The effect of protein concentration on ion binding.

The concentration of protein in a solution has been found to have a significant effect on ion binding affinity. It is well known that an increase in ionic strength of the solvent medium by addition of salt modulates the ion-binding affinity of a charged protein due to electrostatic screening. In recent Monte Carlo simulations, a similar screening has been detected to arise from an increase in the concentration of the protein itself. Experimental results are presented here that verify the theoretical predictions; high concentrations of the negatively charged proteins calbindin D9k and calmodulin are found to reduce their affinity for divalent cations. The Ca(2+)-binding constant of the C-terminal site in the Asn-56 --> Ala mutant of calbindin D9k has been measured at seven different protein concentrations ranging from 27 microM to 7.35 mM by using 1H NMR. A 94% reduction in affinity is observed when going from the lowest to the highest protein concentration. For calmodulin, we have measured the average Mg(2+)-binding constant of sites I and II at 0.325, 1.08, and 3.25 mM protein and find a 13-fold difference between the two extremes. Monte Carlo calculations have been performed for the two cases described above to provide a direct comparison of the experimental and simulated effects of protein concentration on metal ion affinities. The overall agreement between theory and experiment is good. The results have important implications for all biological systems involving interactions between charged species.

Frances Trollope : her life and literary work from George III to Victoria /

Includes index.

Market reform and state paternalism in Hungary: a path-dependent approach

Hungary is one of the worst-hit countries of the current financial crisis in Central and Eastern Europe. The deteriorating economic performance of the country is, however, not a recent phenomenon. A relatively high ratio of redistribution, a high and persistent public deficit and accelerated indebtedness characterised the country not just in the last couple of years but also well before the transformation, which also continued in the postsocialist years. The gradualist success of the country – which dates back to at least 1968 – in the field of liberalisation, marketisation and privatisation was accompanied by a constant overspending in the general government. The paper attempts to explore the reasons behind policymakers’ impotence to reform public finances. By providing a path-dependent explanation, it argues that both communist and postcommunist governments used the general budget as a buffer to compensate losers of economic reforms, especially microeconomic restructuring. The ever-widening circle of net benefiters of welfare provisions paid from the general budget, however, has made it simply unrealistic to implement sizeable fiscal adjustment, putting the country onto a deteriorating path of economic development.

Na 1 Nachlass Max Horkheimer, 325 - Korrespondenzen u.a. mit Frances Bartlett Kinne und Otto Kirchheimer (p. V 101, 1-197)

75 Briefe mit Beilagen zwischen Prof. Frances Bartlett Kinne und Max Horkheimer, 1956-1973; 7 Briefe mit Beilagen zwischen Prof. Otto Kirchheimer und Max Horkheimer, 1952-1954; 19 Briefe mit Beilagen zwischen Prof. Guido Kisch und Max Horkheimer, 1955-1956; 23 Briefe mit Beilagen zwischen Walter Kittel (Oberbaurat i. R.), 1964-1973; 14 Briefe mit Beilagen zwischen Jules Klanfer und Max Horkheimer, 1963-1964; 4 Briefe mit Beilagen zwischen Prof. Otto Klineberg und Max Horkheimer, 1960-1961; 1 Brief von Max Horkheimer an Otto Klineberg (Psychologe), 22.6.1960;

Na 1 Nachlass Max Horkheimer, 520 - Korrespondenzen mit Walter Benjamin (Kopien) (p. VI 5A, 168 - 325)

4 Briefe zwischen Walter Benjamin und Cecilia Razovsky; 6 Briefe zwischen Cecilia Razovsky und Max Horkheimer; 1 Brief von Cecilia Razovsky an den American Consul, 17.11.1939; 1 Brief von Antonio Sols an Max Horkheimer, 30.10.1940; 1 Brief von Max Horkheimer an Antonio Sols, 11.10.1940; 1 Brief (Abschrift, Auszug) an A. R. L. Gurland von Frau Gurland, 11.10.1940; 3 Briefe zwischen dem Emergency Rescue Committee (New York) und Max Horkheimer, August 1940; 1 Brief von Max Horkheimer an Pastor del Rio, 17.07.1940; 1 Brief von Max Horkheimer an J. Wavrinek, 17.07.1940; 1 Brief von Theodor W. Adorno an Gershom Scholem, 16.07.1940; 1 Brief von Max Horkheimer an Hans Schaudinger, 13.07.1940; 1 Brief von Max Horkheimer an George S. Messersmith, 08.07.1940; 1 Brief von Max Horkheimer an Adolph Kates, 05.07.1940; 1 Brief von Max Horkheimer an Adolph Kates, 29.06.1940; 2 Briefe zwischen dem Refugee Section of the American Friends Service Committee (Philadelphia) und Max Horkheimer, Mai 1940; 2 Briefe von Egon Wissing an Max Horkheimer, 1940; 1 Brief von Max Horkheimer an die Economy Blue Print Co. (New York), 25.05.1940; 1 Brief von Werner Kraft an Max Horkheimer, 30.04.1940;

