Showing papers by "DSM published in 1992"

Irregular glacial interstadials recorded in a new Greenland ice core

Abstract: THE Greenland ice sheet offers the most favourable conditions in the Northern Hemisphere for obtaining high-resolution continuous time series of climate-related parameters. Profiles of 18O/<16O ratio along three previous deep Greenland ice cores1–3 seemed to reveal irregular but well-defined episodes of relatively mild climate conditions (interstadials) during the mid and late parts of the last glaciation, but there has been some doubt as to whether the shifts in oxygen isotope ratio were genuine representations of changes in climate, rather than artefacts due to disturbed stratification. Here we present results from a new deep ice core drilled at the summit of the Greenland ice sheet, where the depositional environ-ment and the flow pattern of the ice are close to ideal for core recovery and analysis. The results reproduce the previous findings to such a degree that the existence of the interstadial episodes can no longer be in doubt. According to a preliminary timescale based on stratigraphic studies, the interstadials lasted from 500 to 2,000 years, and their irregular occurrence suggests complexity in the behaviour of the North Atlantic ocean circulation.

Design parameters estimation for scale-up of high-pressure bubble columns

Abstract: Experiments were carried out in bubble columns for a number of liquids at pressures between 0.1 and 2.0 MPa for two column sizes. Based on the experimental results as well as extensive literature data, the extent of the effect column dimensions have on gas holdup were determined, both at low and high pressures (which is of importance to scale-up). It was also demonstrated that none of the published empirical gas holdup equations incorporate the influence of gas density accurately. Therefore, a new improved gas hold-up equation is developed that incorporates the influence of gas and liquid properties with an average error of approximately 10%. Finally, it is also discussed to what extent the influence of pressure on other important design parameters such as the interfacial area, the liquid volumetric mass transfer coefficient, and gas and liquid mixing, can be estimated on the basis of empirical equations.

Confocal Raman Microspectroscopy: Theory and Application to Thin Polymer Samples:

Abstract: Raman microspectroscopy can be used effectively to study very small samples or to study small areas within a transparent sample. With the application of the technique of confocal microscopy to a Raman microscope, the depth resolution of the instrument can be enhanced considerably. Confocal microscopy uses a pinhole, placed in the back image plane of the microscope objective, to block light from outside the focal plane. In this way the signal from the small volume element one wants to study can be better separated from the signals arising from the surrounding material. In this paper we show that the performance of the confocal Raman microscope can be described satisfactorily by geometrical optics. Furthermore, we have performed measurements to determine the depth resolution of our system for different combinations of objectives and pinholes. Finally, we report on the applications of this technique to different polymer systems, such as multilayer foils, fibers, and fiber composites.

Oxidation of phenolic arylglycerol .beta.-aryl ether lignin model compounds by manganese peroxidase from Phanerochaete chrysosporium: oxidative cleavage of an .alpha.-carbonyl model compound

Abstract: Manganese peroxidase (MnP) oxidized 1-(3,5-dimethoxy-4-hydroxyphenyl)-2-(4-(hydroxymethyl)-2-methoxyphenoxy) -1,3-dihydroxypropane (I) in the presence of MnII and H2O2 to yield 1-(3,5-dimethoxy-4-hydroxyphenyl)- 2-(4-(hydroxymethyl)-2-methoxyphenoxy)-1-oxo-3-hydroxypropane (II), 2,6-dimethoxy-1,4-benzoquinone (III), 2,6-dimethoxy-1,4-dihydroxybenzene (IV), 2-(4-(hydroxymethyl)-2-methoxyphenoxy)-3-hydroxypropanal (V), syringaldehyde (VI), vanillyl alcohol (VII), and vanillin (VIII). MnP oxidized II to yield 2,6-dimethoxy-1,4-benzoquinone (III), 2,6-dimethoxy-1,4-dihydroxybenzene (IV), vanillyl alcohol (VII), vanillin (VIII), syringic acid (IX), and 2-(4-(hydroxymethyl)-2-methoxyphenoxy)-3-hydroxypropanoic acid (X). A chemically prepared MnIII-malonate complex catalyzed the same reactions. Oxidation of I and II in H2(18)O under argon resulted in incorporation of one atom of 18O into the quinone III and into the hydroquinone IV. Incorporation of one atom of oxygen from H2(18)O into syringic acid (IX) and the phenoxypropanoic acid X was also observed in the oxidation of II. These results are explained by mechanisms involving the initial one-electron oxidation of I or II by enzyme-generated MnIII to produce a phenoxy radical. This intermediate is further oxidized by MnIII to a cyclohexadienyl cation. Loss of a proton, followed by rearrangement of the quinone methide intermediate, yields the C alpha-oxo dimer II as the major product from substrate I. Alternatively, cyclohexadienyl cations are attacked by water. Subsequent alkyl-phenyl cleavage yields the hydroquinone IV and the phenoxypropanal V from I, and IV and the phenoxypropanoic acid X from II, respectively. The initial phenoxy radical also can undergo C alpha-C beta bond cleavage, yielding syringaldehyde (VI) and a C6-C2-ether radical from I and syringic acid (IX) and the same C6-C2-ether radical from II. The C6-C2-ether radical is scavenged by O2 or further oxidized by MnIII, subsequently leading to release of vanillyl alcohol (VII). VII and IV are oxidized to vanillin (VIII) and the quinone III, respectively.

