Chemical approaches to penicillin allergy—IV. Binding of carrier receptor protein with penicillin and its analogues

The availability of electrophoretically homogeneous rabbit penicillin carrier receptor protein (CRP) by affinity chromatography afforded an idealin vitro system to calculate the thermodynamic parameters of binding of penicillin and analogues with CRP as well as competitive binding of such analogues with CRP in presence of14C-penicillin G. The kinetics of association of CRP with 7-deoxy penicillin which does not bind covalently with CRP have been studied through equilibrium dialysis with14C-7-deoxybenzyl penicillin and found to be K=2·79×106M−1.−ΔG=8·106 k cal/mole as well as fluorescence quenching studies with exciter λ 280 K=3·573×106M−1,−ΔG=8·239 k cal/mole. The fluorescence quenching studies have been extended to CRP-benzyl penicillin and CRP-6-aminopenicillanic acid (6APA) systems also. The fluorescence data with benzyl penicillin indicate two conformational changes in CRP—a fast change corresponding to the non-covalent binding to CRP with 7-deoxy penicillin and a slower change due to covalent bond formation. With 6-APA the first change is not observed but the conformational change corresponding to covalent binding is only seen. Competitive binding studies indicate that the order of binding of CRP with the analogues of penicillin is as follows: methicillin > 6APA > carbenicillin >o-nitrobenzyl penicillin > cloxacillin ≈ benzyl penicillin ≈ 6-phenyl acetamido penicillanyl alcohol ≈ 7 phenyl acetamido desacetoxy cephalosporanic acid ≈p-amino benzyl penicillin ≈p-nitro benzyl penicillin > ticarcillin >o-amino benzyl penicillin > amoxycillin > 7-deoxy benzyl penicillin > ampicillin.From these data it has been possible to delineate partially the topology of the penicillin binding cleft of the CRP as well as some of the functional groups in the cleft responsible for the binding process.

Phase relationships in the system Ni-W-O and thermodynamic properties of NiWO,

The phase diagram of the Ni-W-O system at 1200 K was established by metallographic and X-ray identification of the phases present after equilibration at controlled oxygen potentials. The oxygen partial pressures over the samples were fixed by metered streams of CO+CO2 gas mixtures. There was only one ternary oxide, nickel tungstate (NiWO4), in the Ni-W-O system at a total pressure of 1 atm, and this compound decomposed to a mixture of Ni+WO2.72 on lowering the oxygen potential. The Gibbs' free energy of formation of NiWO4 was determined from the measurement of the e.m.f. of the solid oxide galvanic cell, Pt, Ni+NiWO4+WO2.72/CaO-ZrO2/Ni+NiO, Pt and thermodynamic properties of tungsten and nickel oxides available in the literature. For the reaction, NiO(s)+WO3(s)rarrNiWO4(s) DeltaG°=–10500–0.708 T (±250) cal mol–1.

Ab initio studies of the structure and vibrational spectra of methyl isocyanide-borane and acetonitrile-borane

The SCF/DZP and MP2/DZP methods of ab initio quantum chemistry have been utilized to study the structure, vibrational spectra, binding energy, and barrier to internal rotation of methyl isocyanide-borane and acetonitrile-borane adducts. The eclipsed conformation of the complexes was predicted to be a minimum, and the staggered form is a transition state with a barrier height of about 10 cal/mol. The vibrational analyses of CH3NC-BH3 and CH3CN-BH3 and several of their isotopomers have been carried out by the GF matrix method. Computations have also been carried out for free CH3NC and CH3CN in order to investigate the changes in CH3NC and CH3CN as a result of their complex formation with BH3. To obtain an acceptable set of force constants, a recently proposed procedure ''RECOVES'' has been utilized. The increase in the N=C/C=N stretching force constant of CH3NC/CH3CN on adduct formation is interpreted with the help of Parr and Borkman's model. The binding energies for the two adducts have been determined taking basis set superposition error (BSSE) into consideration. The effect of the BSSE on structure, dipole moment, and vibrational frequencies of CH3CN and CH3NC is also evaluated. The predicted infrared band intensities for the two complexes are in good agreement with the experimentally observed features, and they have been utilized in the assignment of vibrational frequencies.

