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711.
Abdul K. Labban Edgar F. Westrum Jr. Helmer Fjellvg Fredrik Grnvold Arne Kjekshus Svein Stlen 《Journal of solid state chemistry》1987,70(2)
The heat capacity of MnAs0.88P0.12 has been measured by adiabatic shield calorimetry from 10 to 500 K. It is shown that very small energy changes are connected with two magnetic order-order transitions, indicating that these can be regarded as mainly “noncoupled” magnetic transitions. At higher temperatures contributions to the excess heat capacity arises from a magnetic order-disorder transition, a conversion from low- to high-spin state for manganese, and a MnP- to NiAs-type structural transition. The observed heat capacity is resolved into contributions from the different physical phenomena, and the character of the transitions is discussed. In particular it is substantiated that the dilational contribution, which includes magnetoelastic and magnetovolume terms as well as normal anharmonicity terms, plays a major role in MnAs0.88P0.12. The entropy of the magnetic order-disorder transition is smaller than should be expected from a complete randomization of the spins, assuming a purely magnetic transition. Thermodynamic functions have been evaluated and the respective values of Cp, {SOm(T) - SOm(0)}, and -{GOm(T) - HOm(0)}/T at 298.15 K are 68.74, 72.09, and 32.30 J K−1 mole−1, and at 500 K 56.05, 108.12, and 56.64 J K−1 mole−1. 相似文献
712.
Optoelectronic devices made from semiconductor polymers often employ partially phase-separated binary polymer blends with "distributed heterojunctions" in the polymer film, and the migration of bulk excitons towards these heterojunctions crucially influences the device performance. Here, we investigate exciton migration in blend films of two polyfluorene derivatives. Localized exciplex states form in electron-hole capture at the heterojunction between the two polymers and these can be thermally excited to transfer to bulk excitons. Rapid radiative emission from these excitons can then allow efficient light-emitting diode operation. We show here that when these excitons migrate to another heterojunction site within their lifetime they are re-trapped at the interface and again form exciplex states or dissociate completely. We demonstrate that in polymer blend light-emitting diodes this can reduce the exciton population by more than 54% and can strongly influence the emission spectrum. We then analyze exciton re-trapping in detail using time-resolved photoluminescence spectroscopy on blends with different morphologies and find that for nanometer-scale phases exciton emission is completely suppressed. We show that the data agree well with a simple kinetic model which confirms the importance of the blend morphology for the exciton trapping efficiency. 相似文献
713.
Matthias Koch Almuth Liebich Tin Win Irene Nehls Arne Lund Kvernheim Oddvar Ringstad Frøydis Oreld 《Accreditation and quality assurance》2006,11(3):122-129
The 2-year international joint project HYCREF (Contract-No. G6RD-CT-2002-00854), funded by the European Commission in the 5th Framework programme, aimed to develop methods to prepare homogenous and stable water-, soil- and waste reference materials contaminated with mineral oil hydrocarbons and to test certify the mineral oil content by gas chromatographic methods. As mineral oil products are important sources for environmental contaminations, appropriate reference materials certified by using the new gas chromatographic methods (soil: ISO/FDIS 16703, waste: prEN 14039 and KW/04, water: ISO 9377-2) are highly needed. Additional to the HYCREF-results presented in part I–mineral contaminated soils–this second paper gives an overview of the feasibility study for the preparation and test certification of three waste reference materials (offshore marine sediment, building material and industrial waste). The following specifications, which had been defined in the project work plan, were reached successfully: uncertainty of the mineral oil content resulting from the certification exercise ≤5% and a between-bottle inhomogeneity of ≤3%. All three materials have been evaluated for long- and short term stability. They contain different levels and types of mineral oil and cover the full application range of ISO/FDIS 16703 and prEN 14039 (100–10,000 mg/kg). The expanded uncertainties U
cert of the three materials are about 6%. In this way, they are comparable to ERM®-CC015a (U
cert=7.1%, mineral oil in a river sediment) and are suited to close the present gap of commercially available CRM for mineral oil determination in waste. 相似文献
714.
