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Pressure Effects (pressure + effects)
Selected AbstractsDramatic Pressure Effects on the Selectivity of the Aqueous/Organic Biphasic Hydrogenation of trans -Cinnamaldehyde Catalyzed by Water-Soluble Ru(II)-Tertiary Phosphane ComplexesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 1-2 2003Gábor Papp Abstract In a water/chlorobenzene biphasic reaction, the hydrogenation of trans- cinnamaldehyde, catalyzed by water-soluble Ru(II)-phosphane complexes at pH,3.04 (phosphate buffer), produces a 61:39 mixture of cinnamyl alcohol and dihydrocinnamaldehyde at 1,bar H2; however, the selectivity is increased to 93:7 by increasing the hydrogen pressure to 8,bar. [source] Temperature and Pressure Effects on Local Structure and Chain Packing in cis -1,4-Polybutadiene from Detailed Molecular Dynamics SimulationsMACROMOLECULAR THEORY AND SIMULATIONS, Issue 5 2006Georgia Tsolou Abstract Summary: We present results for the temperature and pressure dependence of local structure and chain packing in cis -1,4-polybutadiene (cis -1,4-PB) from detailed molecular dynamics (MD) simulations with a united-atom model. The simulations have been executed in the NPT statistical ensemble with a parallel, multiple time step MD algorithm, which allowed us to access simulation times up to 1 µs. Because of this, a 32 chain C128cis -1,4-PB system was successfully simulated over a wide range of temperature (from 430 to 195 K) and pressure (from 1 atm to 3 kbar) conditions. Simulation predictions are reported for the temperature and pressure dependence of the: (a) density; (b) chain characteristic ratio, Cn; (c) intermolecular pair distribution function, g(r), static structure factor, S(q), and first peak position, Qmax, in the S(q) pattern; (d) free volume around each monomer unit along a chain for the simulated polymer system. These were thoroughly compared against available experimental data. One of the most important findings of this work is that the component of the S(q) vs. q plot representing intramolecular contributions in a fully deuterated cis -1,4-PB sample exhibits a monotonic decrease with q which remains completely unaffected by the pressure. In contrast, the intermolecular contribution exhibits a distinct peak (at around 1.4 Å,1) whose position shifts towards higher q values as the pressure is raised, accompanied by a decrease in its intensity. 3D view of the simulation box containing 32 chains of C128cis -1,4-polybutadiene at density ,,=,0.849 g,·,cm,3 and the conformation of a single C128cis -1,4-PB chain fully unwrapped in space. [source] Enantioselective [4+2]-Cycloaddition Reaction of a Photochemically Generated o -Quinodimethane: Mechanistic Details, Association Studies, and Pressure EffectsCHEMISTRY - A EUROPEAN JOURNAL, Issue 9 2004Benjamin Grosch Dipl. Abstract 1,2,3,4-Tetrahydro-2-oxoquinoline-5-aldehyde (2) was prepared from m -aminobenzoic acid and 3-ethoxyacryloyl chloride (4) in 19,% overall yield. Compound 2 underwent a photochemically induced [4+2]-cycloaddition reaction with various dienophiles upon irradiation in toluene solution. The exo product 10,a was obtained with acrylonitrile (9,a) as the dienophile, whereas methyl acrylate (9,b) and dimethyl fumarate (9,c) furnished the endo products 11,b and 11,c (69,77,% yield). The reactions proceeded at ,60,°C in the presence of the chiral complexing agent 1 (1.2 equiv) with excellent enantioselectivity (91,94,% ee). The enantiomeric excess increases in the course of the photocycloaddition as a result of the lower product association to 1. The intermediate (E)-dienol 8 was spectroscopically detected at ,196,°C in an EPA (diethyl ether/isopentane/ethanol) glass matrix. The association of the substrate 2 to the complexing agent 1 was studied by circular dichroism (CD) titration. The measured association constant (KA) was 589,M,1 at room temperature (25,°C) and normal pressure (0.1 MPa). An increase in pressure led to an increased association. At 400 MPa the measured value of KA was 703,M,1. Despite the stronger association the enantioselectivity of the reaction decreased with increasing pressure. At 25,°C the enantiomeric excess for the enantioselective reaction 2 + 9,a,10,a decreased from 68,% ee at 0.1 MPa to 58,% ee at 350 MPa. This surprising behavior is explained by different activation volumes for the diastereomeric transition states leading to 10,a and ent - 10,a. 1,2,3,4-Tetrahydro-2-oxochinolin-5-aldehyd (2) wurde ausgehend von m -Aminobenzoesäure und 