Specific Anion Binding to Sulfobetaine Micelles and Kinetics of Nucleophilic Reactions

Substrates containing a P3 aspartic residue are in general cleaved poorly by thrombin. This may be partly due to an unfavourable interaction between the P3 aspartate and Glu192 in the active site of thrombin. In Protein C activation and perhaps also thrombin receptor cleavage, binding of ligands at the anion-binding exosite of thrombin seems to improve the activity of thrombin with substrates containing a P3 aspartate. To investigate the importance of Glu192 and exosite-binding in modulating thrombin's interactions with a P3 aspartate, peptidyl chloromethanes based on the sequence of the thrombin receptor (containing a P3 aspartate) have been synthesized and the kinetics of their inactivation of α-thrombin and the mutant Glu192 → Gln determined. The values of the inactivation rate constant (ki) for the chloromethanes containing a P3 aspartate were about two-fold higher with the Glu192 → Gln mutant. A peptide based on the sequence of hirudin (rhir52Ő65), which binds to the anion-binding exosite of thrombin, was an allosteric modulator of the amidolytic activity of the Glu192 → Gln mutant; a 5-fold decrease in the Km value for the substrate d-Phe-pipecolyl-Arg-p-nitroanilide was observed in the presence of saturating concentrations of rhir52Ő65. This exosite-binding peptide also increased the ki values of chloromethanes containing a P3 aspartate with both α-thrombin and the Glu192 → Gln mutant. However, the increases in the ki values were greater with the Glu192 → Gln mutant (5-fold compared with 2-fold for α-thrombin). Thus exosite binding does not seem to mitigate putative unfavourable interactions between Glu192 and the P3 aspartate. Moreover, increases in the ki caused by exosite binding were not unique to chloromethanes containing a P3 aspartate; increases of the same magnitude were also observed when the P3 position was occupied by the favourable d-phenylalanine in place of the unfavourable aspartate. The results obtained were consistent with exosite binding's causing changes in the conformation of the S2 and/or S1 sites of thrombin.

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Kinetics of bicarbonate and chloride transport in human red cell membranes.

The Journal of General Physiology ◽

10.1085/jgp.97.2.321 ◽

1991 ◽

Vol 97 (2) ◽

pp. 321-349 ◽

Cited By ~ 20

Author(s):

P K Gasbjerg ◽

J Brahm

Keyword(s):

Chloride Transport ◽

Anion Binding ◽

Maximum Flux ◽

Half Saturation Constant ◽

Binding Inhibition ◽

Filtering Technique ◽

Red Cell Membranes ◽

Kinetics Of ◽

Bicarbonate And Chloride Transport ◽

Human Red Cells

Unidirectional [14C]HCO3- and 36Cl- efflux from human red cells and ghosts was studied under self-exchange conditions at pH 7.8 and 0 degrees C by means of the Millipore-Swinnex filtering technique. Control bicarbonate experiments showed that 14CO2 loss from the cells to the efflux medium was insignificant. The anion flux was determined under (a) symmetric variations of the anion concentration (C(i) = C(o) = 5-700 mM), and (b) asymmetric conditions with CAn constant on one side and varied on the other side of the membrane. Simple Michaelis-Menten-like kinetics (MM fit: J(eff) = J(eff)max.C/(K1/2 + C)) was used to describe anion flux dependence on C for (a) C(i) = C(o) = 5-100 mM, (b) C(i) = 6-100 mM, C(o) = constant, and (c) C(i) = constant, C(o) = 1-25 mM. At higher cellular concentrations noncompetitive self-inhibition by anion binding (inhibition constant Ki mM) to an intracellular site was included in the model (MS fit): J(eff) = J(eff)max.C(i)/[(K1/2 + C(i)).(1 + C(i)/Ki)]. The MM fits show that the external half-saturation constant, Ko1/2 ( = C(o)An for J(eff,o) = 1/2.j(eff,o)max) at C(o) = 1-25 mM is 1.5-2.4 mM (HCO3-) and 1.8-2.6 mM (Cl-). At C(o) = 1-260 mM Ko1/2 is 1.2-1.5 mM (HCO3-) and 1.4-1.8 mM (Cl-). The respective maximum flux, J(eff,o)max (nmol/[cm2.s]), for C(o) = 1-25 mM is 0.41-0.51 (HCO3-) and 0.28-0.38 (Cl-), and for C(o) = 1-260 mM 0.39-0.44 (HCO3-) and 0.27-0.31 (Cl-). The internal half-saturation constant, Ki1/2 mM is: MM fit (C(i) = 6-100 mM, C(o) = 50 mM), 18.0 mM (HCO3-) and 23.8 mM (Cl-); MS fit (C(i) = 6-920 mM, C(o) = 50 mM), 32.0 mM (HCO3-) and 45.1 mM (Cl-). The maximum flux, J(eff,i)max (nmol/[cm2.s]) is: MM fit; 0.50 (HCO3-) and 0.34 (Cl-); MS fit, 0.70 (HCO-3) and 0.50 (Cl-). The half-inhibition constants of the MS fit, Ki, are 393 mM (HCO3-) and 544 mM (Cl-). The MM fit shows that the symmetric half-saturation constant, Ks1/2, is 20.2 (HCO-3) and 23.9 (Cl-) mM, and J(eff,s)max is 0.51 (HCO3-) and 0.32 (Cl-) nmol/(cm2.s). The MS fit shows that for C = 5-700 mM Ks1/2 is 30.4 nM (HCO3-) and 50.1 mM (Cl-), and Ki is 541 mM (HCO3-) and 392 mM (Cl-).(ABSTRACT TRUNCATED AT 400 WORDS)

