Covazzi Harriague, A.; Giglio, F.; La Ferla, R.; Rappazzo, A. C.; Azzaro, M.

2017-11-01

Electron transport system activity (ETSa) and particulate organic matter (POM) concentrations and composition were measured in three areas of the continental shelf of the Ross Sea during summer 2014, in the framework of the Ross Sea Mesoscale Experiment (ROME) project. We aimed at testing whether in the epipelagic layer (0-200 m) ETS showed different activity depending on the geographical position and on the different hydrological structures that characterised each area, as eddy and fronts, and whether the ETSa of the microplanktonic fraction depended on POM quantitative and qualitative features. ETSa showed differences between the three areas, but within each of them the different hydrological conditions did not influence significantly the respiration activity. ETSa displayed significant correlations with POM, especially in the offshore areas characterised by residual ice influence and by a mesoscale eddy structure. In these zones ETSa was enhanced by good trophic value of POM, i.e. showing dominance of proteins and PON over structural carbohydrates and POC, respectively. The role of the phytoplanktonic fraction in ETSa was higher in the eddy-influenced area, that showed significantly higher chlorophyll-a concentrations. On the other hand, in the area placed coastward, the relationships between ETSa and POM changed. High ETSa were found in the subsurface layer and down to 100 m depth and were related to more refractory POM, whose utilization would require higher energy. Different ETSa-POM relationships were consistent with the anomalous phytoplanktonic bloom detected in the coastward area, characterised by Phaeocystis. Thus, the anomalies of the primary producers are reflected by changes in POM respiration and potential C utilization.

A peptidomic approach for monitoring and characterising peptide cyanotoxins produced in Italian lakes by matrix-assisted laser desorption/ionisation and quadrupole time-of-flight mass spectrometry.

PubMed

Ferranti, Pasquale; Nasi, Antonella; Bruno, Milena; Basile, Adriana; Serpe, Luigi; Gallo, Pasquale

2011-05-15

In recent years, the occurrence of cyanobacterial blooms in eutrophic freshwaters has been described all over the world, including most European countries. Blooms of cyanobacteria may produce mixtures of toxic secondary metabolites, called cyanotoxins. Among these, the most studied are microcystins, a group of cyclic heptapeptides, because of their potent hepatotoxicity and activity as tumour promoters. Other peptide cyanotoxins have been described whose structure and toxicity have not been thoroughly studied. Herein we present a peptidomic approach aimed to characterise and quantify the peptide cyanotoxins produced in two Italian lakes, Averno and Albano. The procedure was based on matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry mass spectrometry (MALDI-TOF-MS) analysis for rapid detection and profiling of the peptide mixture complexity, combined with liquid chromatography/electrospray ionisation quadrupole time-of- flight tandem mass spectrometry (LC/ESI-Q-TOF-MS/MS) which provided unambiguous structural identification of the main compounds, as well as accurate quantitative analysis of microcystins. In the case of Lake Averno, a novel variant of microcystin-RR and two novel anabaenopeptin variants (Anabaenopeptins B(1) and Anabaenopeptin F(1)), presenting homoarginine in place of the commonly found arginine, were detected and characterised. In Lake Albano, the peculiar peptide patterns in different years were compared, as an example of the potentiality of the peptidomic approach for fast screening analysis, prior to fine structural analysis and determination of cyanotoxins, which included six novel aeruginosin variants. This approach allows for wide range monitoring of cyanobacteria blooms, and to collect data for evaluating possible health risks to consumers, through the panel of the compounds produced along different years. Copyright © 2011 John Wiley & Sons, Ltd.

Early changes in tissue amino acid metabolism and nutrient routing in rats fed a high-fat diet: evidence from natural isotope abundances of nitrogen and carbon in tissue proteins.

PubMed

Mantha, Olivier L; Polakof, Sergio; Huneau, Jean-François; Mariotti, François; Poupin, Nathalie; Zalko, Daniel; Fouillet, Helene

2018-05-01

Little is known about how diet-induced obesity and insulin resistance affect protein and amino acid (AA) metabolism in tissues. The natural relative abundances of the heavy stable isotopes of C (δ 13C) and N (δ 15N) in tissue proteins offer novel and promising biomarkers of AA metabolism. They, respectively, reflect the use of dietary macronutrients for tissue AA synthesis and the relative metabolic use of tissue AA for oxidation v. protein synthesis. In this study, δ 13C and δ 15N were measured in the proteins of various tissues in young adult rats exposed perinatally and/or fed after weaning with a normal- or a high-fat (HF) diet, the aim being to characterise HF-induced tissue-specific changes in AA metabolism. HF feeding was shown to increase the routing of dietary fat to all tissue proteins via non-indispensable AA synthesis, but did not affect AA allocation between catabolic and anabolic processes in most tissues. However, the proportion of AA directed towards oxidation rather than protein synthesis was increased in the small intestine and decreased in the tibialis anterior muscle and adipose tissue. In adipose tissue, the AA reallocation was observed in the case of perinatal or post-weaning exposure to HF, whereas in the small intestine and tibialis anterior muscle the AA reallocation was only observed after HF exposure that covered both the perinatal and post-weaning periods. In conclusion, HF exposure induced an early reorganisation of AA metabolism involving tissue-specific effects, and in particular a decrease in the relative allocation of AA to oxidation in several peripheral tissues.

Influence of synthesis and sintering parameters on the characteristics of carbonate apatite.

PubMed

Landi, Elena; Tampieri, Anna; Celotti, Giancarlo; Vichi, Lucia; Sandri, Monica

2004-05-01

A new method to synthesise carbonate-substituted hydroxyapatite (CHA) powder has been set up introducing a CO(2) flux, as a source of carbonate, in the HA synthesis process based on the neutralisation reaction. The reactants are abundant and inexpensive. The yield is good compared to other CHA powder synthesis. The reaction may be performed at low temperature and without pH control and does not produce any by-products. The influence of the synthesis parameters (temperature, H(3)PO(4) solution dropping rate, i.e. reaction time, CO(2) flux, ageing time) has been tested to optimise the process conditions in order to obtain the highest carbonation degree and favour the B-type CHA precipitation with respect to A-type one. The prepared powder (5.8wt% of total carbonate with an A/B ratio of 0.78) was thermally treated at various temperatures in the range 500-1400 degrees C in different atmospheres (air, wet and dry carbon dioxide). The thermal treatments were performed with a double aim, to eliminate selectively the carbonate groups in A-position maintaining the B-type substitution, and to evaluate the thermal stability of the CHA and the total loss of carbonate as a function of temperature. The thermal treatment at 900 degrees C in wet CO(2) gave the best result in terms of a high carbonate residue and a low A/B ratio. We also investigate the use of different techniques (inductively coupled plasma, TGA, Fourier transformed infrared spectroscopy, X-ray diffraction) for characterising CHA and calculating sensitivity and accuracy in the quantification of carbonate ions for each molecular site.

Discovery and gram-scale synthesis of BMS-593214, a potent, selective FVIIa inhibitor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Priestley, E. Scott; De Lucca, Indawati; Zhou, Jinglan

A 6-amidinotetrahydroquinoline screening hit was driven to a structurally novel, potent, and selective FVIIa inhibitor through a combination of library synthesis and rational design. An efficient gram-scale synthesis of the active enantiomer BMS-593214 was developed, which required significant optimization of the key Povarov annulation. Importantly, BMS-593214 showed antithrombotic efficacy in a rabbit arterial thrombosis model. A crystal structure of BMS-593214 bound to FVIIa highlights key contacts with Asp 189, Lys 192, and the S2 pocket.

Drug Development of the Antimalarial Agent Artemisinin: Total Synthesis, Analog Synthesis, and Structure-Activity Relationship Studies

DTIC Science & Technology

1990-08-15

16. SUPPLEMENTARY NOTATION 17 COSATi CODES FiELD 07 06 CROUP 03 01 SUB-GROUP IB SUBJECT TERMS (Cont/nu* on rtvtnt if ntctiwy *ne identity b ...number of requisite substituents resulted in the synthesis of ring cleaved analogs and partial structures of artemisinin: (+)-C/D, (+)-A/ B /C, (+)-A/C...in the preparation of the unstable aldehyde 2, and in commendable fashion others have employed an enol ether photo-oxygenation as entry to that

Polyrhythmic Tapping: Examining the Effectiveness of the Strategy of Organizing Rhythmic Structures through Synthesis

ERIC Educational Resources Information Center

Yokus, Hamit; Yokus, Tuba

2015-01-01

In this study the strategy of organizing rhythmic structures through synthesis is named, and defined, and its procedures are described. Its effectiveness for teaching the execution of 3:2, 4:3, 8:3, 5:4, and 3:5 polyrhythmic structures is examined and described. Pre-test and Post-test Control Group Design was employed to test the effectiveness of…

A new feruloyl amide derivative from the fruits of Tribulus terrestris.

PubMed

Zhang, Xiaopo; Wei, Na; Huang, Jian; Tan, Yinfeng; Jin, Dejun

2012-01-01

A new feruloyl amide derivative, named tribulusamide C, was isolated from the fruits of Tribulus terrestris. Its structure was determined on the basis of spectroscopic analysis including IR, 1-D-, 2-D-NMR and HR-ESI-MS. The structure of tribulusamide C was characterised by a unit of pyrrolidine-2,5-dione, which distinguished it from other lignanamides previously isolated from the fruits of T. terrestris.

Mono- and multimeric ferrocene congeners of quinoline-based polyamines as potential antiparasitics

USDA-ARS?s Scientific Manuscript database

A series of mono- and multimeric polyamine-containing ferrocenyl complexes bearing a quinoline motif were prepared. The complexes were characterised by standard techniques. The molecular structure of the monomeric salicylaldimine derivative was elucidated using single crystal X-ray diffraction and w...

Structure-property and composition-property relationships for poly(ethylene terephthalate) surfaces modified by helium plasma-based ion implantation

NASA Astrophysics Data System (ADS)

Tóth, A.; Veres, M.; Kereszturi, K.; Mohai, M.; Bertóti, I.; Szépvölgyi, J.

2011-10-01

The surfaces of untreated and helium plasma-based ion implantation (He PBII) treated poly(ethylene terephthalate) (PET) samples were characterised by reflectance colorimetry, contact angle studies and measurements of surface electrical resistance. The results were related to the structural and compositional data obtained by the authors earlier on parallel samples by XPS and Raman spectroscopy. Inverse correlations between lightness and ID/ IG ratio and between chroma and ID/ IG ratio were obtained, suggesting that the PBII-treated PET samples darken and their colourfulness decreases with the increase of the portion of aromatic sp 2 carbon rings in the chemical structure of the modified layer. Direct correlation between water contact angle and the ID/ IG ratio and inverse correlations between surface energy and ID/ IG ratio and between dispersive component of surface energy and ID/ IG ratio were found, reflecting that surface wettability, surface energy and its dispersive component decrease with the formation of surface structure, characterised again by enhanced portion of aromatic sp 2 carbon rings. The surface electrical resistance decreased with the increase of the surface C-content determined by XPS and also with the increase of the surface concentration of conjugated double bonds, reflected by the increase of the π → π* shake-up satellite of the C 1s peak.