3-Ethoxyacryloylchlorid (4) in fünf Schritten und einer Gesamtausbeute von 19,% hergestellt. Die Verbindung ließ sich in Toluol als Lösungsmittel mit verschiedenen Dienophilen in einer photochemisch induzierten [4+2]-Cycloaddition umsetzen (69,77,% Ausbeute), wobei als Hauptprodukt mit Acrylnitril (9,a) das exo -Produkt 10,a entstand. Methylacrylat (9,b) und Dimethylfumarat (9,c) lieferten die endo -Produkte 11,b and 11,c. In Gegenwart des chiralen Komplexierungsreagenz, 1 (1.2 Äquiv.) verliefen die Reaktionen mit exzellenter Enantioselektivität (91,94,% ee). Der Enantiomerenüberschuß nahm im Verlauf der photochemischen Umsetzung zu, was man auf die relativ zum Substrat 2 niedrigere Assoziation des Produkts zurückführen kann. Das intermediär gebildete (E)-Dienol 8 wurde spektroskopisch in einer EPA (Ether/i -Pentan/Ethanol) Glasmatrix bei ,196,°C nachgewiesen. Die Assoziation des Substrats 2 an das Komplexierungsreagenz 1 wurde durch CD-Titration genauer untersucht. Die Assoziationskonstante (KA) wurde bei Zimmertemperatur (25,°C) und Normaldruck (0.1 MPa) zu 589,M,1bestimmt. Bei höherem Druck beobachtete man eine verstärkte Assoziation und bei 400 MPa wurde eine Assoziationskonstante von KA=703,M,1bestimmt. Trotz der stärkeren Assoziaion nahm die Enantioselektivität mit wachsendem Druck ab. Bei 25,°C sank der Enantiomerenüberschuß der enantioselektiven Reation 2 + 9,a,10,a von 68,% ee bei 0.1 MPa auf 58,% ee bei 350 MPa. Dieses überraschende Verhalten läßt sich möglicherweise durch die unterschiedlichen Aktivierungsvolumina für die Übergangszustände erklären, die zu 10,a und ent - 10,a führen. [source] Pressure effects on the structural, electronic, and optical properties of Sin@SWCNTsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 6 2009Y. H. Zhang Abstract Well-ordered single, double/four parallel, three/four-strands helical chains, and five-strand helical chain with a single atom chain at the center of Si nanowires (NWs) inside single-walled carbon nanotubes (Sin@SWCNTs) are obtained by means of molecular dynamics. On the basis of these optimized structures, the structural evolution of Sin@SWCNTs subjected to axial stress at low temperature is also investigated. Interestingly, the double parallel chains depart at the center and transform into two perpendicular parts, the helical shell transformed into chain, and the strand number of Si NWs increases during the stress load. Through analyzis of pair correlation function (PCF), the density of states (DOS), and the z -axis polarized absorption spectra of Sin@SWCNTs, we find that the behavior of Sin@SWCNTs under stress strongly depends on SWCNTs' symmetry, diameter, as well as the shape of NWs, which provide valuable information for potential application in high pressure cases such as seabed cable. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Pressure effects on inter- and intramolecular vibrations in hydrogen-bonded L -ascorbic acid crystalJOURNAL OF RAMAN SPECTROSCOPY, Issue 1 2008Hiroko Shimada Abstract Pressure effects on the Raman spectra due to the inter- and intramolecular vibrations of the L -ascorbic acid crystal were studied. The intensity of the Raman bands due to the intermolecular vibrations varies in three different ways by application of pressure. The bands of the first group become stronger, those of the second one become weaker and the third group shows no prominent change in their intensity with increasing pressure. The bands due to the intermolecular vibrations show a blue shift, while the bands due to the intramolecular vibrations shift to the blue or red depending on the vibrational modes by application of pressure. The bands assigned to the OH stretching vibrations shift to the red, the bands assigned to the CO and CC stretching vibrations shift a little to the red and the bands assigned to the other vibrations shift to the blue under high pressure. The following conclusions were derived. (1) The hydrogen bonds forming helixes become stronger and the isolated hydrogen bond becomes weaker with increasing pressure. (2) The bands of the first group owing to the intermolecular vibrations are ascribed to the vibrations related to the helix hydrogen bonds and the second group bands to the isolated hydrogen bond. (3) The CO stretching vibration couples with the CC stretching vibration. (4) The phase transitions take place at 1.8 and 4 GPa in the crystal. Copyright © 2007 John Wiley & Sons, Ltd. [source] Crystallization of recombinant human growth hormone at elevated pressures: Pressure