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Direct observations of radiation-enhanced transformations in glass

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100075543 ◽

1983 ◽

Vol 41 ◽

pp. 354-355

Author(s):

J. F. DeNatale ◽

D. G. Howitt

Keyword(s):

Glass Matrix ◽

Diffusion Mechanism ◽

Bubble Formation ◽

Silicate Glasses ◽

Phase Decomposition ◽

Direct Observations ◽

Thin Foils ◽

Oxygen Bubble ◽

Electron Energy Loss ◽

Kinetics Of

The electron irradiation of silicate glasses containing metal cations produces various types of phase separation and decomposition which includes oxygen bubble formation at intermediate temperatures figure I. The kinetics of bubble formation are too rapid to be accounted for by oxygen diffusion but the behavior is consistent with a cation diffusion mechanism if the amount of oxygen in the bubble is not significantly different from that in the same volume of silicate glass. The formation of oxygen bubbles is often accompanied by precipitation of crystalline phases and/or amorphous phase decomposition in the regions between the bubbles and the detection of differences in oxygen concentration between the bubble and matrix by electron energy loss spectroscopy cannot be discerned (figure 2) even when the bubble occupies the majority of the foil depth.The oxygen bubbles are stable, even in the thin foils, months after irradiation and if van der Waals behavior of the interior gas is assumed an oxygen pressure of about 4000 atmospheres must be sustained for a 100 bubble if the surface tension with the glass matrix is to balance against it at intermediate temperatures.

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Irradiation behavior of pyrolytic silicon carbide

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100074288 ◽

1983 ◽

Vol 41 ◽

pp. 72-73

Author(s):

R. J. Lauf

Keyword(s):

Silicon Carbide ◽

Fission Products ◽

Thermodynamics And Kinetics ◽

Neutron Fluences ◽

Fuel Particles ◽

Sic Coatings ◽

Irradiation Behavior ◽

Kinetics Of ◽

Htgr Fuel

Fuel particles for the High-Temperature Gas-Cooled Reactor (HTGR) contain a layer of pyrolytic silicon carbide to act as a miniature pressure vessel and primary fission product barrier. Optimization of the SiC with respect to fuel performance involves four areas of study: (a) characterization of as-deposited SiC coatings; (b) thermodynamics and kinetics of chemical reactions between SiC and fission products; (c) irradiation behavior of SiC in the absence of fission products; and (d) combined effects of irradiation and fission products. This paper reports the behavior of SiC deposited on inert microspheres and irradiated to fast neutron fluences typical of HTGR fuel at end-of-life.

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The Ordered Phase Formation in Ti-Al-Ga Alloys

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100069193 ◽

1970 ◽

Vol 28 ◽

pp. 440-441

Author(s):

Shiro Fujishiro ◽

Harold L. Gegel

Keyword(s):

Thermal Stability ◽

High Temperature ◽

Titanium Alloys ◽

Growth Kinetics ◽

Stoichiometric Composition ◽

Good Potential ◽

Alpha Titanium ◽

Cold Rolled ◽

Kinetics Of ◽

Thermal Stability Of

Ordered-alpha titanium alloys having a DO19 type structure have good potential for high temperature (600°C) applications, due to the thermal stability of the ordered phase and the inherent resistance to recrystallization of these alloys. Five different Ti-Al-Ga alloys consisting of equal atomic percents of aluminum and gallium solute additions up to the stoichiometric composition, Ti3(Al, Ga), were used to study the growth kinetics of the ordered phase and the nature of its interface.The alloys were homogenized in the beta region in a vacuum of about 5×10-7 torr, furnace cooled; reheated in air to 50°C below the alpha transus for hot working. The alloys were subsequently acid cleaned, annealed in vacuo, and cold rolled to about. 050 inch prior to additional homogenization

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Ion Beam Induced Interfacial Reactions in Molybdenum Thin Films on Silicon

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100097466 ◽

1981 ◽

Vol 39 ◽

pp. 162-163

Author(s):

L. J. Chen ◽

L. S. Hung ◽

J. W. Mayer

Keyword(s):