The social ecology of girls' bullying practices: exploratory research in two London schools.

PubMed

Jamal, Farah; Bonell, Chris; Harden, Angela; Lorenc, Theo

2015-06-01

This exploratory study adopts a socio-ecological approach to examine the context of school bullying. It asks: (1) what are students' accounts of bullying practices?; (2) how are these enabled and constrained by the school-environment?; (3) how is gender implicated? Qualitative data were collected from girls in two schools in London via focus groups (one in each school; students aged 12-15) and seven semi-structured interviews (in one school; students aged 16-18); and from school policy documents. Our interpretation of girls' accounts, informed by Giddens' structuration theory, suggests that bullying practices were spatially patterned in the schools and often characterised by the regulation of girls' sexuality and sexual-harassment. Repeated acts of aggression were fluid with regard to the bully and victim role, challenging the dominant view of bullying as characterised by consistent disparities in power between individuals. Schools structured bullying behaviour via policies and practices that ignored these forms of abuse and which focused on and may have been complicit in the making of stable 'bully' and 'victim' roles, thus indirectly contributing to the reproduction of unhealthy relationships between students. In terms of gender, traditional gendered and sexual discourses appear to structure the identities of the schools and girls in our study. © 2015 Foundation for the Sociology of Health & Illness.

Memory CD4 T cell subsets are kinetically heterogeneous and replenished from naive T cells at high levels

PubMed Central

Gossel, Graeme; Hogan, Thea; Cownden, Daniel

2017-01-01

Characterising the longevity of immunological memory requires establishing the rules underlying the renewal and death of peripheral T cells. However, we lack knowledge of the population structure and how self-renewal and de novo influx contribute to the maintenance of memory compartments. Here, we characterise the kinetics and structure of murine CD4 T cell memory subsets by measuring the rates of influx of new cells and using detailed timecourses of DNA labelling that also distinguish the behaviour of recently divided and quiescent cells. We find that both effector and central memory CD4 T cells comprise subpopulations with highly divergent rates of turnover, and show that inflows of new cells sourced from the naive pool strongly impact estimates of memory cell lifetimes and division rates. We also demonstrate that the maintenance of CD4 T cell memory subsets in healthy mice is unexpectedly and strikingly reliant on this replenishment. DOI: http://dx.doi.org/10.7554/eLife.23013.001 PMID:28282024

Memory CD4 T cell subsets are kinetically heterogeneous and replenished from naive T cells at high levels.

PubMed

Gossel, Graeme; Hogan, Thea; Cownden, Daniel; Seddon, Benedict; Yates, Andrew J

2017-03-10

Characterising the longevity of immunological memory requires establishing the rules underlying the renewal and death of peripheral T cells. However, we lack knowledge of the population structure and how self-renewal and de novo influx contribute to the maintenance of memory compartments. Here, we characterise the kinetics and structure of murine CD4 T cell memory subsets by measuring the rates of influx of new cells and using detailed timecourses of DNA labelling that also distinguish the behaviour of recently divided and quiescent cells. We find that both effector and central memory CD4 T cells comprise subpopulations with highly divergent rates of turnover, and show that inflows of new cells sourced from the naive pool strongly impact estimates of memory cell lifetimes and division rates. We also demonstrate that the maintenance of CD4 T cell memory subsets in healthy mice is unexpectedly and strikingly reliant on this replenishment.

Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

NASA Astrophysics Data System (ADS)

Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

2015-12-01

The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies.

Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

PubMed Central

Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

2015-01-01

The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies. PMID:26677949

Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity.

PubMed

Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

2015-12-18

The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies.

The energetics of fish growth and how it constrains food-web trophic structure.

PubMed

Barneche, Diego R; Allen, Andrew P

2018-06-01

The allocation of metabolic energy to growth fundamentally influences all levels of biological organisation. Here we use a first-principles theoretical model to characterise the energetics of fish growth at distinct ontogenetic stages and in distinct thermal regimes. Empirically, we show that the mass scaling of growth rates follows that of metabolic rate, and is somewhat steeper at earlier ontogenetic stages. We also demonstrate that the cost of growth, E m , varies substantially among fishes, and that it may increase with temperature, trophic level and level of activity. Theoretically, we show that E m is a primary determinant of the efficiency of energy transfer across trophic levels, and that energy is transferred more efficiently between trophic levels if the prey are young and sedentary. Overall, our study demonstrates the importance of characterising the energetics of individual growth in order to understand constraints on the structure of food webs and ecosystems. © 2018 John Wiley & Sons Ltd/CNRS.

Nanoscale electro-structural characterisation of ohmic contacts formed on p-type implanted 4H-SiC

NASA Astrophysics Data System (ADS)

Frazzetto, Alessia; Giannazzo, Filippo; Lo Nigro, Raffaella; di Franco, Salvatore; Bongiorno, Corrado; Saggio, Mario; Zanetti, Edoardo; Raineri, Vito; Roccaforte, Fabrizio

2011-12-01

This work reports a nanoscale electro-structural characterisation of Ti/Al ohmic contacts formed on p-type Al-implanted silicon carbide (4H-SiC). The morphological and the electrical properties of the Al-implanted layer, annealed at 1700°C with or without a protective capping layer, and of the ohmic contacts were studied using atomic force microscopy [AFM], transmission line model measurements and local current measurements performed with conductive AFM. The characteristics of the contacts were significantly affected by the roughness of the underlying SiC. In particular, the surface roughness of the Al-implanted SiC regions annealed at 1700°C could be strongly reduced using a protective carbon capping layer during annealing. This latter resulted in an improved surface morphology and specific contact resistance of the Ti/Al ohmic contacts formed on these regions. The microstructure of the contacts was monitored by X-ray diffraction analysis and a cross-sectional transmission electron microscopy, and correlated with the electrical results.

Combined techniques for characterising pasta structure reveals how the gluten network slows enzymic digestion rate.

PubMed

Zou, Wei; Sissons, Mike; Gidley, Michael J; Gilbert, Robert G; Warren, Frederick J

2015-12-01

The aim of the present study is to characterise the influence of gluten structure on the kinetics of starch hydrolysis in pasta. Spaghetti and powdered pasta were prepared from three different cultivars of durum semolina, and starch was also purified from each cultivar. Digestion kinetic parameters were obtained through logarithm-of-slope analysis, allowing identification of sequential digestion steps. Purified starch and semolina were digested following a single first-order rate constant, while pasta and powdered pasta followed two sequential first-order rate constants. Rate coefficients were altered by pepsin hydrolysis. Confocal microscopy revealed that, following cooking, starch granules were completely swollen for starch, semolina and pasta powder samples. In pasta, they were completely swollen in the external regions, partially swollen in the intermediate region and almost intact in the pasta strand centre. Gluten entrapment accounts for sequential kinetic steps in starch digestion of pasta; the compact microstructure of pasta also reduces digestion rates. Copyright © 2015 Elsevier Ltd. All rights reserved.

Comparison of the Rheology of Bauxite Residue Suspensions

NASA Astrophysics Data System (ADS)

Pashias, N.; Boger, D. V.; Summers, J.; Glenister, D. J.

The paper presents an overview on the rheology of bauxite residue suspensions. Comparative viscosity and yield stress data are presented for bauxite residues generated in Australia, Jamaica, Surinam, and the USA. A yield stress for optimum dry disposal is specified as is the concentration for minimum energy consumption for the pumping of the four different materials. The data show that bauxite residues can be characterised at two structural states: the initial and the equilibrium or time-independent state. Data can be collected and reproduced for different muds providing there is an understanding of the time dependent nature of the material. The four red mud samples obtained from around the world have been characterised in both the initial and final equilibrium state. A comparison shows that after the course particle fraction has been removed the US, Surinam, and three samples from Western Australia all show similar rheological characteristics in the reduced structural state. A fundamental understanding of the basic rheology of bauxite residue is necessary for establishing an optimal waste disposal strategy.

Chromium and yttrium-doped magnesium aluminum oxides prepared from layered double hydroxides

NASA Astrophysics Data System (ADS)

García-García, J. M.; Pérez-Bernal, M. E.; Ruano-Casero, R. J.; Rives, V.

2007-12-01

Layered double hydroxides with the hydrotalcite-like structures, containing Mg 2+ and Al 3+, doped with Cr 3+ and Y 3+, have been prepared by precipitation at constant pH. The weight percentages of Cr 3+ and Y 3+ were 1, 2, or 3%, and 0.5 or 1%, respectively. Single phases were obtained in all cases, whose crystallinity decreased as the content in Cr and Y was increased. The solids have been characterised by element chemical analysis, powder X-ray diffraction, thermal analyses (differential, thermogravimetric and programmed reduction), FT-IR and UV-vis spectroscopies; the specific surface areas have been determined from nitrogen adsorption isotherms at -196 °C. Upon calcination at 1200 °C for 5 h in air all solids display a mixed structure (spinel and rock salt for MgO); these solids have also been characterised by these techniques and their chromatic coordinates (CIE - L∗a∗b∗) have been determined. Their pink colour makes these solids suitable for being used as ceramic pigments.

Natural products as an inspiration in the diversity-oriented synthesis of bioactive compound libraries

PubMed Central

Cordier, Christopher; Morton, Daniel; Murrison, Sarah; O'Leary-Steele, Catherine

2008-01-01

The purpose of diversity-oriented synthesis is to drive the discovery of small molecules with previously unknown biological functions. Natural products necessarily populate biologically relevant chemical space, since they bind both their biosynthetic enzymes and their target macromolecules. Natural product families are, therefore, libraries of pre-validated, functionally diverse structures in which individual compounds selectively modulate unrelated macromolecular targets. This review describes examples of diversity-oriented syntheses which have, to some extent, been inspired by the structures of natural products. Particular emphasis is placed on innovations that allow the synthesis of compound libraries that, like natural products, are skeletally diverse. Mimicking the broad structural features of natural products may allow the discovery of compounds that modulate the functions of macromolecules for which ligands are not known. The ability of innovations in diversity-oriented synthesis to deliver such compounds is critically assessed. PMID:18663392

Assessing genetic structure and diversity of airborne bacterial communities by DNA fingerprinting and 16S rDNA clone library

NASA Astrophysics Data System (ADS)

Maron, Pierre-Alain; Lejon, David P. H.; Carvalho, Esmeralda; Bizet, Karine; Lemanceau, Philippe; Ranjard, Lionel; Mougel, Christophe

The density, genetic structure and diversity of airborne bacterial communities were assessed in the outdoor atmosphere. Two air samples were collected on the same location (north of France) at two dates (March 2003 (sample1) and May 2003 (sample 2)). Molecular culture -independent methods were used to characterise airborne bacterial communities regardless of the cell culturability. The automated-ribosomal intergenic spacer analysis (A-RISA) was performed to characterise the community structure in each sample. For both sampling dates, complex A-RISA patterns were observed suggesting a highly diverse community structure, comparable to those found in soil, water or sediment environments. Furthermore, differences in the genetic structure of airborne bacterial communities were observed between samples 1 and 2 suggesting an important variability in time. A clone library of 16S rDNA directly amplified from air DNA of sample 1 was constructed and sequenced to analyse the community composition and diversity. The Proteobacteria group had the greatest representation (60%), with bacteria belonging to the different subdivisions α- (19%), β-(21%), γ-(12%) and δ-(8%). Firmicute and Actinobacteria were also well represented with 14% and 12%, respectively. Most of the identified bacteria are known to be commonly associated with soil or plant environments suggesting that the atmosphere is mainly colonised transiently by microorganisms from local sources, depending on air fluxes.