effects on PEG-induced volume exclusion interactionsBIOTECHNOLOGY & BIOENGINEERING, Issue 4 2010Ryan L. Crisman Abstract Crystallization of recombinant human growth hormone (rhGH) at elevated pressures was investigated in the presence of 6,000 molecular weight poly(ethylene glycol; PEG-6000). Crystallization of rhGH at atmospheric pressure occurred at a protein concentration of 15,mg/mL in 6% PEG-6000. Crystallization did not occur in the same solutions at 250,MPa. In contrast, at a pressure of 250,MPa in the presence of 8% PEG-6000, rhGH readily crystallized from solutions containing 35,mg/mL rhGH, whereas amorphous precipitate formed in the same solutions at atmospheric pressure. Osmotic virial coefficients were determined from static light scattering measurements and combined with a hard-sphere activity coefficient model to predict rhGH activity coefficients as a function of pressure and PEG concentration. Predicted activity coefficients quantitatively matched those determined from equilibrium solubility measurements. The ability to adjust the thermodynamic non-ideality with pressure provides a valuable tool to study protein crystallization in addition to providing a methodology for obtaining crystals at elevated pressures. Biotechnol. Bioeng. 2010;107:663,672. © 2010 Wiley Periodicals, Inc. [source] Thermodynamic Equilibrium Calculations for the Reforming of Coke Oven Gas with Gasification GasCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 1 2007B. Li Abstract Thermodynamic analyses of the reforming of coke oven gas with gasification gas for syngas were investigated as a function of coke oven gas-to-gasification gas ratio (1,3), oxygen-to-methane ratio (0,1.56), pressure (25,35,bar) and temperature (700,1100,°C). Thermodynamic equilibrium results indicate that the operating temperature should be approximately 1100,°C and the oxygen-to-methane ratio should be approximately 0.39, where about 80,% CH4 and CO2 can be converted at 30,bar. Increasing the operating pressure shifts the equilibrium toward the reactants (CH4 and CO2); increasing the pressure from 25 to 35,bar decreases the conversion of CO2 from 73.7,% to 67.8,%. The conversion ratio of CO2 is less than that in the absence of O2. For a constant feed gas composition (7,% O2, 31,% gasification gas, and 62,% coke oven gas), a H2/CO ratio of about 2 occurs at temperatures of 950,°C and above. Pressure effects on the H2/CO ratio are negligible for temperatures greater than 750,°C. The steam produced has an effect on the hydrogen selectivity, but its mole fraction decreases with temperature; trace amounts of other secondary products are observed. [source] 2,2,-Nitrophenylisatogen potentiates P2X1 receptor mediated vascular contraction and blood pressure elevationDRUG DEVELOPMENT RESEARCH, Issue 1 2003Anna-Karin Wihlborg Abstract The objective of this research was to examine the effects of chemical compounds with possible P2 receptor modulating effects and to characterize the potentiating effects of 2,2,-nitrophenylisatogen (NPI) on P2X1 receptors in vitro and in vivo. Chemical compounds were tested in an in vitro pharmacological assay using vascular segments from the rat mesenteric artery stimulated by P2 receptor-specific agonists. Contractions were expressed as a percentage of 60 mM K+ -induced contractions. Blood pressure was evaluated in pithed rats. NPI (30 ,M) added 15 min before addition of the P2X1 receptor-specific agonist ,,-MeATP increased the maximum vasoconstriction from 23% to 49% (an increase of 113%). Furthermore, NPI prevented the desensitization of repeated ,,-MeATP contractions. Related compounds were examined, and 2-(3-methoxy-phenyl)-1-oxy-indol-3-one (MPI) had similar effects as NPI, but several others lacked effect. NPI had no effect on ADP,S (P2Y1) or acetylcholine-mediated vasodilatation, nor on UTP (P2Y2/4), UDP (P2Y6), or noradrenaline-mediated contractions. In pithed rats, the blood pressure response to 50 nmol/kg-infusion of ,,-MeATP was increased from 50±6 to 63±5 mmHg (P<0.05), but had no effect on basal blood pressure or on the cardiovascular response to preganglionic nerve stimulation. In conclusion, NPI and MPI potentiates P2X1 receptor vascular contractions in vitro and (NPI) blood pressure effects in vivo. It is possible that the effect is mediated by an inhibition of P2X1 receptor desensitization. Drug Dev. Res. 59:82,87, 2003. © 2003 Wiley-Liss, Inc. [source] Research and Prospects of Iron-Based SuperconductorsADVANCED MATERIALS, Issue 45 2009Zhi-An Ren Abstract