Crystal and molecular structure of synthetic cholesterol compounds vitamin D3-analogues (I) 24(S)-hydroxy coprastan-3-one & (II) 24(R)-hydroxy coprastan-3-one

The title compound I (24-(S)-Hydroxy Coprastan-3-one) crystallises in orthorhombic space group P2(1)2(1)2(1) with Z = 4. The unit cell dimensions are a = 6.701(2)Angstrom, b = 11.506(8)Angstrom, c = 32.183(4)Angstrom, V = 2481(2)Angstrom (3), D-cal = 1.077 Mg/m(3). The tide compound II (24-(R)-Hydroxy Coprastan-3-one) crystallises in orthorhombic space group P212121 with two molecules per assymetric unit and with Z = 8. The Unit cell dimensions are a = 10.954(2)Angstrom, b = 21.757(6)Angstrom, c = 21.130(7)Angstrom, V = 5035.0(2)Angstrom (3), D-cal = 1.062 Mg/m(3). In compound I and in both the molecules of compound II, the rings A, B & C are in chair conformation and the five membered ring D is in envelope conformation. The priority sequence attached to the chiral carbon C24 has "S" designation in compound I and "R" designation in compound II. The structures are stabilized by C-H . . .O and O-H---O hydrogen bonds.

Denaturant mediated unfolding of both native and molten globule states of maltose binding protein are accompanied by large [Delta]Cp's

Maltose binding protein (MBP) is a large, monomeric two domain protein containing 370 amino acids. In the absence of denaturant at neutral pH, the protein is in the native state, while at pH 3.0 it forms a molten globule. The molten globule lacks a tertiary circular dichroism signal but has secondary structure similar to that of the native state. The molten globule binds 8-anilino-1-naphthalene sulfonate (ANS). The unfolding thermodynamics of MBP at both pHs were measured by carrying out a series of isothermal urea melts at temperatures ranging from 274–329 K. At 298 K, values of [Delta]G°, [Delta]Cp, and Cm were 3.1 ± 0.2 kcal mol−1, 5.9 ± 0.8 kcal mol−1 K−1 (15.9 cal (mol-residue)−1 K−1), and 0.8 M, respectively, at pH 3.0 and 14.5 ± 0.4 kcal mol−1, 8.3 ± 0.7 kcal mol−1 K−1 (22.4 kcal (mol-residue)−1 K−1), and 3.3 M, respectively, at pH 7.1. Guanidine hydrochloride denaturation at pH 7.1 gave values of [Delta]G° and [Delta]Cp similar to those obtained with urea. The m values for denaturation are strongly temperature dependent, in contrast to what has been previously observed for small globular proteins. The value of [Delta]Cp per mol-residue for the molten globule is comparable to corresponding values of [Delta]Cp for the unfolding of typical globular proteins and suggests that it is a highly ordered structure, unlike molten globules of many small proteins. The value of [Delta]Cp per mol-residue for the unfolding of the native state is among the highest currently known for any protein.

Nonstandard, strongly interacting spin one $t \bar t$ resonances

Examining theories with an extended strong interaction sector such as axigluons or flavour universal colorons, we find that the constraints obtained from the current data on $t \bar t$ production at the Tevatron are in the range of $\sim {\cal O}$ TeV and thus competitive with those obtained from the dijet data. We point out that for large axigluon/coloron masses, the limits on the coloron mass may be different than those for the axigluon even for $\cot \xi = 1$. We also compute the expected forward-backward asymmetry for the case of the axigluons which would allow it to be discriminated against the SM as also the colorons. We further find that at the LHC, the signal should be visible in the $t \bar t$ invariant mass spectrum for a wide range of axigluon and coloron masses that are still allowed. We point out how top polarisation may be used to further discriminate the axigluon and coloron case from the SM as well as from each other.