Analysis of 3D Prints by X-ray Computed Microtomography and Terahertz Pulsed Imaging.

PubMed

Markl, Daniel; Zeitler, J Axel; Rasch, Cecilie; Michaelsen, Maria Høtoft; Müllertz, Anette; Rantanen, Jukka; Rades, Thomas; Bøtker, Johan

2017-05-01

A 3D printer was used to realise compartmental dosage forms containing multiple active pharmaceutical ingredient (API) formulations. This work demonstrates the microstructural characterisation of 3D printed solid dosage forms using X-ray computed microtomography (XμCT) and terahertz pulsed imaging (TPI). Printing was performed with either polyvinyl alcohol (PVA) or polylactic acid (PLA). The structures were examined by XμCT and TPI. Liquid self-nanoemulsifying drug delivery system (SNEDDS) formulations containing saquinavir and halofantrine were incorporated into the 3D printed compartmentalised structures and in vitro drug release determined. A clear difference in terms of pore structure between PVA and PLA prints was observed by extracting the porosity (5.5% for PVA and 0.2% for PLA prints), pore length and pore volume from the XμCT data. The print resolution and accuracy was characterised by XμCT and TPI on the basis of the computer-aided design (CAD) models of the dosage form (compartmentalised PVA structures were 7.5 ± 0.75% larger than designed; n = 3). The 3D printer can reproduce specific structures very accurately, whereas the 3D prints can deviate from the designed model. The microstructural information extracted by XμCT and TPI will assist to gain a better understanding about the performance of 3D printed dosage forms.

Thioether coordination to divalent selenium halide acceptors--synthesis, properties and structures.

PubMed

Jolleys, Andrew; Levason, William; Reid, Gillian

2013-02-28

The tetravalent SeCl(4) and SeBr(4) are reduced in the presence of thioether ligands L (SMe(2), tht) or L-L (MeS(CH(2))(n)SMe (n = 2 or 3), o-C(6)H(4)(SMe)(2)) in MeCN solution at 0 °C, forming Se(II) thioether complexes, including the crystallographically characterised halo-bridged chain polymers [SeX(2)(SMe(2))] (X = Cl or Br), molecular trans-[SeX(2)(tht)(2)], cis-[SeBr(2){MeS(CH(2))(2)SMe}] and the thioether-bridged polymer [SeBr(2){MeS(CH(2))(3)SMe}], as the main products, together with halogenated ligand. The [SeX(2)(L)(2)] and [SeX(2)(L-L)] complexes are all based upon distorted square planar coordination, with two Se-based lone pairs assumed to occupy the (vacant) axial sites, and Se-S bond distances of ca. 2.4-2.6 Å. The 1:1 species [SeX(2)(SMe(2))] are T-shaped with trans X groups and weak intermolecular SeX contacts. The SeCl(2)-thioether complexes are less stable than the bromides, both in solution in CH(2)Cl(2) and as solids at ambient temperature. Reaction of SeBr(4) with o-C(6)H(4)(SMe(2))(2) leads to the red complex cis-[SeBr(2){κ(1)-o-C(6)H(4)(SMe)(2)}(2)] as the major product; together with a minor (yellow) product formed via bromination of the aromatic ring, [SeBr(2){4-Br-1,2-(SMe)(2)-C(6)H(3)}(2)]. The crystal structure confirms a V-shaped SeBr(2) unit with long (weak) κ(1)-interactions to one S donor (meta to the Br) from two brominated ligands--an extremely rare coordination mode for an o-phenylene dithioether. Similar reaction of o-C(6)H(4)(SMe(2))(2) with SeCl(4) leads to several species, including monosulfonium cation, [1](+) formed by coupling of one thioether group to the C4-position of the phenylene backbone in an adjacent molecule, confirmed crystallographically. Carbon-sulfur coupling is also evident in the reaction of SeX(4) with o-C(6)H(4)(CH(2)SMe)(2), leading to two related cyclic sulfonium species, [2](+) and [3](+), which were structurally characterised as [SeBr(4)](2-) and [Se(2)Cl(6)](2-) salts respectively. Reaction of SeX(4) with SeMe(2) leads to halogenation of the ligand to form Me(2)SeX(2) and reduction of the SeX(4) to elemental selenium.

Total synthesis and structural revision of the marine macrolide neopeltolide.

PubMed

Custar, Daniel W; Zabawa, Thomas P; Scheidt, Karl A

2008-01-23

The total synthesis and structural revision of the marine natural product neopeltolide is reported. The key bond-forming step involves a Lewis acid-catalyzed intramolecular cyclization to install the tetrahydropyran ring and the macrocycle simultaneously. This type of cyclization is the first of its kind and assembles the carbon backbone of the natural product efficiently. The synthesis of the reported structure revealed differences in the data between the natural and synthetic material. After significant investigation, the diastereomeric molecule with the C11 and C13 configurations inverted was synthesized using the initial route. This compound matches the data reported for neopeltolide (1H, 13C, HRMS, IR, NOESY, [alpha]), thereby establishing the correct overall structure for this potent macrolide natural product, including the relative and absolute stereochemistry.

Barriers, facilitators, strategies and outcomes to engaging policymakers, healthcare managers and policy analysts in knowledge synthesis: a scoping review protocol.

PubMed

Tricco, Andrea C; Zarin, Wasifa; Rios, Patricia; Pham, Ba'; Straus, Sharon E; Langlois, Etienne V

2016-12-23

Engaging policymakers, healthcare managers and policy analysts in the conduct of knowledge synthesis can help increase its impact. This is particularly important for knowledge synthesis studies commissioned by decision-makers with limited timelines, as well as reviews of health policy and systems research. A scoping review will be conducted to assess barriers, facilitators, strategies and outcomes of engaging these individuals in the knowledge synthesis process. We will follow the Joanna Briggs Institute guidance for scoping reviews. Literature searches of electronic databases (eg, MEDLINE, EMBASE, Cochrane Library, ERIC, PsycINFO) will be conducted from inception onwards. The electronic search will be supplemented by searching for sources that index unpublished/difficult to locate studies (eg, GreyNet International database), as well as through scanning of reference lists of reviews on related topics. All study designs using either qualitative or quantitative methodologies will be eligible if there is a description of the strategies, barriers or facilitators, and outcomes of engaging policymakers, healthcare managers and policy analysts in the knowledge synthesis process. Screening and data abstraction will be conducted by 2 team members independently after a calibration exercise across the team. A third team member will resolve all discrepancies. We will conduct frequency analysis and thematic analysis to chart and characterise the literature, identifying data gaps and opportunities for future research, as well as implications for policy. This project was commissioned by the Alliance for Health Policy and Systems Research, WHO. The results will be used by Alliance Review Centers of health policy and systems research in low-income and middle-income countries that are conducting knowledge synthesis to inform health policymaking and decision-making. Our results will also be disseminated through conference presentations, train-the-trainer events, peer-reviewed publication and a 1-page policy brief that will be posted on the authors' websites. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/.

Characterisation of large scale structures in starch granules via small-angle neutron and X-ray scattering.

PubMed

Doutch, James; Gilbert, Elliot P

2013-01-02

Small angle scattering (SAS) techniques have a distinguished track record in illuminating the semi-crystalline lamellar structure of the starch granule. To date, there have been few attempts to use SAS techniques to characterise larger-scale structures reported from imaging techniques such as growth rings, blocklets or pores, nor how these structures would modulate the well-known scattering arising from the semi-crystalline lamellar structure. In this study, SAS data collected over an extended q range were gathered from dry and hydrated starch powders from varied botanical sources. The use of neutrons and X-rays, as well as comparing dry and hydrated granules, allowed different levels of contrast in scattering length density to be probed and therefore selected structural regions to be highlighted. The lowest q range, 0.002-0.04 Å(-1), was found to be dominated by scattering from the starch granules themselves, especially in the dry powders; however an inflection point from a low contrast structure was observed at 0.035 Å(-1). The associated scattering was interpreted within a unified scattering framework with the inflexion point correlating with a structure with radius of gyration ~90 Å - a size comparable to small blocklets or superhelices. In hydrated starches, it is observed that there is an inflection point between lamellar and q(-4) power-law scattering regions at approximately 0.004 Å(-1) which may correlate with growth rings and large blocklets. The implications of these findings on existing models of starch lamellar scattering are discussed. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

A Minimalist NMR Approach for the Structural Revision of Mucoxin

PubMed Central

Yan, Jun; Garzan, Atefeh; Narayan, Radha S.

2011-01-01

In an attempt to revise the structural assignment of mucoxin, and faced with 64 diastereomeric possibilities, we resorted to the synthesis of truncated structures that contained the core stereochemical sites. Twelve stereochemical analogues were synthesized, their 1H and 13C NMR spectra were analyzed and four recurring stereochemical trends were distilled from the data. Applying the observed trends to the diastereomeric population pared the possible choices for the correct structure of mucoxin from 64 to 4. Synthesis of these analogues led to the identification of the correct structure of mucoxin. PMID:21089037

Nanoindentation characterisation of human colorectal cancer cells considering cell geometry, surface roughness and hyperelastic constitutive behaviour

NASA Astrophysics Data System (ADS)

Boccaccio, Antonio; Uva, Antonio E.; Papi, Massimiliano; Fiorentino, Michele; De Spirito, Marco; Monno, Giuseppe

2017-01-01

Characterisation of the mechanical behaviour of cancer cells is an issue of crucial importance as specific cell mechanical properties have been measured and utilized as possible biomarkers of cancer progression. Atomic force microscopy certainly occupies a prominent place in the field of the mechanical characterisation devices. We developed a hybrid approach to characterise different cell lines (SW620 and SW480) of the human colon carcinoma submitted to nanoindentation measurements. An ad hoc algorithm was written that compares the force-indentation curves experimentally retrieved with those predicted by a finite element model that simulates the nanoindentation process and reproduces the cell geometry and the surface roughness. The algorithm perturbs iteratively the values of the cell mechanical properties implemented in the finite element model until the difference between the experimental and numerical force-indentation curves reaches the minimum value. The occurrence of this indicates that the implemented material properties are very close to the real ones. Different hyperelastic constitutive models, such as Arruda-Boyce, Mooney-Rivlin and Neo-Hookean were utilized to describe the structural behaviour of indented cells. The algorithm was capable of separating, for all the cell lines investigated, the mechanical properties of cell cortex and cytoskeleton. Material properties determined via the algorithm were different with respect to those obtained with the Hertzian contact theory. This demonstrates that factors such as: the cell geometry/anatomy and the hyperelastic constitutive behaviour, which are not contemplated in the Hertz’s theory hypotheses, do affect the nanoindentation measurements. The proposed approach represents a powerful tool that, only on the basis of nanoindentation measurements, is capable of characterising material at the subcellular level.