Recent results on the biology of Hodgkin and Reed-Sternberg cells. I. Biopsy material.

Abstract: The most recent sophisticated investigations have provided new and revealing, but also contradictory and controversial information on the biological nature and the cellular origin of Hodgkin and Reed-Sternberg cells (H-RS). Immunophenotypic analyses have shown variable phenotypic antigen expression; but, on balance the data suggest a lymphoid cell expressing T- and/or B-cell-associated markers and certain activation antigens while lacking immunological features of monocytes-macrophages or other lineages. Molecular genetic studies have demonstrated heterogenous findings with respect to rearrangements of T-cell receptor and immunoglobulin genes. Only a small percentage of the cases has rearrangements; this might be due to the threshold of sensitivity of the method combined with the scarcity of the malignant cells. Epstein-Barr virus (EBV) genomes are clonally integrated in the H-RS cells of about half the cases. The significance of these findings--whether EBV is a causative agent or an epiphenomenon--remains to be elucidated. H-RS cells express mRNA and proteins of various cytokines and cytokine receptors implying a predominant role for cytokines in the pathophysiology of HD. The mononuclear and polynuclear H-RS cells are capable of DNA synthesis and nuclear division; the lack of cellular division leads to multinuclearity through the process of endomitosis. Mutations and expression of only a limited number of oncogenes have been tested thus far. Whether the bcl-2 oncogene is involved in HD remains a matter of debate. Aneuploidy and non-random chromosomal abnormalities are the results of cytogenetic analyses of H-RS cells. However, no chromosomal marker specific for HD has yet been found. Thus, while studies of EBV involvement, growth factor production, oncogene expression and chromosomal abnormalities contributed a fair amount of new data on the nature of H-RS cells, only immunophenotyping and genotyping provided some indication of the cellular derivation: an activated lymphoid cell that possibly expresses oncogenes, that probably is infected with EBV, that most likely produces cytokines, that certainly has multiple karyotypic abnormalities.

Breakdown phenomena related to trapping/detrapping processes in wide band gap insulators

Abstract: Mechanisms of breakdown phenomena related to charge carrier trapping and detrapping are investigated in wide band gap insulators. Trapping occurs in potential wells due to the presence of polarization charge at the border of domains having different permittivities and conductivities. Findings in this work are related to (1) the calculation of the polarization energy of the medium surrounding a trapped charge, (2) the investigation of the mechanism of space charge destabilization, and (3) the explanation of the breakdown mechanism from the polarization energy dissipation after detrapping. An experimental method to produce breakdowns is recalled. In this method electron trapping is produced under keV energy electron irradiation and the space charge destabilization is obtained under low energy electron irradiation. Depending on the experimental arrangement, the method makes it possible to produce flashover or bulk breakdown. The formation of a plasma, the melting of the sample, and the formation of treeing or thermal etched pits are observed. >

On the Mechanism of Oxidation of Non-Phenolic Lignin Model Compounds by the Laccase-ABTS Couple

Abstract: On the Mechanism of Oxidation of Non-Phenolic Lignin Model Compounds by the Laccase-ABTS Couple By Andreas Muheim, Armin Fiechter, Patricia J. Harvey and Hans E. Schoemaker 1 Eidgen ssische Technische Hochschule Z rich, Institut f r Biotechnologie, ETH-H nggerberg, CH-8093 Z rich, Switzerland 2 Imperial College of Science,Technology and Medicine, Department of Biology, Prince Consort Road, London SW7 2BB, United Kingdom 3 DSM Research, Bio-organic Chemistry Section, P.O. Box 18, NL-6160 MD Geleen,The Netherlands

Evidence for an early Holocene climatic optimum in the Antarctic deep ice-core record

Abstract: In the interpretation of the Antarctic deep ice-core data, little attention has been given to the Holocene part of the records. As far as translation of the stable isotope content in terms of temperature is concerned, this can be understood because expected temperature changes may be obscured by isotopic noise of various origins and because no 14C dating has yet been available for this type of sequence. In this article, we focus on the Dome C and Vostok cores and on a new 850-m long ice core drilled out at Komsomolskaia by the Soviet Antarctic Expeditions. These three sites are located in East Antarctica, on the Antarctic plateau, in a region essentially undisturbed by ice-flow conditions, so that their detailed intercomparison may allow us to identify the climatically significant isotopic signal. Our results compare well with the proximal records of Southern Hemisphere high latitudes and support the existence of a warmer “climatic optimum” between 10 and 6 ka y BP. Maximum temperatures are reached just at the end of the last deglaciation, which confirms previous observations at high latitudes, in contrast with later dates for the Atlantic and hypsithermal optima in Europe and North America.