The discovery of a new superconductor, LaFeAsO1,xFx with a superconducting critical temperatureT,c, of 26,K in 2008, has quickly renewed interest in the exploration of iron-based superconductors. More than 70 new superconductors have been discovered within several months, with the highest Tc of up to 55,K being observed in the SmFeAsO1,x compound. High Tcs have previously only been observed in cuprates; these new iron-based superconductors have been added as second members of the high- Tc family. The crystal structure of these compounds contains an almost 2D Fe,As layer formed by FeAs4 tetrahedrons, which can be separated by an oxide or metal layer that provides extra electrons to the Fe,As layer, and the itinerant iron 3d electrons form an antiferromagnetic (AFM) order state in the undoped parent compounds at around 100,200,K. Superconductivity can be induced by carrier doping, which destroys the AFM ground state. In this Review, the most recent findings on and basic experimental facts about this class of high- Tc materials will be presented, including the various superconducting structures, the synthesis methods, the physical properties of the parent compounds, the doping methods that could produce superconductivity, pressure effects, and the prospects for this new iron-based high- Tc family. [source] Along-channel mathematical modelling for proton exchange membrane fuel cellsINTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 12 2005Wenbo Huang Abstract Proper water and thermal management is essential for obtaining high performance of proton exchange membrane fuel cells (PEMFCs). A steady, two-dimensional water and thermal management model was developed, aiming at considering pressure effects (i.e. the effects of local pressure on the cell performance), pressure drop, open circuit voltage variation with stack temperature, water vapour effects on membrane conductivity, which made the model physically more reasonable and more suitable for various operating conditions. The model could predict the distributions of a series of important parameters along the flow channel, and thus the effects of various operating and design parameters on the fuel cell performance could be investigated easily by numerical trial-and-error method. The modelling results compared well with the available experimental results from the literatures. The results also showed that the humidification of both anode and cathode is crucial for the performance of PEMFCs. The model could be a very useful engineering tool for the optimization of PEMFCs. Copyright © 2005 John Wiley & Sons, Ltd. [source] Event study concerning international bond price effects of credit rating actionsINTERNATIONAL JOURNAL OF FINANCE & ECONOMICS, Issue 2 2001Manfred Steiner Abstract The influence of credit ratings on eurobond prices has been neglected for a long time. It is questionable whether non-US investors relate their investment decisions on US ratings and whether ratings from US agencies are relevant information sources for international capital markets. This paper examines daily excess eurobond returns associated with announcements of watchlistings and rating changes by Standard & Poor's and Moody's. Significant bond price reactions are observed for announcements of downgradings and negative watchlistings while upgradings and positive watchlistings do not cause announcement effects. Distinct from the results on national capital markets the international evidence shows that besides actual yield level and issuer type the issuer nationality is a key factor that determines the intensity of price reactions after downgrades. The price reaction is also significantly stronger for downgrades into speculative grade. This indicates, that the announcement effects can in part be explained by price pressure effects due to regulatory constraints rather than original information content of rating changes. Copyright © 2001 John Wiley & Sons, Ltd. [source] Temperature and pressure effects on structural formations in a ternary microemulsionJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 3-1 2000M. Nagao Small angle neutron scattering experiments were conducted on a temperature-induced phase transition in a ternary microemulsion composed of AOT (dioctyl sulfosuccinate sodium salt), D2 O and n -decane and the results were compared with those of pressure-induced one. Although the static features of both the temperature- and the pressure-induced phase behaviour were similar, a temperature dependence of its characteristic