Synthesis, structure and imaging of oligodeoxyribonucleotides with tellurium-nucleobase derivatization.

PubMed

Sheng, Jia; Hassan, Abdalla E A; Zhang, Wen; Zhou, Jianfeng; Xu, Bingqian; Soares, Alexei S; Huang, Zhen

2011-05-01

We report here the first synthesis of 5-phenyl-telluride-thymidine derivatives and the Te-phosphoramidite. We also report here the synthesis, structure and STM current-imaging studies of DNA oligonucleotides containing the nucleobases (thymine) derivatized with 5-phenyl-telluride functionality (5-Te). Our results show that the 5-Te-DNA is stable, and that the Te-DNA duplex has the thermo-stability similar to the corresponding native duplex. The crystal structure indicates that the 5-Te-DNA duplex structure is virtually identical to the native one, and that the Te-modified T and native A interact similarly to the native T and A pair. Furthermore, while the corresponding native showed weak signals, the DNA duplex modified with electron-rich tellurium functionality showed strong topographic and current peaks by STM imaging, suggesting a potential strategy to directly image DNA without structural perturbation. © The Author(s) 2011. Published by Oxford University Press.

Synthesis, structure and imaging of oligodeoxyribonucleotides with tellurium-nucleobase derivatization

PubMed Central

Sheng, Jia; Hassan, Abdalla E. A.; Zhang, Wen; Zhou, Jianfeng; Xu, Bingqian; Soares, Alexei S.; Huang, Zhen

2011-01-01

We report here the first synthesis of 5-phenyl–telluride–thymidine derivatives and the Te-phosphoramidite. We also report here the synthesis, structure and STM current-imaging studies of DNA oligonucleotides containing the nucleobases (thymine) derivatized with 5-phenyl-telluride functionality (5-Te). Our results show that the 5-Te-DNA is stable, and that the Te-DNA duplex has the thermo-stability similar to the corresponding native duplex. The crystal structure indicates that the 5-Te-DNA duplex structure is virtually identical to the native one, and that the Te-modified T and native A interact similarly to the native T and A pair. Furthermore, while the corresponding native showed weak signals, the DNA duplex modified with electron-rich tellurium functionality showed strong topographic and current peaks by STM imaging, suggesting a potential strategy to directly image DNA without structural perturbation. PMID:21245037

Synthesis Structure and Imaging of Oligodeoxyribonucleotides with Tellurium-nucleobase Derivatization

DOE Office of Scientific and Technical Information (OSTI.GOV)

J Sheng; A Hassan; W Zhang

2011-12-31

We report here the first synthesis of 5-phenyl-telluride-thymidine derivatives and the Te-phosphoramidite. We also report here the synthesis, structure and STM current-imaging studies of DNA oligonucleotides containing the nucleobases (thymine) derivatized with 5-phenyl-telluride functionality (5-Te). Our results show that the 5-Te-DNA is stable, and that the Te-DNA duplex has the thermo-stability similar to the corresponding native duplex. The crystal structure indicates that the 5-Te-DNA duplex structure is virtually identical to the native one, and that the Te-modified T and native A interact similarly to the native T and A pair. Furthermore, while the corresponding native showed weak signals, the DNAmore » duplex modified with electron-rich tellurium functionality showed strong topographic and current peaks by STM imaging, suggesting a potential strategy to directly image DNA without structural perturbation.« less

Synthesis, structure and imaging of oligodeoxyribonucleotides with tellurium-nucleobase derivatization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheng, J.; Soares, A.; Hassan, A. E. A.

2011-05-01

We report here the first synthesis of 5-phenyl-telluride-thymidine derivatives and the Te-phosphoramidite. We also report here the synthesis, structure and STM current-imaging studies of DNA oligonucleotides containing the nucleobases (thymine) derivatized with 5-phenyl-telluride functionality (5-Te). Our results show that the 5-Te-DNA is stable, and that the Te-DNA duplex has the thermo-stability similar to the corresponding native duplex. The crystal structure indicates that the 5-Te-DNA duplex structure is virtually identical to the native one, and that the Te-modified T and native A interact similarly to the native T and A pair. Furthermore, while the corresponding native showed weak signals, the DNAmore » duplex modified with electron-rich tellurium functionality showed strong topographic and current peaks by STM imaging, suggesting a potential strategy to directly image DNA without structural perturbation.« less

Materials and structures for stretchable energy storage and conversion devices.

PubMed

Xie, Keyu; Wei, Bingqing

2014-06-11

Stretchable energy storage and conversion devices (ESCDs) are attracting intensive attention due to their promising and potential applications in realistic consumer products, ranging from portable electronics, bio-integrated devices, space satellites, and electric vehicles to buildings with arbitrarily shaped surfaces. Material synthesis and structural design are core in the development of highly stretchable supercapacitors, batteries, and solar cells for practical applications. This review provides a brief summary of research development on the stretchable ESCDs in the past decade, from structural design strategies to novel materials synthesis. The focuses are on the fundamental insights of mechanical characteristics of materials and structures on the performance of the stretchable ESCDs, as well as challenges for their practical applications. Finally, some of the important directions in the areas of material synthesis and structural design facing the stretchable ESCDs are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fundamental Studies of Crystal Growth of Microporous Materials

NASA Technical Reports Server (NTRS)

Singh, Ramsharan; Doolittle, John, Jr.; Payra, Pramatha; Dutta, Prabir K.; George, Michael A.; Ramachandran, Narayanan; Schoeman, Brian J.

2003-01-01

Microporous materials are framework structures with well-defined porosity, often of molecular dimensions. Zeolites contain aluminum and silicon atoms in their framework and are the most extensively studied amongst all microporous materials. Framework structures with P, Ga, Fe, Co, Zn, B, Ti and a host of other elements have also been made. Typical synthesis of microporous materials involve mixing the framework elements (or compounds, thereof) in a basic solution, followed by aging in some cases and then heating at elevated temperatures. This process is termed hydrothermal synthesis, and involves complex chemical and physical changes. Because of a limited understanding of this process, most synthesis advancements happen by a trial and error approach. There is considerable interest in understanding the synthesis process at a molecular level with the expectation that eventually new framework structures will be built by design. The basic issues in the microporous materials crystallization process include: (a) Nature of the molecular units responsible for the crystal nuclei formation; (b) Nature of the nuclei and nucleation process; (c) Growth process of the nuclei into crystal; (d) Morphological control and size of the resulting crystal; (e) Surface structure of the resulting crystals; and (f) Transformation of frameworks into other frameworks or condensed structures.

ACCESS 1: Approximation Concepts Code for Efficient Structural Synthesis program documentation and user's guide

NASA Technical Reports Server (NTRS)

Miura, H.; Schmit, L. A., Jr.

1976-01-01

The program documentation and user's guide for the ACCESS-1 computer program is presented. ACCESS-1 is a research oriented program which implements a collection of approximation concepts to achieve excellent efficiency in structural synthesis. The finite element method is used for structural analysis and general mathematical programming algorithms are applied in the design optimization procedure. Implementation of the computer program, preparation of input data and basic program structure are described, and three illustrative examples are given.

Fungi-assisted silver nanoparticle synthesis and their applications.

PubMed

Khan, Azhar U; Malik, Nazia; Khan, Masudulla; Cho, Moo Hwan; Khan, Mohammad Mansoob

2018-01-01

Nanotechnology is a rapidly developing field because of its wide range of applications in science, nanoscience and biotechnology. Nanobiotechnology deals with nanomaterials synthesised or modified using biotechnology. Fungi are used to synthesise metal nanoparticles and they have vast applications in wound healing, pathogen detection and control, food preservation, textiles, fabrics, etc. The present review describes the different types of fungi used for the biosyntheses of silver nanoparticles (AgNPs), along with their characterisation and possible biological applications. AgNPs synthesised by other physical and chemical methods are expensive and have toxic substances adsorbed onto them. Therefore, green, simple and effective approaches have been chosen for the biosynthesis of AgNPs, which are very important because of their lower toxicity and environmentally friendly behaviour. AgNPs synthesised using fungi have high monodispersity, specific composition and a narrow size range. In this regard, among the different biological methods used for metal nanoparticle synthesis, fungi are considered to be a superior biogenic method owing to their diversity and better size control. To further understand the biosynthesis of AgNPs using various fungi and evaluate their potential applications, this review discusses the antimicrobial, antibacterial, antifungal, antiviral, antidermatophytic, anti-inflammatory, antitumor, hepatoprotective, cytotoxic, hypotensive, and immunomodulatory activities of these AgNPs. The synthesis of AgNPs using fungi is a clean, green, inexpensive, eco-friendly, reliable, and safe method that can be used for a range of applications in real life for the benefit of human beings.

Manufacturing of Smart Structures Using Fiber Placement Manufacturing Processes

NASA Technical Reports Server (NTRS)

Thomas, Matthew M.; Glowasky, Robert A.; McIlroy, Bruce E.; Story, Todd A.

1996-01-01

Smart structures research and development, with the ultimate aim of rapid commercial and military production of these structures, are at the forefront of the Synthesis and Processing of Intelligent Cost-Effective Structures (SPICES) program. As part of this ARPA-sponsored program, MDA-E is using fiber placement processes to manufacture integrated smart structure systems. These systems comprise advanced composite structures with embedded fiber optic sensors, shape memory alloys, piezoelectric actuators, and miniature accelerometers. Cost-effective approaches and solutions to smart material synthesis in the fiber-placement process, based upon integrated product development, are discussed herein.

A decentralized linear quadratic control design method for flexible structures

NASA Technical Reports Server (NTRS)

Su, Tzu-Jeng; Craig, Roy R., Jr.

1990-01-01

A decentralized suboptimal linear quadratic control design procedure which combines substructural synthesis, model reduction, decentralized control design, subcontroller synthesis, and controller reduction is proposed for the design of reduced-order controllers for flexible structures. The procedure starts with a definition of the continuum structure to be controlled. An evaluation model of finite dimension is obtained by the finite element method. Then, the finite element model is decomposed into several substructures by using a natural decomposition called substructuring decomposition. Each substructure, at this point, still has too large a dimension and must be reduced to a size that is Riccati-solvable. Model reduction of each substructure can be performed by using any existing model reduction method, e.g., modal truncation, balanced reduction, Krylov model reduction, or mixed-mode method. Then, based on the reduced substructure model, a subcontroller is designed by an LQ optimal control method for each substructure independently. After all subcontrollers are designed, a controller synthesis method called substructural controller synthesis is employed to synthesize all subcontrollers into a global controller. The assembling scheme used is the same as that employed for the structure matrices. Finally, a controller reduction scheme, called the equivalent impulse response energy controller (EIREC) reduction algorithm, is used to reduce the global controller to a reasonable size for implementation. The EIREC reduced controller preserves the impulse response energy of the full-order controller and has the property of matching low-frequency moments and low-frequency power moments. An advantage of the substructural controller synthesis method is that it relieves the computational burden associated with dimensionality. Besides that, the SCS design scheme is also a highly adaptable controller synthesis method for structures with varying configuration, or varying mass and stiffness properties.