Electrochemical Determination of the Stability of Mono- and Dicalcium Stannates

he thermodynamic properties of mono- and dicalcium stannates have been determined in the temperature range 973–-1423°K from the electromotive force measurements on solid oxide galvanic cells[dformula Pt, Ni + NiO//CaO - ZrO[sub 2]/Y[sub 2]0[sub 3] - ThO[sub 2]//SnO[sub 2] + Sn, W, Pt][dformula Pt, Ni + NiO//CaO - ZrO[sub 2]/Y[sub 2]O[sub 3] - ThO[sub 2]//CaSnO[sub 3] + SnO[sub 2] + Sn, W, Pt][dformula Pt, Ni + NiO//CaO - ZrO[sub 2]/Y[sub 2]O[sub 3] - ThO[sub 2]/Ca[sub 2]SnO[sub 4] + CaSnO[sub 3] + Sn, W, Pt]and [dformula Pt, Ni + NiO//CaO - ZrO[sub 2]sol;Y[sub 2]O[sub 3] - ThO[sub 2]//Ca[sub 2]SnO[sub 4] + CaO, W, Pt] The Gibbs free energy changes accompanying the formation of the stannates from component oxides may be represented by the equations[dformula 2CaO + SnO[sub 2] --> Ca[sub 2]SnO[sub 4]][dformula Delta G[degree] = - 17,040 + 0.85T ([plus-minus]300) cal][dformula CaO + SnO[sub 2] --> CaSnO[sub 3]][dformula Delta G[degree] = - 17,390 + 2.0T ([plus-minus]300) cal]The partial pressures of the tin bearing oxide species resulting from the decomposition of the stannates have been calculated as a function of the oxygen partial pressure by combining the results of this study with published information on the partial pressures and composition of oxide species over stannic oxide.

The oxygen potential of the systems Fe+FeCr2O4+ Cr2O3 and Fe+FeV2O4+ V2O3 in the temperature range 750 1600o C

From electromotive force (emf) measurements using solid oxide galvanic cells incorporating ZrOz-CaO and ThOz-YO~.s electrolytes, the chemical potentials of oxygen over the systems Fe + FeCrzO 4 + Cr20 ~ and Fe + FeV204 + V203 were calculated. The values may be represented by the equations: 2Fe(s, I) + Oz(g) + 2Cr2Oa(s) -- 2FeCr204 (s)Akto2 = - 151,400 + 34.7T (• cal= -633,400 + 145.5T(• J (750 to 1536~ A~tO2 = -158,000 + 38.4T(• cal= -661,000 + 160.5T(*1250) J (1536 to 1700~2Fe (s, I) + O2 (g) + 2V203 (s) -- 2FeV204 (s) A/~Oz = - 138,000 + 29.8T(+300) cal= - 577,500 + 124.7T (• J (750 to 1536~A/IO2 = -144,600 + 33.45T(-300) cal = -605,100 + 140.0T(~-1250) J (1536 to 1700~At the oxygen potentials corresponding to Fe + FeCrzO a + Cr203 equilibria, the electronic contribution to the conductivity of ZrO2-CaO electrolyte was found to affect the measured emf. Application of a small 60 cycle A.C. voltage with an amplitude of 50 mv across the cell terminals reduced the time required to attain equilibrium at temperatures between 750 to 9500C by approximately a factor of two. The second law entropy of iron chromite obtained in this study is in good agreement with that calculated from thermal data. The entropies of formation of these spinel phases from the component oxides can be correlated to cation distribution and crystal field theory.

Evidence of residual entropy in the cubic spinel Zn2TiO4

The standard free energies of formation of Zn2Ti04 and ZnTi03 have been determined in the temperature range 930° to i ioo'x from electromotive force measurements on reversible solid oxide galvanic cells;Ag-5at%znll I Pt, + CaO-Zr02 ZnO I II Ag-5at%Zn Y20r Th02 CaO-Zr02 + ,Pt Zn2Ti04+ ZnTi03 and II Ag-5at%Zn CaO-Zr02 + ,Pt ZnTi03+ Ti02 The values may be expressed by the equations,2ZnO (wurtz) + Ti02(rut) -> Zn2Ti04(sp), f:!:.Go = -750-2-46T (±75)cal;ZnO(wurtz) +Ti02(rut) -> ZnTi03(ilmen) ,f:!:.Co = -]600-0·]99T(±50)cal.Combination of the free energy values with the calorimetric heat of formation, and low-temperature and high-temperature heat capacity of Zn2Ti04 reported in literature, suggests a residual entropy of ],9 (±0·6) cal K-1 mol ? for the cubic spinel. Ideal mixing of Zn2+ and Ti4+ ions on the octahedral sites would result in a configurational contribution to the entropy of 2· 75 cal K-1 rnol ".The difference is indicative of short-range ordering of cations on octahedral sites.