repeat distance at high temperature was quite different from a pressure dependence of that at high pressure. Neutron spin echo experiments were also performed on both the phase transitions. The dynamics of the high temperature phase was different from that of the high pressure phase. These results indicated that the effect of pressure on the structural formation was different from that of temperature. [source] Substance loss caused by scaling with different sonic scaler inserts , an in vitro studyJOURNAL OF CLINICAL PERIODONTOLOGY, Issue 1 2001Thomas Kocher Abstract Background, aims: Depending on the phase of periodontal treatment, power-driven inserts with different power levels are necessary: during initial treatment and flap operations, it must be possible to remove calculus which firmly adheres to the root surface with great efficiency; in contrast, gentle root-surface instrumentation has a high priority during maintenance treatment. Recently, modified sonic scaler inserts have been introduced: diamond-coated inserts for open flap operations and slim probe-shaped sonic scaler inserts for deplaqueing during maintenance. Method: We compared the substance removal by these inserts to that of a conventional insert. In a bench system which allows application force, stroke height, and width and frequency of instrumentation to be monitored and also permits assessment of the topography before and after instrumentation (yielding depth removal and removed volume), we instrumented aluminum rods in triplicate and bovine roots in a 5-fold repetition. Results: With high application forces (1.0 N), the diamond-coated inserts removed 30 to 50% more substance than the conventional one. Except for the slim inserts, there was a significant linear relationship between increasing force and removed volume. Probe-shaped inserts do not remove considerable substance even with increasing pressures. Conclusions: Diamond-coated inserts remove tooth substance very effectively and must thus be handled with care: more pressure effects more removal. Probe-shaped inserts can be used without risk during maintenance visits. [source] EFFECT OF HIGH-PRESSURE TREATMENT OF MILK ON LIPASE AND ,-GLUTAMYL TRANSFERASE ACTIVITYJOURNAL OF FOOD BIOCHEMISTRY, Issue 6 2004P. K. PANDEY ABSTRACT High-pressure (HP) treatment (0,180 min at 300,400 MPa) was applied to milk to evaluate the pressure effects on the activities of lipoprotein lipase and ,-glutamyl transferase. Short time pressure exposure resulted in some enhancement in the activity of both enzymes, and for lipase, there was no inactivation during the entire pressure hold time (up to 100 min). With ,-glutamyl transferase, the extent of enhancement in activity was pressure level dependent, with lower pressure resulting in a greater enhancement. Furthermore, longer pressure treatment times resulted in inactivation of ,-glutamyl transferase, following a first order kinetic model. The pressure sensitivity of the inactivation parameters (k and D -values) for ,-glutamyl transferase was adequately described by the pressure death time and Arrhenius models with a zpof 543 MPa and an associated volume of activation, ,V,, of ,3.28 × 10,8 m3/mole. [source] Direct Evidence for Imidazoline (I1) Receptor Modulation of Ethanol Action on Norepinephrine-Containing Neurons in the Rostral Ventrolateral Medulla in Conscious Spontaneously Hypertensive RatsALCOHOLISM, Issue 4 2007Guichu Li Background: Enhancement of the rostral ventrolateral medulla (RVLM) presympathetic (norepinephrine, NE) neuronal activity represents a neurochemical mechanism for the pressor effect of ethanol. In this study, we tested the hypothesis that ethanol action on RVLM presympathetic neurons is selectively influenced by the signaling of the local imidazoline (I1) receptor. To support a neuroanatomical and an I1 -signaling selectivity of ethanol, and to circumvent the confounding effects of anesthesia, the dose-related neurochemical and blood pressure effects of ethanol were investigated in the presence of selective pharmacological interventions that cause reduction in the activity of RVLM or nucleus tractus solitarius (NTS) NE neurons via local activation of the I1 or the ,2 -adrenergic receptor in conscious spontaneously hypertensive rats. Results: Local activation of the I1 receptor by rilmenidine (40 nmol) or by the I1/,2 receptor mixed agonist clonidine (1 nmol), and local activation of the ,2 -adrenergic receptor (,2AR) by the pure ,2AR agonist , -methylnorepinephrine (, -MNE, 10 