Oxidative condensation reactions of (diethylenetriamine)cobalt(III) complexes with substituted bis(pyridin-2-yl)methane ligands

NASA Astrophysics Data System (ADS)

Zhou, Xiangting; Hockless, David C. R.; Willis, Anthony C.; Jackson, W. Gregory

2005-04-01

The synthesis and characterisation of Co(III) complexes derived from a condensation reaction with a central or terminal nitrogen of a dien ligand and the α-carbon of a range of substituted bis(pyridin-2-yl)methane ligands are described. Aerial oxidation of bpm {bis(pyridin-2-yl)methane with Co(II)/dien or direct reaction with Co(dien)Cl 3 provided in low yield a single C-N condensation product 1 (at the primary terminal NH 2) after the pyridyl -CH 2- is formally oxidised to -CH +-. The methyl substituted ligand bpe {1,1-bis(pyridin-2-yl)ethane} behaves likewise, except both terminal (prim) and central (sec) amines condense to yield isomeric products 2 and 3. Two of these three materials have been characterised by single crystal X-ray crystallography. The corresponding reactions for the bis(pyridyl) ligand bpk {bis(pyridin-2-yl)ketone} provided C-N condensation products without the requirement for oxidation at the α-C center; two carbinolamine complexes in different geometrical configurations resulted, mer-anti-[Co(dienbpc)Cl]ZnCl 4, 5, and unsym- fac-[Co(dienbpc)Cl]ZnCl 4, 6, {dienbpc=[2-(2-aminoethylamino)-ethylamino]-di-pyridin-2-yl-methanol}. In addition, a novel complex, [Co(bpk)(bpd-OH)Cl]ZnCl 4, 4, in which one bidentate N, N-bonded bpk ligand and one tridentate N, O, N-bonded bpd (the diol from bpk+OH -) were coordinated, was obtained via the Co(II)/O 2 synthetic route. When the bpc ligand (bpc=bis(pyridin-2-yl)methanol) was employed directly as a reagent along with dien, no condensation reactions were observed, but rather a single isomeric complex [Co(dien)(bpc)]Cl.ZnCl 4, 7, in which the ligand bpc acted as a N,N,O-bonded tridentate ligand rather than as a N,N-bidentate ligand was isolated. 13C, 1D and 2D 1H NMR studies are reported for all the complexes; they establish the structures unambiguously.

Synthesis and characterisation of the n = 2 Ruddlesden–Popper phases Ln{sub 2}Sr(Ba)Fe{sub 2}O{sub 7} (Ln = La, Nd, Eu)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurusinghe, Nicola N.M.; Figuera, Juand de la; Marco, José F.

2013-09-01

Graphical abstract: - Highlights: • Some Ruddlesden–Popper phases have been characterised. • Substitution on the A site influences cationic order. • The magnetic moment redirects with temperature - Abstract: A series of n = 2 Ruddlesden–Popper phases A{sub 2}B{sub 2}O{sub 7} of composition Ln{sub 2}Sr(Ba)Fe{sub 2}O{sub 7} (Ln = La, Nd, Eu) have been prepared. La{sub 2}SrFe{sub 2}O{sub 7} and La{sub 2}BaFe{sub 2}O{sub 7} crystallise in the tetragonal space group I4/mmm. The structures of Eu{sub 2}SrFe{sub 2}O{sub 7} and Nd{sub 2}SrFe{sub 2}O{sub 7} are best described in space group P4{sub 2}/mnm. Substitution on the A site with smaller lanthanide- andmore » larger alkaline metal- ions leads to enhanced cationic order in these phases and reflects increasing differences in cationic radii. All the compounds are antiferromagnetically ordered between 298 and 2 K. In La{sub 2}SrFe{sub 2}O{sub 7} the magnetic moment lies along [1 1 0] at all temperatures between 298 and 2 K whereas in La{sub 2}BaFe{sub 2}O{sub 7} the magnetic moment at 298 K lies along the crystallographic x-axis but redirects from the [1 0 0] to the [1 1 0] direction between 210 and 190 K and is retained in this direction until 2 K. In Nd{sub 2}SrFe{sub 2}O{sub 7} the magnetic moment at 298 K lies along [1 1 0] but rotates from [1 1 0] to [0 0 1] between 17 and 9 K. A series of {sup 57}Fe Mössbauer spectra recorded from La{sub 2}SrFe{sub 2}O{sub 7} between 290 and 600 K indicate a magnetic ordering temperature of T{sub N} ≥ 535 K.« less

Folate/NIR 797-Conjugated Albumin Magnetic Nanospheres: Synthesis, Characterisation, and In Vitro and In Vivo Targeting Evaluation

PubMed Central

Liu, Dongfang; Liu, Peidang; Zhang, Dongsheng

2014-01-01

A practical and effective strategy for synthesis of Folate-NIR 797-conjugated Magnetic Albumin Nanospheres (FA-NIR 797-MAN) was developed. For this strategy, Magnetic Albumin Nanospheres (MAN), composed of superparamagnetic iron oxide nanoparticles (SPIONs) and bovine serum albumin (BSA), were covalently conjugated with folic acid (FA) ligands to enhance the targeting capability of the particles to folate receptor (FR) over-expressing tumours. Subsequently, a near-infrared (NIR) fluorescent dye NIR 797 was conjugated with FA-conjugated MAN for in vivo fluorescence imaging. The FA-NIR 797-MAN exhibited low toxicity to a human nasopharyngeal epidermal carcinoma cell line (KB cells). Additionally, in vitro and in vivo evaluation of the dynamic behaviour and targeting ability of FA-NIR 797-MAN to KB tumours validated the highly selective affinity of FA-NIR 797-MAN for FR-positive tumours. In summary, the FA-NIR 797-MAN prepared here exhibited great potential for tumour imaging, since the near-infrared fluorescence contrast agents target cells via FR-mediated endocytosis. The high fluorescence intensity together with the targeting effect makes FA-NIR 797-MAN a promising candidate for imaging, monitoring, and early diagnosis of cancer at the molecular and cellular levels. PMID:25188308

Characters related to higher starch accumulation in cassava storage roots

PubMed Central

Li, You-Zhi; Zhao, Jian-Yu; Wu, San-Min; Fan, Xian-Wei; Luo, Xing-Lu; Chen, Bao-Shan

2016-01-01

Cassava (Manihot esculenta) is valued mainly for high content starch in its roots. Our understanding of mechanisms promoting high starch accumulation in the roots is, however, still very limited. Two field-grown cassava cultivars, Huanan 124(H124) with low root starch and Fuxuan 01(F01) with high root starch, were characterised comparatively at four main growth stages. Changes in key sugars in the leaves, stems and roots seemed not to be strongly associated with the final amount of starch accumulated in the roots. However, when compared with H124, F01 exhibited a more compact arrangement of xylem vascular bundles in the leaf axils, much less callose around the phloem sieve plates in the stems, higher starch synthesis-related enzymatic activity but lower amylase activity in the roots, more significantly up-regulated expression of related genes, and a much higher stem flow rate (SFR). In conclusion, higher starch accumulation in the roots results from the concurrent effects of powerful stem transport capacity highlighted by higher SFR, high starch synthesis but low starch degradation in the roots, and high expression of sugar transporter genes in the stems. A model of high starch accumulation in cassava roots was therefore proposed and discussed. PMID:26892156

Characters related to higher starch accumulation in cassava storage roots.

PubMed

Li, You-Zhi; Zhao, Jian-Yu; Wu, San-Min; Fan, Xian-Wei; Luo, Xing-Lu; Chen, Bao-Shan

2016-02-19

Cassava (Manihot esculenta) is valued mainly for high content starch in its roots. Our understanding of mechanisms promoting high starch accumulation in the roots is, however, still very limited. Two field-grown cassava cultivars, Huanan 124(H124) with low root starch and Fuxuan 01(F01) with high root starch, were characterised comparatively at four main growth stages. Changes in key sugars in the leaves, stems and roots seemed not to be strongly associated with the final amount of starch accumulated in the roots. However, when compared with H124, F01 exhibited a more compact arrangement of xylem vascular bundles in the leaf axils, much less callose around the phloem sieve plates in the stems, higher starch synthesis-related enzymatic activity but lower amylase activity in the roots, more significantly up-regulated expression of related genes, and a much higher stem flow rate (SFR). In conclusion, higher starch accumulation in the roots results from the concurrent effects of powerful stem transport capacity highlighted by higher SFR, high starch synthesis but low starch degradation in the roots, and high expression of sugar transporter genes in the stems. A model of high starch accumulation in cassava roots was therefore proposed and discussed.

Calcium silicates synthesised from industrial residues with the ability for CO2 sequestration.

PubMed

Morales-Flórez, Victor; Santos, Alberto; López, Antonio; Moriña, Isabel; Esquivias, Luis

2014-12-01

This work explored several synthesis routes to obtain calcium silicates from different calcium-rich and silica-rich industrial residues. Larnite, wollastonite and calcium silicate chloride were successfully synthesised with moderate heat treatments below standard temperatures. These procedures help to not only conserve natural resources, but also to reduce the energy requirements and CO2 emissions. In addition, these silicates have been successfully tested as carbon dioxide sequesters, to enhance the viability of CO2 mineral sequestration technologies using calcium-rich industrial by-products as sequestration agents. Two different carbon sequestration experiments were performed under ambient conditions. Static experiments revealed carbonation efficiencies close to 100% and real-time resolved experiments characterised the dynamic behaviour and ability of these samples to reduce the CO2 concentration within a mixture of gases. The CO2 concentration was reduced up to 70%, with a carbon fixation dynamic ratio of 3.2 mg CO2 per g of sequestration agent and minute. Our results confirm the suitability of the proposed synthesis routes to synthesise different calcium silicates recycling industrial residues, being therefore energetically more efficient and environmentally friendly procedures for the cement industry. © The Author(s) 2014.

Quality of life of people with mental health problems: a synthesis of qualitative research

PubMed Central

2012-01-01

Purpose To identify the domains of quality of life important to people with mental health problems. Method A systematic review of qualitative research undertaken with people with mental health problems using a framework synthesis. Results We identified six domains: well-being and ill-being; control, autonomy and choice; self-perception; belonging; activity; and hope and hopelessness. Firstly, symptoms or ‘ill-being’ were an intrinsic aspect of quality of life for people with severe mental health problems. Additionally, a good quality of life was characterised by the feeling of being in control (particularly of distressing symptoms), autonomy and choice; a positive self-image; a sense of belonging; engagement in meaningful and enjoyable activities; and feelings of hope and optimism. Conversely, a poor quality life, often experienced by those with severe mental health difficulties, was characterized by feelings of distress; lack of control, choice and autonomy; low self-esteem and confidence; a sense of not being part of society; diminished activity; and a sense of hopelessness and demoralization. Conclusions Generic measures fail to address the complexity of quality of life measurement and the broad range of domains important to people with mental health problems. PMID:23173689

Strategies for the profiling, characterisation and detailed structural analysis of N-linked oligosaccharides.