Solubility and activity of oxygen in liquid gallium and gallium copper alloys

The solubility of oxygen in liquid gallium in the temperature range 775 –1125 °C and in liquid gallium-copper alloys at 1100 °C, in equilibrium with β-Ga2O3, has been measured by an isopiestic equilibrium technique. The solubility of oxygen in pure gallium is given by the equation log (at.% O) = −7380/T + 4.264 (±0.03) Using recently measured values for the standard free energy of formation of β-Ga2O3 and assuming that oxygen obeys Sievert's law up to the saturation limit, the standard free energy of solution of oxygen in liquid gallium may be calculated : View the MathML sourceΔ°298 = −52 680 + 6.53T (±200) cal where the standard state for dissolved oxygen is an infinitely dilute solution in which the activity is equal to atomic per cent. The effect of copper on the activity of oxygen dissolved in liquid gallium is found to be in good agreement with that predicted by a recent quasichemical model in which it was assumed that each oxygen is interstitially coordinated to four metal atoms and that the nearest neighbour metal atoms lose approximately half their metallic cohesive energies.

Solubility and activity of oxygen in liquid indium and copper indium alloys

The solubility of oxygen in liquid indium in the temperature range 650–820 °C and in liquid copper-indium alloys at 1100 °C in equilibrium with indium sesquioxide has been measured by a phase equilibration technique. The solubility of oxygen in pure indium is given by the relation log(at.% O) = −4726/T + 3.73 (±0.08) Using the recently measured values for the standard free energy of formation of In2O3 and assuming that oxygen obeys Sievert's law up to saturation, the standard free energy of solution of molecular oxygen in liquid indium is calculated as View the MathML sourceΔG°= −51 440 + 8.07 T (±500) cal where the standard state for dissolved oxygen is an infinitely dilute solution in which activity is equal to atomic per cent. The effect of indium additions on the activity coefficient of oxygen dissolved in liquid copper was measured by a solid oxide galvanic cell. The interaction parameter ϵ0In is given by View the MathML source The experimentally determined variation of the activity coefficient of oxygen in dilute solution in Cu-In alloys is in fair agreement with that predicted by a quasichemical model in which each oxygen atom is assumed to be interstitially coordinated to four metal atoms and the nearest neighbour metal atoms are assumed to lose approximately half their metallic cohesive energies.

Solubility and activity of oxygen in liquid germanium and germanium copper alloys

The solubility of oxygen in liquid germanium in the temperature range 1233 to 1397 K, and in liquid germanium-copper alloys at 1373 K, in equilibrium with GeO2 has been measured by the phase equilibration technique. The solubility of oxygen in pure germanium is given by the relation R470 log(at. pct 0)=-6470/T+4.24 (±0.07). The standard free energy of solution of oxygen in liquid germanium is calculated from the saturation solubility, and recently measured values for the free energy of formation of GeO2, assuming that oxygen obeys Sievert’s law up to the saturation limit. For the reaction, 1/2 O2(g)→ OGe ΔG° =-39,000 + 3.21T (±500) cal = -163,200 + 13.43T (±2100) J. where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct), in the limit, as concentration approaches zero. The effect of copper on the activity of oxygen dissolved in liquid germanium is found to be in good agreement with that predicted by a quasichemical model in which each oxygen was assumed to be bonded to four metal atoms and the nearest neighbor metal atoms to an oxygen atom are assumed to lose approximately half of their metallic bonds.

Correlations between structure and thermodynamic properties of spinels and their applications in technology