PCR technology for screening and quantification of genetically modified organisms (GMOs) 总被引:28,自引:0,他引:28
Holst-Jensen A Rønning SB Løvseth A Berdal KG 《Analytical and bioanalytical chemistry》2003,375(8):985-993
Although PCR technology has obvious limitations, the potentially high degree of sensitivity and specificity explains why it has been the first choice of most analytical laboratories interested in detection of genetically modified (GM) organisms (GMOs) and derived materials. Because the products that laboratories receive for analysis are often processed and refined, the quality and quantity of target analyte (e.g. protein or DNA) frequently challenges the sensitivity of any detection method. Among the currently available methods, PCR methods are generally accepted as the most sensitive and reliable methods for detection of GM-derived material in routine applications.The choice of target sequence motif is the single most important factor controlling the specificity of the PCR method. The target sequence is normally a part of the modified gene construct, for example a promoter, a terminator, a gene, or a junction between two of these elements. However, the elements may originate from wildtype organisms, they may be present in more than one GMO, and their copy number may also vary from one GMO to another. They may even be combined in a similar way in more than one GMO. Thus, the choice of method should fit the purpose. Recent developments include event-specific methods, particularly useful for identification and quantification of GM content. Thresholds for labelling are now in place in many countries including those in the European Union. The success of the labelling schemes is dependent upon the efficiency with which GM-derived material can be detected. We will present an overview of currently available PCR methods for screening and quantification of GM-derived DNA, and discuss their applicability and limitations. In addition, we will discuss some of the major challenges related to determination of the limits of detection (LOD) and quantification (LOQ), and to validation of methods. 相似文献
715.
Haaland A Shorokhov DJ Tutukin AV Volden HV Swang O McGrady GS Kaltsoyannis N Downs AJ Tang CY Turner JF 《Inorganic chemistry》2002,41(25):6646-6655
The molecular structures of Zr[(mu-H)(3)BH](4) and U[(mu-H)(3)BH](4) have been investigated by density functional theory (DFT) calculations and gas electron diffraction (GED). The triply bridged bonding mode of the tetrahydroborate groups in the former is confirmed, but both DFT calculations and GED structure refinements indicate that the BH(4) groups are rotated some 12 degrees away from the orientation in which the three bridging B-H bonds are staggered with respect to the opposing ZrB(3) fragment. As a result the symmetry of the equilibrium conformation is reduced from T(d) to T. Bond distances and valence angles are as follows (DFT/GED): Zr-B = 232.2/232.4(5) pm; Zr-H(b) = 214.8/214.4(6) pm; B-H(b) = 125.3/127.8(8) pm; B-H(t) = 119.4/118.8(17) pm; angle ZrBH(b) = 66.2/65.6(3) degrees; the smallest dihedral angle of type tau(BZrBH(b)) = 48/45(2) degrees. DFT calculations on Hf(BH(4))(4) indicate that the structure of this molecule is very similar to that of the Zr analogue. Matrix-isolation IR spectroscopy and DFT calculations on U(BH(4))(4) show that while the polymeric solid-state structure is characterized by terminal triply bridging and metal-metal bridging bidentate BH(4) groups, all BH(4) groups are triply bridging in the gaseous monomer. Calculations with one of the two nonbonding 5f electrons on U occupying an a(1) and the other distributed equally among the three t(2) orbitals indicate that the equilibrium conformation has T(d) symmetry, i.e. that the three B-H(b) bonds of each tetrahydroborate group are exactly staggered with respect to the opposing UB(3) fragment with tau(BUBH(b)) = 60 degrees. Calculations including spin-orbit interactions indicate that Jahn-Teller distortions from T(d) symmetry are either absent or very small. The best agreement between observed and calculated GED intensity data was obtained for a model of T(d) symmetry, but models of T symmetry with dihedral angles tau(BUBH(b)) > 42 degrees cannot be ruled out. Bond distances and valence angles are as follows (DFT/GED): U-B = 248.8/251.2(4) pm; U-H(b) = 227.7/231.5(6) pm; B-H(b) = 126.0/131.6(5) pm, B-H(t) = 119.5/117.8(11) pm; angle UBH(b) = 65.6/63.1(3) degrees. It is suggested that the different equilibrium conformations of the three molecules are determined primarily by repulsion between bridging H atoms in different tetrahydroborate groups. 相似文献
716.