nmol) caused reductions in RVLM NE, and blood pressure. Intra-RVLM ethanol (1, 5, or 10 ,g), microinjected at the nadir of the neurochemical and hypotensive responses, elicited dose-dependent increments in RVLM NE and blood pressure in the presence of local I1,but not ,2 -receptor activation. Only intra-NTS , -MNE, but not rilmenidine or clonidine, elicited reductions in local NE and blood pressure; ethanol failed to elicit any neurochemical or blood pressure responses in the presence of local activation of the ,2AR within the NTS. Conclusion: The findings support the neuroanatomical selectivity of ethanol, and support the hypothesis that the neurochemical (RVLM NE), and the subsequent cardiovascular, effects of ethanol are selectively modulated by I1 receptor signaling in the RVLM. [source] Hydrostatic pressure effects on the structural and electronic properties of carbon nanotubesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 14 2004Rodrigo B. Capaz This issue's Editor's Choice [1] is a theoretical study of the properties of single-wall carbon nanotubes (SWNTs) under hydro-static pressure. The cover picture is a snapshot of room-temperature molecular dynamics simulations of a chiral (8,7) SWNT at a pressure of 4 GPa, where a symmetry-breaking collapse of the tube into a flat shape is observed. This paper is an invited presentation from the 11th Interna-tional Conference on High Pressure Semiconductor Physics (HPSP-11), held in Berkeley, California, USA, 2,5 August 2004. The Proceedings of this conference series have been published for the fifth time in physica status solidi (b). The first author, Rodrigo Barbosa Capaz, is Associate Professor of Physics at Universidade Federal do Rio de Janeiro and works on electronic properties and computer modeling of materials. [source] Hydrostatic pressure effects on the donor impurity-related photoionization cross-section in cylindrical-shaped GaAs/GaAlAs quantum well wiresPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 14 2004J. D. Correa Abstract Using a variational method the binding energy has been calculated for a shallow donor impurity and the donor-related photoionization cross-section in 1D and 0D GaAs low-dimensional systems. The dependence on the binding energy and the photoionization cross-section for a hydrogenic donor impurity in the finite potential model are discussed and the results are presented as a function of the radius, polarization of the photon, applied hydrostatic pressure, and photon energy. The calculations for the pressure effects are performed both in the direct and indirect GaAs gap regime. Calculations are presented for an on-axis (on-center) impurity in the wire (in the dot). (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Pressure measurements of TO-phonon anharmonicity in isotopic ZnSPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 3 2004R. E. Tallman Abstract We have measured the dependence on pressure of the line-widths of the TO and LO Raman phonons of ,-ZnS. In order to enhance the phenomena observed, and to eliminate possible effects of isotopic disorder, we have measured a nearly isotopically pure crystal, 68Zn32S. The strongly structured pressure effects observed are interpreted on the basis of anharmonic decay and the corresponding two-phonon density of states. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] High gas pressure effects on yeastBIOTECHNOLOGY & BIOENGINEERING, Issue 4 2008V. Espinasse Abstract Dried microorganisms are particularly resistant to high hydrostatic pressure effects. However, exposure to high pressures of nitrogen proved to be effective in inactivating dried yeasts. In this study, we tried to elucidate this mechanism on Saccharomyces cerevisiae. High-pressure treatments were performed using different inert gases at 150 MPa and 25°C with holding time values up to 12 months. The influence of cell hydration was also investigated. For fully hydrated cells, pressurized gases had little specific effect: cell inactivation was mainly due to compression effects. However, dried cells were sensitive to high pressure of gases. In this latter case, two inactivation kinetics were observed. For holding time up to 1 h, the inactivation rate increased to 4 log and was linked to a loss of membrane integrity and the presence of damage on the cell wall. In such case cell inactivation would be due to gas sorption and desorption phenomena which would rupture dried cells during a fast pressure release. Gas sorption would occur in cell lipid phases. For longer holding times, the inactivation rate increased more slightly due to compression effects and/or to a slower gas sorption. Water therefore played a key role in cell sensitivity to fast gas pressure release. Two hypotheses were proposed to explain this phenomenon: the rigidity of vitrified dried cells and the presence of glassy solid phases which would favor intracellular gas expansion. Our results showed that dried microorganisms can be ruptured and inactivated by a fast pressure release with gases. Biotechnol. Bioeng. 