Measurements a/the Gibbs' energy enthalpy and entrupy vffarmation oj chromites, vanadites and alumlnat.:s 0/ F", Ni. Co'. Mn, Zn Mg and Cd, using solid oxide galvanic cells over a ternperature range extending approximately lOOO°C, have shown that the '~'Ilir"!,,, J'JrIl/iJ~ tion 0/ cubic 2-3 oxide spinel phases (MX!O,), from component oxide (MO) with rock-salt and X.Os whir c(1f'l/!ldwn st!'llt'lw,·. call b,' represented by a semi-empirical correlalion, ~S~ = --LiS + L'i,SM +~S~:"d(±O.3) cal.deg-1 mol-1 where /',.SM Is the entropy 0/calian mixing oillhe tetrahedral alld octahedral sites o/the spinel and Sr:~ is tlie enfropy associaf,'d Wifh Ih,' randomization a/the lahn-Telier distortions. A review a/the methods/or evaluating the cation distriblltion lfl spille!s suggeJ{j' l/r,l! Ihe most promising scheme is based Oil octahedral site preference energies from the crystal field theory for the Iral1silioll IIIl'f"! IlIIL';. For I/""-Irallsifioll melal cal ions site preference energies are derived relative /0 thol'lt fLI, [ransilion metal ions from measured high tClllP('ftJi ure Cal iUlI disll iiJuriol1 in spine! phases thar contail! one IransilioJl metal and another non-transition metal carion. For 2-3 srinds compulatiorrs b,IS"J Oil i.!c[J;' Temkin mixing on each catioll subialtice predici JistributionJ that are In fair agreement with X-ray and 1I1'IIIrOll ditTraction, /IIdg""!ic dll.! electrical propcrries, and spectroscopic measurements. In 2-4 spineis mixing vI ions do not foliow strictly ideal slllIistli:al Jaws, Th,' OIl/up) associated with the randomizalion 0/the Jllhn-Teller dislOriioll" appear to be significant, only ill spinels witll 3d'. 3d', 3d' (ifld~UI' iOtls in tetrahedral and 3d' and 3d9 ions in octahedral positions. Application 0/this structural model for predicting the thermodynamic proputies ofspinel solid .,olutiofl5 or,' illustrated. F,lr complex systems additional contributions arising from strain fields, redox equilibria and off-center ions have to be qllalllififti. The entropy correlation for spinels provides a method for evaluating structure tran:.jormafiofl entropies in silllple o.\id.-s, ["founlllion on the relative stabilities ofoxides in different crystallCtructures is USe/III for computer ea/culaliof! a/phase dfugrullls ofIlIrer,',,1 III (N.lll1ie5 by method, similar to thost: used by Kaufman and Bernstein for refractory alloy systems. Examples oftechnoiogical appliCation tnclude the predictioll ofdeoxidation equilibria in Fe-Mn-AI-O s),slelll at 1600°C duj ,'Ulllpltfalion 0/phase relutions in Fe-Ni-Cr-S system,

Flux density calibration in diffuse optical tomographic systems

The solution of the forward equation that models the transport of light through a highly scattering tissue material in diffuse optical tomography (DOT) using the finite element method gives flux density (Phi) at the nodal points of the mesh. The experimentally measured flux (U-measured) on the boundary over a finite surface area in a DOT system has to be corrected to account for the system transfer functions (R) of various building blocks of the measurement system. We present two methods to compensate for the perturbations caused by R and estimate true flux density (Phi) from U-measured(cal). In the first approach, the measurement data with a homogeneous phantom (U-measured(homo)) is used to calibrate the measurement system. The second scheme estimates the homogeneous phantom measurement using only the measurement from a heterogeneous phantom, thereby eliminating the necessity of a homogeneous phantom. This is done by statistically averaging the data (U-measured(hetero)) and redistributing it to the corresponding detector positions. The experiments carried out on tissue mimicking phantom with single and multiple inhomogeneities, human hand, and a pork tissue phantom demonstrate the robustness of the approach. (C) 2013 Society of Photo-Optical Instrumentation Engineers (SPIE) DOI: 10.1117/1.JBO.18.2.026023]

Three-dimensional acoustic analysis of an elliptical chamber muffler with a side inlet and a side outlet

The acoustical behaviour of an elliptical chamber muffler having a side inlet and side outlet port is analyzed in this paper, wherein a uniform velocity piston source is assumed to model the 3-D acoustic field in the elliptical chamber cavity. Towards this end, we consider the modal expansion of the acoustic pressure field in the elliptical cavity in terms of the angular and radial Mathieu func-tions, subjected to the rigid wall condition. Then, the Green's function due to the point source lo-cated on the side (curved) surface of the elliptical chamber is obtained. On integrating this function over the elliptical piston area on the curved surface of the elliptical chamber and subsequent divi-sion by the area of the elliptic piston, one obtains the acoustic pressure field due to the piston driven source which is equivalent to considering plane wave propagation in the side ports. Thus, one can obtain the acoustic pressure response functions, i.e., the impedance matrix (Z) parameters due to the sources (ports) located on the side surface, from which one may also obtain a progressive wave rep-resentation in terms of the scattering matrix (S). Finally, the acoustic performance of the muffler is evaluated in terms of the Transmission loss (TL) which is computed in terms of the scattering pa-rameters. The effect of the axial length of the muffler and the angular location of the ports on the TL characteristics is studied in detail. The acoustically long chambers show dominant axial plane wave propagation while the TL spectrum of short chambers indicates the dominance of the trans-versal modes. The 3-D analytical results are compared with the 3-D FEM simulations carried on a commercial software and are shown to be in an excellent agreement, thereby validating the analyti-cal procedure suggested in this work.