Intramolecular charge transfer and trans-cis isomerization of the DCM styrene dye in polar solvents. A CS INDO MRCI study

Abstract: The solvent-induced changes of trans-cis isomerization efficiency and electronic structure of the excited state of the DCM dye have been considered by means of CS INDO MRCI calculations. The potential energy curves, dipole moments and atomic charge densities as a function of two internal coordinates, namely the rotation angle about the central “double” bond and the twisting of the dimethylamino group, have been obtained for the ground state and the lowest excited states. The structural requirements for the existence of ICT (intramolecular charge transfer) excited states have been investigated by considering internal rotations about three single bonds. The reliability of the potential surfaces and of the solvation models has been discussed with reference to test-calculations on the DMABN molecule. In the first excited singlet state of DCM, the low-energy barrier for the trans-cis isomerization has been found unaffected by the solvent polarity. The only singlet excited state presenting a large ICT character has been found to be the S 2 state for a perpendicularly twisted conformation of the dimethylamino group (TICT state). The assumption of a deactivation of the trans-isomer in the locally excited state through the TICT funnel has been largely discussed with reference to the simplifications of the present theoretical approach.

Particle sizing by photon correlation spectroscopy. Part III: Mono and bimodal distributions and data analysis

Abstract: The possibilities and limitations of photon correlation spectroscopy (PCS) as a practical tool for particle sizing are reviewed. In this part the most frequently used methods of data analysis are briefly surveyed. The practical performances for the determination of particle size distributions were evaluated by a comparative study with different kinds of users (industrial and academic research groups and manufacturers). The PCS results were also compared with electron microscopy (EM) and static light scattering (SLS) results. Thereby it was confirmed that the amount of reliable information that can be obtained by PCS about particle size distributions with measuring times of the order of minutes is limited by the ill-conditioning of the data inversion procedure, among other factors. Nevertheless, the information obtained from the PCS measurements agrees essentially with the EM and SLS results.

Crystal and molecular deformation in strained high‐performance polyethylene fibers studied by wide‐angle x‐ray scattering and Raman spectroscopy

Abstract: Wide-angle x-ray scattering (WAXS) and Raman spectroscopic data show that on both the crystal and molecular levels, a bimodal stress distribution exists in strained high-performance polyethylene fibers. In part of the crystalline PE the microscopic strain level is high (ca. 70% of macroscopic strain); in the remainder, the microscopic strain level is low (independent of macroscopic strain, ca. 0.4%). During stress relaxation the fraction of highly strained PE decreases with time. WAXS revealed no indication of a change in the a and b unit-cell dimensions. Furthermore, no indications for stress-induced formation of monoclinic and/or hexagonal PE and for crystal breaking were found. From the latter it can be deduced that all chains within one crystal are equally strained. The WAXS results are used to calibrate the stress-induced frequency shifts of Raman bands.

Process for the preparation of a bridged metallocene compound as well as a catalyst component and a process for the polymerization of olefins

Abstract: The invention relates to a process for the preparation of a bridged metallocene compound in which: (I) a bridged double ligand, reacting with a proton acceptor, is converted into a bridged double anion (II) the double anion is converted into the bridged metallocene compound through reaction with a compound of a group 4b, 5b or 6b metal from the Periodic System of Elements. reaction (II) being carried out in a liquid dispersant which a) comprises one or more weak Lewis bases, the conjugated acid of which has a dissociation constant pK a for which the following holds: pK.sub.a ≦-2.5, b) contains at most 1 mole equivalent, relevant to the metal compound, of strong Lewis base, the conjugated acid of which has a pK a that is higher than -2.5. The invention further relates to a catalyst component for the polymerization of olefins and a process for the polymerization of olefins and a polyolefin.

Origin of July Antarctic precipitation and its influence on deuterium content: a GCM analysis

Abstract: The NASA/GISS GCM is used to estimate the evaporative contributions of several oceanic regions (defined by temperature) to Antarctica's July precipitation. Tracer diagnostics in the GCM suggest that the weighted average evaporative source temperature for Antarctic precipitation as a whole is about 12°C. The average source temperature for local precipitation there varies from 9° C to 14° C. To examine the effect of evaporative source on water isotope concentration, the GCM also follows a global deuterium (HDO) tracer and deuterium tracers evaporating from each oceanic region. The results suggest that although evaporative source temperature does affect the concentrations of the individual HDO tracers, differences in evaporative source do not explain the scatter in the roughly linear relationship between condensation temperature and isotope concentration.