Structure of 1 lct-Hydroxyeon-1,4,18-trienine-3-one

C21H27NO2, Mr=325.5 , orthorhombic,P21212,, a = 7.516 (2), b = 13.430 (2), c =18.047 (2) A, U= 1821.79 A 3, Z = 4, D x =1.186 Mg m -a, 2(Cu Ka) = 1.5418 A, # = 0.56 mm -1, F(000) = 704, T= 293 K, final R = 0.04 for 1892 reflections with I _> 3a(I). Ring A is planar, and rings B and C adopt a chair conformation. Rings D and E are envelopes, with C(14) and C(17) displaced from their respective planes by 0.643 (3) and 0.482 (3)A. The ring system A/B shows quasi-trans fusion, whilst ring systems B/C and C/D are trans fused about C(8)-C(9) and C(13)-C(14) respectively. The D/E junction shows cis fusion.

Organometallic Chemistry of Diphosphazanes. 11. Reactions of fac-[Mo(CO)3(MeCN){.eta.2-Ph2PN(Pri)PPh(DMP)}] (DMP = 3,5-Dimethyl-1-Pyrazolyl) with Diphosphazanes and Diphosphinoalkanes and Oxidative Addition with Iodine

The use of fac-[Mo(CO)(3)(MeCN)(eta(2)-L(1))] (1a) {L(1) = Ph(2)PN(Pr-i)PPh(DMP)}(2) as a precursor to metalloligands and bimetallic, heterotrimetallic, and heptacoordinated complexes is reported. The reaction of 1a with diphosphazane, dppa, or a diphosphinoalkane such as dppm or dppe yields the fac-eta(1)-diphosphine substituted metalloligands, fac-[Mo(CO)(3)(eta(2)-L(1))(eta(1)-PXP)] {PXP = dppa (2), dppm (3), and dppe (4)}. These undergo isomerization to yield the corresponding mer-diphosphine complexes (5-7). Oxidation of the uncoordinated phosphorus atom of the mer-eta(1)-dppm-substituted complex eventually provides mer-[Mo(CO)(3)-(eta(2)-L(1)){eta(1)-Ph(2)PCH(2)P(O)Ph(2)}](8). The structure of the latter complex has been confirmed by single crystal X-ray diffraction {triclinic system, P ($) over bar 1; a = 11.994(3), b = 14.807(2), c = 15.855(3) Angstrom; alpha = 114.24(1), beta = 91.35(2), and gamma = 98.95(1)degrees; Z = 2, 4014 data (F-0 > 5 sigma(F-0)), R = 0.066, R(W) = 0.069}. Treatment of the dppe metalloligand 7 with [PtCl2(COD)] yields the heterotrimetallic complex cis-[PtCl2{mer-[Mo(CO)(3)(eta(2)-L(1))(eta(1)-dppe]}(2)] (9). Attempts to prepare a related trimetallic complex with the dppm-containing metalloligand were unsuccessful; only the tetracarbonyl complex cis-[Mo(CO)(4)(eta(2)-L(1))] (1b) and cis-[PtCl2(eta(2)-dppm)] were obtained. Reaction of la with dppe in the ratio 2:1 yields the mer-mer dinuclear complex [{mer-[Mo(CO)(3)(eta(2)-L(1))]}(2)(mu-dppe)] (10) bridged by dppe. Oxidation of 1a with iodine yields the Mo(II) heptacoordinated complex [MoI2(CO)(2)(eta(3)-L(1))] (11) with tridentate PPN coordination. The same Mo(II) complex 11 is also obtained by the direct oxidation of the tetracarbonyl complex cis-[Mo(CO)(4)(eta(2)-L(1))] (1b) with iodine. The structure of 11 has been confirmed by X-ray diffraction studies {monoclinic system, Cc; a = 10.471(2), b = 19.305(3), c = 17.325(3) Angstrom; beta = 95.47(2)degrees; Z = 4, 3153 data (F-0 > 5 sigma(F-0)), R = 0.049, R(W) = 0.051}. This complex exhibits an unusual capped-trigonal prismatic geometry around the metal. A similar heptacoordinated complex 12 with a chiral diphosphazane ligand {L(3) = (S,R)-P(h)2PN-(*CHMePh)*PPh(DMP)} has also been synthesized.