Ion Beam ◽

Chemical Vapor ◽

Interfacial Reactions ◽

Practical Applications ◽

Microelectronic Devices ◽

Recent Emergence ◽

Chemical Vapor Deposited ◽

Atomic Mixing ◽

Silicon Interface ◽

Kinetics Of

When an energetic ion penetrates through an interface between a thin film (of species A) and a substrate (of species B), ion induced atomic mixing may result in an intermixed region (which contains A and B) near the interface. Most ion beam mixing experiments have been directed toward metal-silicon systems, silicide phases are generally obtained, and they are the same as those formed by thermal treatment.Recent emergence of silicide compound as contact material in silicon microelectronic devices is mainly due to the superiority of the silicide-silicon interface in terms of uniformity and thermal stability. It is of great interest to understand the kinetics of the interfacial reactions to provide insights into the nature of ion beam-solid interactions as well as to explore its practical applications in device technology.About 500 Å thick molybdenum was chemical vapor deposited in hydrogen ambient on (001) n-type silicon wafer with substrate temperature maintained at 650-700°C. Samples were supplied by D. M. Brown of General Electric Research & Development Laboratory, Schenectady, NY.

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In situ study of electron beam-induced chemical vapor deposition of Au in an environmental TEM

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100137653 ◽

1995 ◽

Vol 53 ◽

pp. 256-257

Author(s):

J. Drucker ◽

R. Sharma ◽

J. Kouvetakis ◽

K.H.J. Weiss

Keyword(s):

Electron Beam ◽

Chemical Vapor Deposition ◽

Vapor Deposition ◽

Quantum Effect ◽

Line Drawing ◽

Chemical Vapor ◽

Environmental Cell ◽

Engineering Changes ◽

Kinetics Of

Patterning of metals is a key element in the fabrication of integrated microelectronics. For circuit repair and engineering changes constructive lithography, writing techniques, based on electron, ion or photon beam-induced decomposition of precursor molecule and its deposition on top of a structure have gained wide acceptance Recently, scanning probe techniques have been used for line drawing and wire growth of W on a silicon substrate for quantum effect devices. The kinetics of electron beam induced W deposition from WF6 gas has been studied by adsorbing the gas on SiO2 surface and measuring the growth in a TEM for various exposure times. Our environmental cell allows us to control not only electron exposure time but also the gas pressure flow and the temperature. We have studied the growth kinetics of Au Chemical vapor deposition (CVD), in situ, at different temperatures with/without the electron beam on highly clean Si surfaces in an environmental cell fitted inside a TEM column.

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Investigation of irradiation-induced nucleation processes in silicon and germanium

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100137495 ◽

1995 ◽

Vol 53 ◽

pp. 224-225

Author(s):

Harry A. Atwater ◽

C.M. Yang ◽

K.V. Shcheglov

Keyword(s):

Room Temperature ◽

Crystal Size ◽

Initial Distribution ◽

Engineering Control ◽

Size Evolution ◽

Silicon And Germanium ◽

Ge Quantum Dot ◽

And Control ◽

Germanium Quantum Dots ◽

Kinetics Of

Studies of the initial stages of nucleation of silicon and germanium have yielded insights that point the way to achievement of engineering control over crystal size evolution at the nanometer scale. In addition to their importance in understanding fundamental issues in nucleation, these studies are relevant to efforts to (i) control the size distributions of silicon and germanium “quantum dots𠇍, which will in turn enable control of the optical properties of these materials, (ii) and control the kinetics of crystallization of amorphous silicon and germanium films on amorphous insulating substrates so as to, e.g., produce crystalline grains of essentially arbitrary size.Ge quantum dot nanocrystals with average sizes between 2 nm and 9 nm were formed by room temperature ion implantation into SiO2, followed by precipitation during thermal anneals at temperatures between 30°C and 1200°C[1]. Surprisingly, it was found that Ge nanocrystal nucleation occurs at room temperature as shown in Fig. 1, and that subsequent microstructural evolution occurred via coarsening of the initial distribution.

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In situ observation of the martensitic transformation in (Mg,Y)-PSZ

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100144036 ◽

1986 ◽

Vol 44 ◽

pp. 500-501

Author(s):

R-R. Lee

Keyword(s):

Martensitic Transformation ◽

High Strength ◽

Nucleation And Growth ◽

In Situ Observation ◽

Considerable Potential ◽

Transmission Electron ◽

Structural Applications ◽

Applied Stresses ◽

Kinetics Of

Partially-stabilized ZrO2 (PSZ) ceramics have considerable potential for advanced structural applications because of their high strength and toughness. These properties derive from small tetragonal ZrO2 (t-ZrO2) precipitates in a cubic (c) ZrO2 matrix, which transform martensitically to monoclinic (m) symmetry under applied stresses. The kinetics of the martensitic transformation is believed to be nucleation controlled and the nucleation is always stress induced. In situ observation of the martensitic transformation using transmission electron microscopy provides considerable information about the nucleation and growth aspects of the transformation.

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