2008;101: 729,738. © 2008 Wiley Periodicals, Inc. [source] True and Apparent Temperature Dependence of Protein Adsorption Equilibrium in Reversed-Phase HPLCBIOTECHNOLOGY PROGRESS, Issue 6 2002Szabelski The adsorption behavior of bovine insulin on a C8 -bonded silica stationary phase was investigated at different column pressures and temperatures in isocratic reversed-phase HPLC. Changes in the molar volume of insulin (, Vm) upon adsorption were derived from the pressure dependence of the isothermal retention factor ( k,). The values of , Vm were found to be practically independent of the temperature between 25 and 50 °C at ,96 mL/mol and to increase with increasing temperature, up to ,108 mL/mol reached at 50 °C. This trend was confirmed by two separate series of measurements of the thermal dependence of ln( k,). In the first series the average column pressure was kept constant. The second series involved measurements of ln( k,) under constant mobile-phase flow rate, the average column pressure varying with the temperature. In both cases, a parabolic shape relationship was observed between ln( k,) and the temperature, but the values obtained for ln k, were higher in the first than in the second case. The relative difference in ln( k,), caused by the change in pressure drop induced by the temperature, is equivalent to a systematic error in the estimate of the Gibbs free energy of 12%. Thus, a substantial error is made in the estimates of the enthalpy and entropy of adsorption when neglecting the pressure effects associated with the change in the molar volume of insulin. This work proves that the average column pressure must be kept constant during thermodynamic measurements of protein adsorption constants, especially in RPLC and HIC. Our results show also that there is a critical temperature, Tc , 53 °C, at which ln( k,) is maximum and the insulin adsorption process changes from an exothermic to an endothermic one. This temperature determines also the transition point in the molecular mechanism of insulin adsorption that involves successive unfolding of the protein chain. [source] L-Dihydroxyphenylserine (L-DOPS): A Norepinephrine ProdrugCARDIOVASCULAR THERAPEUTICS, Issue 3-4 2006David S. Goldstein ABSTRACT L- threo -3,4-dihydroxyphenylserine (L-DOPS, droxydopa) is a synthetic catecholamino acid. When taken orally, L-DOPS is converted to the sympathetic neurotransmitter, norepinephrine (NE), via decarboxylation catalyzed by L-aromatic-amino-acid decarboxylase (LAAAD). Plasma L-DOPS levels peak at about 3 h, followed by a monoexponential decline with a half-time of 2 to 3 h. Plasma levels of NE and of its main neuronal metabolite, dihydroxyphenylglycol (DHPG) peak approximately concurrently but at much lower concentrations. The relatively long half-time for disappearance of L-DOPS from plasma, compared to that of NE, explains their very different attained plasma concentrations. In patients with neurogenic orthostatic hypotension, L-DOPS increases blood pressure and ameliorates orthostatic intolerance. Inhibition of LAAAD, such as by treatment with carbidopa, which does not penetrate the blood-brain barrier, prevents the blood pressure effects of the drug, indicating that L-DOPS increases blood pressure by augmenting NE production outside the brain. Patients with pure autonomic failure (which usually entails loss of sympathetic noradrenergic nerves), and patients with multiple system atrophy (in which noradrenergic innervation remains intact) have similar plasma NE responses to L-DOPS. This suggests mainly non-neuronal production of NE from L-DOPS. L-DOPS is very effective in treatment of deficiency of dopamine-beta-hydroxylase (DBH), the enzyme required for conversion of dopamine to NE in sympathetic nerves. L-DOPS holds promise for treating other much more common conditions involving decreased DBH activity or NE deficiency, such as a variety of syndromes associated with neurogenic orthostatic hypotension. [source] | |||||||||||||||||||