PubMed

Tharmalingam, Tharmala; Adamczyk, Barbara; Doherty, Margaret A; Royle, Louise; Rudd, Pauline M

2013-02-01

Many post-translational modifications, including glycosylation, are pivotal for the structural integrity, location and functional activity of glycoproteins. Sub-populations of proteins that are relocated or functionally changed by such modifications can change resting proteins into active ones, mediating specific effector functions, as in the case of monoclonal antibodies. To ensure safe and efficacious drugs it is essential to employ appropriate robust, quantitative analytical strategies that can (i) perform detailed glycan structural analysis, (ii) characterise specific subsets of glycans to assess known critical features of therapeutic activities (iii) rapidly profile glycan pools for at-line monitoring or high level batch to batch screening. Here we focus on these aspects of glycan analysis, showing how state-of-the-art technologies are required at all stages during the production of recombinant glycotherapeutics. These data can provide insights into processing pathways and suggest markers for intervention at critical control points in bioprocessing and also critical decision points in disease and drug monitoring in patients. Importantly, these tools are now enabling the first glycome/genome studies in large populations, allowing the integration of glycomics into other 'omics platforms in a systems biology context.

Characterisation of microbial communities in Chinese liquor fermentation starters Daqu using nested PCR-DGGE.

PubMed

Zhang, Liqiang; Wu, Chongde; Ding, Xiaofei; Zheng, Jia; Zhou, Rongqing

2014-12-01

In this study, characterises of the microbial community structures of three typical Chinese liquor Daqu, as well as different kinds of light flavour Daqu were investigated using nested PCR-denaturing gradient gel electrophoresis (DGGE). The results showed that microbial diversity was considerably different, and the microfloral compositions were highly variable among various Daqu. Lactic acid bacteria, which accounted for 30.95 % of all identified bacteria, were dominant in all Daqu samples, whereas Bacillus species were also predominant in the Luzhou (14.8 %) and Langjiu Daqu (18.2 %). Citrobacter and Burkholderia were first identified in light flavour Daqu. Aspergillus was the dominant moulds, and the non-Saccharomyces yeast species, Saccharomycopsis fibuligera, Wallemia sebi, Wallemia muriae, and Pichia subpelliculosa, were the dominant yeasts. Rasamsonia, Galactomyces, Geotrichum and Wallemia were first identified using nested PCR-DGGE. Cluster analysis indicated that the microbial community structures of different Daqu samples exhibited some differences. These may be ascribed to the different peak production temperatures, raw material constituents and microhabitats around the liquor enterprises. The current study provides insights into the microbial community structures of three typical Daqu samples, and may facilitate the development of starter cultures for manufacturing Chinese liquor.

Surface analysis characterisation of gum binders used in modern watercolour paints

NASA Astrophysics Data System (ADS)

Sano, Naoko; Cumpson, Peter J.

2016-02-01

Conducting this study has demonstrated that not only SEM-EDX but also XPS can be an efficient tool for characterising watercolour paint surfaces. We find that surface effects are mediated by water. Once the powdered components in the watercolour come into contact with water they dramatically transform their chemical structures at the surface and show the presence of pigment components with a random dispersion within the gum layer. Hence the topmost surface of the paint is confirmed as being composed of the gum binder components. This result is difficult to confirm using just one analytical technique (either XPS or SEM-EDX). In addition, peak fitting of C1s XPS spectra suggests that the gum binder in the commercial watercolour paints is probably gum arabic (by comparison with the reference materials). This identification is not conclusive, but the combination techniques of XPS and SEM shows the surface structure with material distribution of the gum binder and the other ingredients of the watercolour paints. Therefore as a unique technique, XPS combined with SEM-EDX may prove a useful method in the study of surface structure for not only watercolour objects but also other art objects; which may in future help in the conservation for art.

Mid-infrared and near-infrared spectroscopic study of selected magnesium carbonate minerals containing ferric iron-Implications for the geosequestration of greenhouse gases.

PubMed

Frost, Ray L; Reddy, B Jagannadha; Bahfenne, Silmarilly; Graham, Jessica

2009-04-01

The proposal to remove greenhouse gases by pumping liquefied CO(2) several kilometres below the ground implies that many carbonate containing minerals will be formed. Among these minerals brugnatellite and coalingite are probable. Two ferric ion bearing minerals brugnatellite and coalingite with a hydrotalcite-like structure have been characterised by a combination of infrared and near-infrared (NIR) spectroscopy. The infrared spectra of the OH stretching region are characterised by OH and water stretching vibrations. Both the first and second fundamental overtones of these bands are observed in the NIR spectra in the 7030-7235 cm(-1) and 10,490-10,570 cm(-1) regions. Intense (CO(3))(2-) symmetric and antisymmetric stretching vibrations support the concept that the carbonate ion is distorted. The position of the water bending vibration indicates the water is strongly hydrogen bonded in the mineral structure. Split NIR bands at around 8675 and 11,100 cm(-1) indicate that some replacement of magnesium ions by ferrous ions in the mineral structure has occurred. Near-infrared spectroscopy is ideal for the assessment of the formation of carbonate minerals.

Metabolism of the broad-spectrum neuropeptide growth factor antagonist: [D-Arg1, D-Phe5, D-Trp7,9, Leu11]-substance P.

PubMed Central

Jones, D. A.; Cummings, J.; Langdon, S. P.; Maclellan, A. J.; Higgins, T.; Rozengurt, E.; Smyth, J. F.

1996-01-01

Broad-spectrum neuropeptide growth factor antagonists, such as [D-Arg1, D-Phe5, D-Trp7,9, Leu11]substance P (antagonist D) and [Arg6, D-Trp7,9, NmePhe8]substance P(6-11) (antagonist G), are currently being investigated as possible anti-tumour agents. These compounds are hoped to be effective against neuropeptide-driven cancers such as small-cell lung cancer. Antagonist D possesses a broader antagonistic spectrum than antagonist G and hence may be of greater therapeutic use. The in vitro metabolism of antagonist D has been characterised and the structures of two major metabolites have been elucidated by amino acid analysis and mass spectrometry. Metabolism was confined to the C-terminus where serine carboxypeptidase action produced [deamidated]-antagonist D (metabolite 1) and [des-Leu11]-antagonist D (metabolite 2) as the major metabolites. Biological characterisation of the metabolites demonstrated that these relatively minor changes in structure resulted in a loss of antagonist activity. These results provide some of the first structure-activity information on the factors that determine which neuropeptides these compounds inhibit and on the relative potency of that inhibition. PMID:8611370

Identification and topographical characterisation of microbial nanowires in Nostoc punctiforme.

PubMed

Sure, Sandeep; Torriero, Angel A J; Gaur, Aditya; Li, Lu Hua; Chen, Ying; Tripathi, Chandrakant; Adholeya, Alok; Ackland, M Leigh; Kochar, Mandira

2016-03-01

Extracellular pili-like structures (PLS) produced by cyanobacteria have been poorly explored. We have done detailed topographical and electrical characterisation of PLS in Nostoc punctiforme PCC 73120 using transmission electron microscopy (TEM) and conductive atomic force microscopy (CAFM). TEM analysis showed that N. punctiforme produces two separate types of PLS differing in their length and diameter. The first type of PLS are 6-7.5 nm in diameter and 0.5-2 µm in length (short/thin PLS) while the second type of PLS are ~20-40 nm in diameter and more than 10 µm long (long/thick PLS). This is the first study to report long/thick PLS in N. punctiforme. Electrical characterisation of these two different PLS by CAFM showed that both are electrically conductive and can act as microbial nanowires. This is the first report to show two distinct PLS and also identifies microbial nanowires in N. punctiforme. This study paves the way for more detailed investigation of N. punctiforme nanowires and their potential role in cell physiology and symbiosis with plants.

pTcGW plasmid vectors 1.1 version: a versatile tool for Trypanosoma cruzi gene characterisation

PubMed Central

Kugeratski, Fernanda G; Batista, Michel; Inoue, Alexandre Haruo; Ramos, Bruno Dias; Krieger, Marco Aurelio; Marchini/, Fabricio K

2015-01-01

The functional characterisation of thousands of Trypanosoma cruzi genes remains a challenge. Reverse genetics approaches compatible with high-throughput cloning strategies can provide the tool needed to tackle this challenge. We previously published the pTcGW platform, composed by plasmid vectors carrying different options of N-terminal fusion tags based on Gateway® technology. Here, we present an improved 1.1 version of pTcGW vectors, which is characterised by a fully flexible structure allowing an easy customisation of each element of the vectors in a single cloning step. Additionally, both N and C-terminal fusions are available with new tag options for protein complexes purification. Three of the newly created vectors were successfully used to determine the cellular localisation of four T. cruzi proteins. The 1.1 version of pTcGW platform can be used in a variety of assays, such as protein overexpression, identification of protein-protein interaction and protein localisation. This powerful and versatile tool allows adding valuable functional information to T. cruzi genes and is freely available for scientific community. PMID:26200713

From an 'ice-see' perspective: The current use, potential and limitations of Structure-from-Motion photogrammetry for cryospheric applications

NASA Astrophysics Data System (ADS)

Westoby, Matthew; Dunning, Stuart; Allan, Mark; Smith, Mark; Quincey, Duncan; Carrivick, Jonathan; Watson, C. Scott

2016-04-01

Structure-from-Motion with Multi-View Stereo (SfM-MVS) methods are rapidly becoming the tool of choice for geoscientists who require a relatively low-cost and viable alternative to traditional surveying technologies for characterising the form and short-term evolution of Earth surface landforms and landscapes. Uptake of SfM-MVS methods by workers in the cryospheric science community has been particularly rapid. The choice to use SfM-MVS has many logistical benefits which promote its adoption in remote glacial environments, namely the requirement for little more than a digital camera and proprietary or open-source software for topographic reconstruction, and a surveyed network of ground control to transform the resultant 3D models into a real-world co-ordinate system, if desired. Optionally, a dedicated aerial photography platform (e.g. kite, blimp, multirotor or fixed-wing UAV) may be used for initial photograph acquisition, which can facilitate glacier-scale observation and analysis. To date, cryospheric applications of SfM-MVS have included: the monitoring of glacier, moraine, and rock glacier movement; the evolution of ice cliffs on debris-covered glaciers; the reconstruction of ice-marginal or deglaciated topography; patch- and moraine-scale sedimentological characterisation; and the characterisation of glacier surfaces to monitor supraglacial drainage development or to inform energy balance modelling. This contribution will showcase existing applications and original data and discuss exciting potential opportunities and current limitations of the SfM-MVS method for the cryospheric sciences.