Roger Appelqvist György Marko-Varga Lo Gorton Arne Torstensson Gillis Johansson 《Analytica chimica acta》1985
A chemically modified electrode for detection of dihydronicotinamide adenine dinucleotide (NADH) and dihydronicotinamide adenine dinucleotide phosphate (NADPH) is described. Graphite rods were modified by dipping them into solutions of-dimethylamino-1,2-benzophenoxzinium salt (Meldola blue). The modified electrodes were mounted in a flow-through cell in a flow-injection manifold. Samples (50 μl) of pure nicotinamide coenzymes produced strictly linear calibration graphs from 1 μM to 10 mM with a repeatability of 0.2–0.6% RSD. A packed-bed enzyme reactor (210 μl) containing immobilized glucose dehydrogenase was inserted in the manifold for glucose determinations. Oxidized coenzyme was also added to the carrier electrolyte. Straight calibration graphs were again obtained up to 1mM β-d-glucose. The detection limit was 0.25 μM β-d-glucose for 50-μl samples. The electrode was kept at ?50 to 0 m V vs. SCE which was low enough to avoid interferences from ascorbic acid, uric acid or quinones. 相似文献
717.
718.
The VP-VAs system has been studied by powder diffraction and magnetic susceptibility measurements. Three regions of solid solubility, separated by two phase regions, are found for VP1–x
As
x
as function of composition (x). An NiAs type phase prevails for 0.00x0.07±0.02, a hexagonal phase of unknown crystal structure for 0.17±0.02x0.63±0.02 and an MnP type phase for 0.83±0.02x1.00. No phase transition is observed between 10 and 1 300 K. The various VP1–x
As
x
phases exhibitPauli paramagnetism.Dedicated to Professor Dr.Kurt L. Komarek on his 60th birthday June 23, 1986. 相似文献
719.
A fabrication platform for electrically mediated optically active biofunctionalized sites in BioMEMS
Powers MA Koev ST Schleunitz A Yi H Hodzic V Bentley WE Payne GF Rubloff GW Ghodssi R 《Lab on a chip》2005,5(6):583-586
We report a new approach for microfluidic optical bioanalysis that is based on the electrically driven assembly of bio-components on a transparent sidewall and the optical detection of the assembled components using planar waveguides. This allows localized electrical signals for bio-assembly and optical signals for bio-detection that can easily be applied in MEMS systems. We demonstrate a BioMEMS design incorporating this scheme and its output signal when using fluorescent detection. 相似文献
720.
It is well known that orientational correlations appear in polymer chain models when the subunits are linked by ball-socket joints implemented as rigid constraint conditions. These correlations do not appear when the subunits are connected by springlike potential forces, even in the limit of infinitely stiff springs. In a widely used class of algorithms for Brownian dynamics simulations, inertia effects are ignored. However, in the recently introduced needle chain and nugget chain algorithms, the rigid constraint correlations depend on the mass and moment of inertia. This inconsistency does not appear in the bead-rod (Kramers) polymer chain model, which also has orientational correlations introduced by rigid constraint conditions. Explicit expressions for the correlation functions are given for thermodynamic equilibrium states. Analytical expressions for the associated forces ("metric forces") and simulation results showing how the rigid constraint correlations influence dynamical properties, are also presented. Further we discuss the physical relevance of these correlations and show via simulations that their influence on stationary and dynamical properties depend significantly on chain length. We further show that if the metric forces are removed, algorithms designed with rigid constraint conditions describe a chain of segments connected by infinitely stiff springs. Finally we show that the results presented here for needle chains are relevant also for the bead-rod (Kramers) chain model, making it possible to simulate a bead-spring chain with infinitely stiff springs. 相似文献