Vibrational spectra of indole and assignments on the basis of ab initio force fields

Abstract: New high-resolution Fourier transform spectra for indole vapour and its N-deuterated analogue and Fourier transform Raman spectra for solid indole are reported. Observed frequencies for normal modes are compared with those calculated from normal coordinate analyses carried out on the basis of ab initio force fields. The latter were calculated using the 3–21G basis set and either the theoretical optimized geometry or that given by microwave spectroscopy. The force field obtained with the optimized geometry was shown to provide and excellent approach for calculating not only frequencies but also IR and Raman intensities. Except for the NH and CH stretching modes, only one scale factor for all the in-plane modes and another for all the out-of-plane modes are needed in order to bring closer the calculated and observed frequencies for indole and for eleven deuterated analogues. Assignments for each normal mode were obtained from potential energy distributions among internal coordinates. Those for normal modes corresponding, in particular, to bands observed also for the tryptophar residue are discussed in detail.

Type 1 ribosome-inactivating proteins depurinate plant 25S rRNA without species specificity

Abstract: Four different type 1 ribosome-inactivating proteins (RIPs) with RNA N-glycosidase activity were tested for their ability to attack the large rRNA of plant ribosomes derived from tobacco plants, as well as from the plant species from which the particular RIP had been isolated. Incubation of tobacco ribosomes with RIPs isolated from either Phytolacca americana L. (pokeweed), Dianthus barbatus L. (carnation), Spinacia oleracea L. (spinach) or Chenopodium amaranthicolor Coste and Reyn. (chenopodium) rendered the 25S rRNA sensitive to aniline-catalyzed hydrolysis, generating a single rRNA-fragment of about 350 nucleotides. The same fragment was generated when rRNAs from pokeweed, carnation, spinach or chenopodium ribosomes were aniline-treated without any deliberate treatment of the ribosomes with the respective RIP. This indicated that ribosomes from all RIP-producing plants were already inactivated by their own RIPs during preparation. These results demonstrate that plant ribosomes are generally susceptible to RIP attack, including modification by their own RIPs. Direct sequencing of the newly generated fragments revealed that a single N-glycosidic bond at an adenosine residue within the highly conserved sequence 5'-AGUACGAGAGGA-3' was cleaved by all of the RIPs investigated, a situation also found in animal, yeast and Escherichia coli ribosomes.

UPS and XPS study of the polymer/metal interface of poly(2-methyl-2-propenenitrile) electropolymerized on an oxidized nickel surface cathode

Abstract: Mechanisms of formation and structure of the interface between an oxidized nickel surface and poly(2-methyl-2-propeneritrile) obtained by electropolymerization under cathodic polaniation are studied by UPS and XPS spectroscopies. The results suggest that a direct interaction takes place between the monomer molecules and surface metallic sites freed by reduction of the metal oxides. The interface between the metal and the resulting polymer is characterized by tbe existence of chemical bonds of the carbon-nickel type

YbNiSn, a ferromagnetic Kondo lattice

Abstract: We present an investigation of the low temperature properties of the ternary intermetallic alloy YbNiSn by X-ray and neutron diffraction, resistivity, magnetisation and 170Yb Mossbauer spectroscopy measurements. It is shown that YbNiSn is a ferromagnet (Tc = 5.65 K) with the Yb3+ magnetic moments lying along the orthorhombic c axis. At low temperatures a strong anisotropy of the interionic exchange coupling is evidenced (λc ≃ 100 kOe/μB, λa ≃ 15 kOe/μB) which competes with the Crystal Electric Field anisotropy (gc ≃ 1.67, ga ≃ 3.72), leading to the unusual situation where the ferromagnetic moments do not lie along the easy magnetisation axis a. Hybridisation of the 4f electrons with band electrons leads to a reduction of the spontaneous moment (saturated value 0.85μB) and is likely to be the origin of the large value of the molecular field constant λc, as well as of the anisotropy of the exchange interaction and of the resistivity.

Process for the production of a microporous film of polyethylene

Abstract: of EP0504954Microporous film of polyethylene with a high degree of moisture vapour transmission rate and permeability to air and a process for the production of such a film from a polyolefine by extruding a solution of the polyolefine in a first solvent, followed by cooling, the removal of the solvent and stretching of the film, in which both sides of the film are brought into close contact with a second solvent for the polyolefine before the film is contacted with the cooling agent.