Synthesis-Structure-Activity Relationships in Co3O4 Catalyzed CO Oxidation

NASA Astrophysics Data System (ADS)

Mingle, Kathleen; Lauterbach, Jochen

2018-05-01

In this work, a statistical design and analysis platform was used to develop cobalt oxide based oxidation catalysts prepared via one pot metal salt reduction. An emphasis was placed upon understanding the effects of synthesis conditions, such as heating regimen and Co2+ concentration on the metal salt reduction mechanism, the resultant nanomaterial properties (i.e. size, crystal structure, and crystal faceting), and the catalytic activity in CO oxidation. This was accomplished by carrying out XRD, TEM, and FTIR studies on synthesis intermediates and products. Additionally, high-throughput experimentation was employed to study the performance of Co3O4 oxidation catalysts over a wide range of reaction conditions using a 16-channel fixed bed reactor equipped with a parallel infrared imaging system. Specifically, Co3O4 nanomaterials of varying properties were evaluated for their performance as CO oxidation catalysts. Figure-of-merits including light-off temperatures and activation energies were measured and mapped back to the catalyst properties and synthesis conditions. Statistical analysis methods were used to elucidate significant property-activity relationships as well as the design rules relevant in the synthesis of active catalysts. It was found that CO oxidation light off temperatures could be decreased to <90°C by utilizing the discovered synthesis-structure-activity relationships.

Preschool Teachers' Views on Children's Learning: An International Perspective

ERIC Educational Resources Information Center

Broström, Stig; Sandberg, Anette; Johansson, Inge; Margetts, Kay; Nyland, Berenice; Frøkjaer, Thorleif; Kieferle, Christa; Seifert, Anja; Roth, Angela; Ugaste, Aino; Vrinioti, Kalliope

2015-01-01

This comparative study investigated the perspectives of preschool teachers in Australia, Denmark, Estonia, German, Greece and Sweden about learning and participation in preschool. A structured survey questionnaire investigated four main questions: What situations can be characterised as learning? What activities are important for learning? What…

Subjective Theories of Indonesian Agronomy and Biology Teacher Students on Environmental Commons Dilemmas

ERIC Educational Resources Information Center

Koch, Sebastian; Barkmann, Jan; Sundawati, Leti; Bogeholz, Susanne

2013-01-01

Fostering the cognitive skills to analyse environmental "commons dilemmas" is an urgent task of environmental education globally. Commons dilemmas are characterised by structural incentives to overexploit a natural resource; their solution is particularly pressing in threatened biodiversity "hotspot" areas. Solutions to these…

Improved reservoir characterisation using fuzzy logic platform: an integrated petrophysical, seismic structural and poststack inversion study

NASA Astrophysics Data System (ADS)

Jafri, Muhammad Kamran; Lashin, Aref; Ibrahim, El-Khedr Hassan; Hassanein, Kamal A.; Al Arifi, Nassir; Naeem, Muhammad

2017-06-01

There is a tendency for applying different integrated geophysical approaches for better hydrocarbon reservoir characterisation and interpretation. In this study, petrophysical properties, seismic structural and poststack seismic inversion results are integrated using the fuzzy logic AND operator to characterise the Tensleep Sandstone Formation (TSF) at Powder River Basin (PRB), Wyoming, USA. TSF is deposited in a coastal plain setting during the Pennsylvanian era, and contains cross-bedded sandstone of Aeolian origin as a major lithology with alternative sabkha dolomite/carbonates. Wireline logging datasets from 17 wells are used for the detailed petrophysical evaluation. Three units of the TSF (A-sandstone, B-dolomite and B-sandstone) are targeted and their major rock properties estimated (i.e. shale/clay volume, Vsh; porosity, φEff permeability, K; fluid saturations, Sw and SH; and bulk volume water, BVW). The B-sandstone zone, with its petrophysical properties of 5-20% effective porosity, 0.10-250 mD permeability and hydrocarbon potential up to 72%, is considered the best reservoir zone among the three studied units. Distributions of the most important petrophysical parameters of the B-sandstone reservoir (Vsh, φEff, K, Sw) are generated as GIS thematic layers. The two-dimensional (2D) and three-dimensional (3D) seismic structural interpretations revealed that the hydrocarbons are entrapped in an anticlinal structure bounded with fault closures at the west of the study area. Poststack acoustic impedance (PSAI) inversion is performed on 3D seismic data to extract the inverted acoustic impedance (AI) cube. Two attribute slices (inverted AI and seismic amplitude) were extracted at the top of the B-sandstone unit as GIS thematic layers. The reservoir properties and inverted seismic attributes were then integrated using fuzzy AND operator. Finally, a fuzzy reservoir quality map was produced, and a prospective reservoir area with best reservoir characteristics is proposed for future exploration. The current study showed that integration of petrophysical, seismic structural and poststack inversion under a fuzzy logic platform can be used as an effective tool for interpreting multiple reservoir zones.

Effect of synthesis conditions on the nanopowder properties of Ce{sub 0.9}Zr{sub 0.1}O{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zimicz, M.G.; Fabregas, I.O.; Lamas, D.G.

Graphical abstract: . The synthesis of nanocrystalline Ce{sub 0.9}Zr{sub 0.1}O{sub 2} powders via the gel-combustion method, using different fuels, and following either stoichiometric or non-stoichiometric pH-controlled routes is investigated. Research highlights: {yields} All samples exhibited the fluorite-type crystal structure, nanometric average crystallite size and negligible carbon content. {yields} Synthesis conditions strongly affect the average crystallite size, the degree of agglomeration, the specific surface area and the pore volume. {yields} Our results indicate that, by controlling the synthesis conditions it is possible to obtain solids with custom-made morphological properties. -- Abstract: In this work, the synthesis of nanocrystalline Ce{sub 0.9}Zr{sub 0.1}O{submore » 2} powders via the gel-combustion method, using different fuels, and following either stoichiometric or non-stoichiometric pH-controlled routes is investigated. The objective is to evaluate the effect of synthesis conditions on the textural and morphological properties, and the crystal structure of the synthesized materials. The solids were characterized by nitrogen physisorption, Scanning Electron Microscopy (SEM), X-ray powder diffraction (XPD), and Carbon-Hydrogen-Nitrogen Elemental Analysis (CHN). All the powders exhibited nanometric crystallite size, fluorite-type structure and negligible carbon content. Synthesis conditions strongly affect the average crystallite size, the degree of agglomeration, the specific surface area and the pore volume. Our results indicate that, by controlling the synthesis conditions it is possible to obtain solids with custom-made morphological properties.« less

Rapid and Convenient Synthesis of the 1,4-Dihydropyridine Privileged Structure

ERIC Educational Resources Information Center

Cheung, Lawrence L. W.; Styler, Sarah A.; Dicks, Andrew P.

2010-01-01

A short, semi-microscale synthesis of two 1,4-dihydropyridine drug analogues via a Hantzsch reaction is described, which is appropriate for a second-year undergraduate organic laboratory. Products are specifically chosen to highlight the biological relevance of this compound type while introducing the notion of a privileged structure.…

Synthesis of "Meso"-Diethyl-2,2'-Dipyrromethane in Water: An Experiment in Green Organic Chemistry

ERIC Educational Resources Information Center

Sobral, Abilio J. F. N.

2006-01-01

Dipyrromethanes (or dipyrrilmethanes) are important building blocks for many of the structures of interest in the areas of porphyrins, materials science, optics, and medicine. A variety of conditions have been established for the synthesis of dipyrromethanes of diverse structures, from substituted pyrroles to unsubstituted pyrrole and carbonyl…

Oligomeric flavanoids. Part 26. Structure and synthesis of the first profisetinidins with epifisetinidol constituent units

Treesearch

Petrus J. Steynberg; Jan P. Steynberg; E. Vincent Brandt; Daneel Ferreira; Richard W. Hemingway

1997-01-01

The natural occurrence of the first oligomeric profisetinidins with (2R,3R}-2,3-cis-epifisetinidol chain extender units is demonstrated in the bark of Pithecellobium dulce (Guamuchil). Semi-synthesis using the appropriate flavan-3-ol and flavan-3,4-diol precursors permits unequivocal structural...

77 FR 58931 - Technical Corrections Relating to the Rules of Origin for Goods Imported Under the NAFTA and for...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-09-25

... from subheading 3502.90; or A change to peptones and their derivatives, other protein substances and..., prostagladins, thromboxanes and leukotrienes, natural or reproduced by synthesis, derivatives and structural..., thromboxanes and leukotrienes, natural or reproduced by synthesis or derivatives, and structural analogues...

Synthesis facilitates an understanding of the structural basis for translation inhibition by the lissoclimides

NASA Astrophysics Data System (ADS)

Könst, Zef A.; Szklarski, Anne R.; Pellegrino, Simone; Michalak, Sharon E.; Meyer, Mélanie; Zanette, Camila; Cencic, Regina; Nam, Sangkil; Voora, Vamsee K.; Horne, David A.; Pelletier, Jerry; Mobley, David L.; Yusupova, Gulnara; Yusupov, Marat; Vanderwal, Christopher D.

2017-11-01

The lissoclimides are unusual succinimide-containing labdane diterpenoids that were reported to be potent cytotoxins. Our short semisynthesis and analogue-oriented synthesis approaches provide a series of lissoclimide natural products and analogues that expand the structure-activity relationships (SARs) in this family. The semisynthesis approach yielded significant quantities of chlorolissoclimide (CL) to permit an evaluation against the National Cancer Institute's 60-cell line panel and allowed us to obtain an X-ray co-crystal structure of the synthetic secondary metabolite with the eukaryotic 80S ribosome. Although it shares a binding site with other imide-based natural product translation inhibitors, CL engages in a particularly interesting and novel face-on halogen-π interaction between the ligand's alkyl chloride and a guanine residue. Our analogue-oriented synthesis provides many more lissoclimide compounds, which were tested against aggressive human cancer cell lines and for protein synthesis inhibitory activity. Finally, computational modelling was used to explain the SARs of certain key compounds and set the stage for the structure-guided design of better translation inhibitors.

Organization of Genes Required for the Oxidation of Methanol to Formaldehyde in Three Type II Methylotrophs

PubMed Central

Bastien, C.; Machlin, S.; Zhang, Y.; Donaldson, K.; Hanson, R. S.

1989-01-01

Restriction maps of genes required for the synthesis of active methanol dehydrogenase in Methylobacterium organophilum XX and Methylobacterium sp. strain AM1 have been completed and compared. In these two species of pink-pigmented, type II methylotrophs, 15 genes were identified that were required for the expression of methanol dehydrogenase activity. None of these genes were required for the synthesis of the prosthetic group of methanol dehydrogenase, pyrroloquinoline quinone. The structural gene required for the synthesis of cytochrome cL, an electron acceptor uniquely required for methanol dehydrogenase, and the genes encoding small basic peptides that copurified with methanol dehydrogenases were closely linked to the methanol dehydrogenase structural genes. A cloned 22-kilobase DNA insert from Methylsporovibrio methanica 81Z, an obligate type II methanotroph, complemented mutants that contained lesions in four genes closely linked to the methanol dehydrogenase structural genes. The methanol dehydrogenase and cytochrome cL structural genes were found to be transcribed independently in M. organophilum XX. Only two of the genes required for methanol dehydrogenase synthesis in this bacterium were found to be cotranscribed. PMID:16348074

Chemical synthesis and NMR characterization of structured polyunsaturated triacylglycerols.

PubMed

Fauconnot, Laëtitia; Robert, Fabien; Villard, Renaud; Dionisi, Fabiola

2006-02-01

The chemical synthesis of pure triacylglycerol (TAG) regioisomers, that contain long chain polyunsaturated fatty acids, such as arachidonic acid (AA) or docosahexaenoic acid (DHA), and saturated fatty acids, such as lauric acid (La) or palmitic acid (P), at defined positions, is described. A single step methodology using (benzotriazol-1-yloxy)-tripyrrolidinophosphonium hexafluorophosphate (PyBOP), an activator of carboxyl group commonly used in peptide synthesis and occasionally used in carboxylic acid esterification, has been developed for structured TAG synthesis. Identification of the fatty acyl chains for each TAG species was confirmed by atmospheric pressure chemical ionisation mass spectrometry (APCI-MS) and fatty acid positional distribution was determined by (1)H and (13)C NMR spectra. The generic described procedures can be applied to a large variety of substrates and was used for the production of specific triacylglycerols of defined molecular structures, with high regioisomeric purity. Combination of MS and NMR was shown to be an efficient tool for structural analysis of TAG. In particular, some NMR signals were demonstrated to be regioisomer specific, allowing rapid positional analysis of LC-PUFA containing TAG.

Carbon nanopipettes and microtubes for electrochemical sensing and microfluidics

NASA Astrophysics Data System (ADS)

Mani, Radhika C.; Bhimarasetti, Gopinath; Lowe, Randall; Sunkara, Mahendra K.

2004-12-01

We present the synthesis of two novel morphologies for carbon tubular structures: Nanopipettes and Micropipes. The synthesis procedures for both these structures are both unique and different from each other and the conventional methods used for carbon nanotubes. Carbon nanopipettes, open at both ends, are made up of a central nanotube (~10-20 nm) surrounded by helical sheets of graphite. Thus nanopipettes have an outer conical structure, with a base size of about a micron, that narrows down to about 10-20 nm at the tip. Due to their unique morphology, the outer walls of the nanopipettes continuously expose edge planes of graphite, giving a very stable and reversible electrochemical response for detecting neurological compounds such as dopamine. The synthesis of carbon nanopipettes is based on high temperature nucleation and growth of carbon nanotubes under conditions of hydrogen etching during growth. Carbon micropipes, on the other hand, are tubular structures whose internal diameters range from a few nanometers to a few microns with a constant wall thickness of 10-20 nm. In addition to tuning the internal diameters, the conical angles of these structures could also be changed during synthesis. Due to their larger inner diameters and thin walls, both the straight and conical micro-tubular structures are suitable for microfluidic devices such as throttle valves, micro-reactors, and distribution channels. The synthesis of carbon micro-tubular structures is based on the wetting behavior of gallium with carbon during growth. The contact angle between gallium and the carbon wall determines the conical angle of the structure. By varying the contact angle, one can alter the conical angles from 400 to -150, and synthesize straight tubes using different N2/O2 dosing compositions. An 'n-step' dosing sequence at various stages of growth resulted in 'n-staged' morphologies for carbon micro-tubular structures such as funnels, tube-on-cone, Y-junctions and dumbbells.

Synthesis and characterisation of ionic liquids based on 1-butyl-3-methylimidazolium chloride and MCl(4), M = Hf and Zr.

PubMed

Campbell, Paul S; Santini, Catherine C; Bouchu, Denis; Fenet, Bernard; Rycerz, Leszek; Chauvin, Yves; Gaune-Escard, Marcelle; Bessada, Catherine; Rollet, Anne-Laure

2010-02-07

Dialkylimidazolium chlorometallate molten salts resulting from the combination of zirconium or hafnium tetrachloride and 1-butyl-3-methylimidazolium chloride, [C(1)C(4)Im][Cl], have been prepared with a molar fraction of MCl(4), R = n(MCl4)/n(MCl4) + n([C1C4IM][Cl]) equal to 0, 0.1, 0.2, 0.33, 0.5, 0.67. The structure and composition were studied by Differential Scanning Calorimetry (DSC), (35)Cl (263 to 333 K), (1)H and (13)C solid state and solution NMR spectroscopy, and electrospray ionisation (ESI) mass spectrometry. The primary anions of the MCl(4)-based ILs were [MCl(5)], [MCl(6)] and [M(2)Cl(9)], whose relative abundances varied with R. For R = 0.33, pure solid [C(1)C(4)Im](2)[MCl(6)], for both M = Zr and Hf are formed (m.p. = 366 and 385 K, respectively). For R = 0.67 pure ionic liquids [C(1)C(4)Im][M(2)Cl(9)] for both M = Zr and Hf are formed (T(g) = 224 and 220 K, respectively). The thermal dissociation has been attempted of [C(1)C(4)Im](2)[HfCl(6)], and [C(1)C(4)Im](2)[ZrCl(6)] monitored by (35)Cl and (91)Zr solid NMR (high temperature up to 551 K).

Thermal stability, optical and Photoluminescence properties of spherical Ce x Zr1‑x O2 (x = 0.05) crystalline blue-emitting nanophosphors synthesized by microwave method

NASA Astrophysics Data System (ADS)

Manjunatha, S.; Dharmaprakash, M. S.

2018-03-01

Nanocrystalline ZrO2 based material is an impressive candidate for the various functional applications owing to their ease of preparation and high thermal stability. This paper reports the synthesis, structural and optical characterization of thermally stable monodispersed CexZr1‑xO2 (x = 0.05) nanoparticles. This method is based on the fact that, microwave irradiation allows the formation of size controlled and single phase cubic ZrO2 nanoparticles containing Ce+4 as a dopant. The XRD and Rietveld analysis revealed the formation of the crystalline cubic fluorite phase. The formation of nanoparticles was confirmed by FTIR. The morphology of the nanophosphors was characterised by FESEM and TEM. The optical band gap was calculated from the UV–visible absorption spectra and was found to vary from 3.93 to 4.25 eV with calcination temperature. It shows the decrease in the optical band gap from the pristine ZrO2. The particle size was measured by using HRTEM, and the average particle size was found to be 22 nm. Under the 268 nm Ultra Violet irradiation excitation a blue emission at 443 nm was observed at room temperature. The possible luminescence mechanism of CexZr1‑xO2 nanophosphor under UV excitation is discussed.

Chemical synthesis, characterisation, and biocompatibility of nanometre scale porous anodic aluminium oxide membranes for use as a cell culture substrate for the vero cell line: a preliminary study.

PubMed

Poinern, Gérrard Eddy Jai; Le, Xuan Thi; O'Dea, Mark; Becker, Thomas; Fawcett, Derek

2014-01-01

In this preliminary study we investigate for the first time the biomedical potential of using porous anodic aluminium oxide (AAO) membranes as a cell substrate for culturing the Cercopithecus aethiops (African green monkey) Kidney (Vero) epithelial cell line. One advantage of using the inorganic AAO membrane is the presence of nanometre scale pore channels that allow the exchange of molecules and nutrients across the membrane. The size of the pore channels can be preselected by adjusting the controlling parameters of a temperature controlled two-step anodization process. The cellular interaction and response of the Vero cell line with an in-house synthesised AAO membrane, a commercially available membrane, and a glass control were assessed by investigating cell adhesion, morphology, and proliferation over a 72 h period. The number of viable cells proliferating over the respective membrane surfaces revealed that the locally produced in-house AAO membrane had cells numbers similar to the glass control. The study revealed evidence of focal adhesion sites over the surface of the nanoporous membranes and the penetration of cellular extensions into the pore structure as well. The outcome of the study has revealed that nanometre scale porous AAO membranes have the potential to become practical cell culture scaffold substrates with the capability to enhance adhesion and proliferation of Vero cells.

Chemical Synthesis, Characterisation, and Biocompatibility of Nanometre Scale Porous Anodic Aluminium Oxide Membranes for Use as a Cell Culture Substrate for the Vero Cell Line: A Preliminary Study

PubMed Central

Poinern, Gérrard Eddy Jai; Le, Xuan Thi; Becker, Thomas; Fawcett, Derek

2014-01-01

In this preliminary study we investigate for the first time the biomedical potential of using porous anodic aluminium oxide (AAO) membranes as a cell substrate for culturing the Cercopithecus aethiops (African green monkey) Kidney (Vero) epithelial cell line. One advantage of using the inorganic AAO membrane is the presence of nanometre scale pore channels that allow the exchange of molecules and nutrients across the membrane. The size of the pore channels can be preselected by adjusting the controlling parameters of a temperature controlled two-step anodization process. The cellular interaction and response of the Vero cell line with an in-house synthesised AAO membrane, a commercially available membrane, and a glass control were assessed by investigating cell adhesion, morphology, and proliferation over a 72 h period. The number of viable cells proliferating over the respective membrane surfaces revealed that the locally produced in-house AAO membrane had cells numbers similar to the glass control. The study revealed evidence of focal adhesion sites over the surface of the nanoporous membranes and the penetration of cellular extensions into the pore structure as well. The outcome of the study has revealed that nanometre scale porous AAO membranes have the potential to become practical cell culture scaffold substrates with the capability to enhance adhesion and proliferation of Vero cells. PMID:24579077

The application of chiroptical spectroscopy (circular dichroism) in quantifying binding events in lanthanide directed synthesis of chiral luminescent self-assembly structures† †Electronic supplementary information (ESI) available. CCDC 999267–999270 and 1026036. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02474e Click here for additional data file. Click here for additional data file.

PubMed Central

Blasco, Salvador; Twamley, Brendan; O'Brien, John; Peacock, Robert D.; Kitchen, Jonathan A.; Martínez-Calvo, Miguel

2015-01-01

The binding of asymmetrical and optically pure tridentate ligands (L = 1(S) and 1(R)) containing one carboxylic group and 2-naphthyl as an antenna to lanthanide ions (M = La(iii) and Eu(iii)) was studied in CH3CN, showing the successive formation of M:L, M:L2 and M:L3 stoichiometric species in solution. The europium complexes EuL3 were also synthesised, structurally characterised and their photophysical properties probed in CH3OH and CH3CN. The changes in the chiroptical properties of both 1(S) and 1(R) were used (by circular dichroism (CD) spectroscopy) to monitor the formation of these chiral self-assemblies in solution. While circularly polarised luminescence (CPL) showed the formation of Eu(1(S))3 and Eu(1(R))3 as enantiomers, with high luminescence dissymmetry factors (g lum), fitting the CD changes allowed for binding constants to be determined that were comparable to those seen in the analyses of absorbance and luminescence changes. PMID:28936303