Thermodynamic analysis of lysozyme adsorbed to silica

The structural stability of hen egg white lysozyme in solution and adsorbed to small colloidal silica particles at various surface concentrations was investigated using hydrogen-deuterium (H/D) exchange in combination with mass spectrometry (HDX-MS) and differential scanning calorimetry (DSC). The combination of HDX-MS and DSC allows a full thermodynamic analysis of the lysozyme structure as both the enthalpy and the Gibbs free energy can be derived from the various measurements. Moreover, both HDX-MS and DSC provide information on the relative structural heterogeneity of lysozyme in the adsorbed state compared to that in solution. Results demonstrated that at high surface coverage, the structural stability of lysozyme was only marginally affected by adsorption to silica particles whereas the unfolding enthalpy decreased by more than 10%, meaning that the entropy of lysozyme increased with a similar value upon adsorption. Furthermore, the structural heterogeneity increased considerably. At lower surface concentrations, the structural heterogeneity increased further whereas the enthalpy of unfolding decreased. Further analyses of the HDX-MS experiments clearly indicated that folding/unfolding of lysozyme occurs through a two-domain process. These two domains had a similar amount of structural elements and a difference in stabilization energy of 8 kJ/mol, regardless if lysozyme was in solution or adsorbed to silica.     

Synthesis and structures of cis- and trans-bis(alkyneselenolato)platinum(II) complexes

The reaction of 2 equiv of LiSeCC-n-C(5)H(11) (1) with cis-PtCl(2)(Ph(3)P)(2) (2) gives a mixture of the cis and trans isomers of Pt(Ph(3)P)(2)(SeCC-n-C(5)H(11))(2) (3), which slowly isomerizes in CH(2)Cl(2) to the preferred trans form trans-3. The closely related cis-[Pt(dppf)(2)(SeCC-n-C(5)H(11))(2)] (4) (dppf = bis(diphenylphosphino)ferrocene) was prepared by a similar metathetical reaction using the platinum chloride complex of the chelating dppf to impose the cis geometry. The structures of the cis and trans complexes have been investigated in solution by heteronuclear NMR ((31)P, (77)Se, and (195)Pt) and, in the cases of trans-3 and 4, characterized in the solid state by single-crystal X-ray diffraction. Changing the coordination geometry from cis to trans induces significant changes in the structural and spectroscopic parameters, which do not comply with the previously anticipated donor-acceptor properties of selenolate ligands.     

Superconductivity in copper, silver, and gold compounds

High-temperature superconductivity exists in layered, square-planar cuprates, but is almost absent in most other Cu(II) compounds and in most Ag(II) and Au(II) compounds. Valence state II is quite unusual in silver and gold and often disproportionates to valence states I and III ("negative-U compounds"). The two-electron difference in oxidation state is suggestive of electron pairing, a prerequisite for superconductivity. In the present paper the connection between disproportionation and geometrical structure on one hand and superconductivity on the other is discussed by using the accepted theory for mixed valence complexes. It is concluded that absence of superconductivity in gold and silver compounds can be connected to the instability of oxidation state II and the large difference in equilibrium geometry between oxidation states I and III.     

Phase-fixed double-group 3-Γ symbols. IV. Real 3-Γ symbols and coupling coefficients for the group hierarchies T* ⊃ C 3 * and T* ⊃ C 2 *

We present sets of real 3- symbols which correspond to explicitly given irreducible matrix representations for the two double group hierarchies T* C ₃ ^* and T* C ₂ ^* . They fit into the formalism exposed in a previous paper [1] on the general theory of 3- symbols and coupling coefficients and illustrate much of the discussion in a subsequent one [2] treating the particular properties of the double groups.     

Theoretical exploration of structure-reactivity relationships in organometallic chemistry: butadiene insertion into the organyltransition-metal bond and conversion of the allyltransition-metal fragment in the [Ni(η-Cp)(η-phenyl)(η-butadiene)] complex

We have theoretically examined the reaction course of the butadiene insertion into the arylNi^II bond in the [Ni^II(η⁵-Cp)(η¹-phenyl)(η²-butadiene)] complex (1), by employing a gradient-corrected DFT method. Critical elementary processes have been scrutinized, viz. monomer insertion, rotational allylic isomerization and allylic η¹-σ→η³-π rearrangement. The first mechanism suggested by Lehmkuhl et al. was refined and supplemented with important details. The critical factors that determine the generation of anti-η³- and syn-η³-allyl isomers of the [Ni^II(η⁵-Cp)(1-benzyl-allyl)] product have been elucidated. This let us to rationalize the experimentally observed, almost exclusive formation of the anti-η³-allyl isomer. Butadiene preferably inserts in η²-mode into the η¹-phenylNi^II bond, initially giving rise to the η¹(C³)-allyl product species, 3σ. The direct formation of the η³-allyl product species, 3π, along the alternative path for η⁴-butadiene insertion, however, is found to be almost entirely disabled kinetically. The thermodynamically favorable η²-trans form of 1 is also shown to be more reactive in accomplishing CC bond formation. Species 3σ is indicated to be a metastable intermediate, occurring in an appreciable stationary concentration. Its respective anti and syn isomeric forms are likely to be in equilibrium, due to the facile rotational isomerization. The subsequent allylic rearrangement into the thermodynamically strongly favorable η³-allylNi^II coordination mode is shown to be the crucial elementary step that discriminates which of the isomeric η³-allyl forms is preferably generated. The higher reactivity of the anti isomer in this process decisively determines the almost exclusive formation of the anti-η³-allyl product species under kinetic control. The requirement of elevated temperatures for the anti-η³-allyl→syn-η³-allyl isomerization to occur, as revealed from experiment, is attributed to the pronounced thermodynamic stability of the η³-allylNi^II coordination.     

Simultaneous determination of albumin and immunoglobulin G with fluorescence spectroscopy and multivariate calibration

A method is proposed for the simultaneous determination of albumin and immunoglobulin G (IgG1) with fluorescence spectroscopy and multivariate calibration with partial least squares regression (PLS). The influence of some instrumental parameters were investigated with two experimental designs comprising 19 and 11 experiments, respectively. The investigated parameters were excitation and emission slit, detection voltage and scan rate. When a suitable instrumental setting had been found, a minor calibration and test set were analysed and evaluated. Thereafter, a larger calibration of albumin and IgG1 was made out of 26 samples (0-42 μg ml⁻¹ albumin and 0-12.7 μg ml⁻¹ IgG1). This calibration was validated with a test set consisting of 14 samples in the same concentration range. The precision of the method was estimated by analysing two test set samples for six times each. The scan modes tested were emission scan and synchronous scan Δ60 nm. The results showed that the method could be used for determination of albumin and IgG1 (albumin, root mean square error of prediction (RMSEP) <2, relative standard error of prediction (RSEP) <6% and IgG1, RMSEP <1, RSEP <8%) in spite of the overlapping fluorescence of the two compounds. The estimated precision was relative standard deviation (R.S.D.) <1.7%. The method was finally applied for the analysis of some sample fractions from an albumin standard used in affinity chromatography.     

Theoretical analysis of the porphyrin-porphyrin exciton interaction in circular dichroism spectra of dimeric tetraarylporphyrins

Chiral bis-porphyrins are currently the subject of intense interest as chiral receptors and as probes in the determination of structure and stereochemistry. To provide an improved framework for interpreting the circular dichroism (CD) spectra of bis-porphyrins, we have calculated the CD spectra of chiral bis-porphyrins from three classes: I, where porphyrins can adopt a relatively wide range of orientations relative to each other; II, porphyrins have a fixed relative orientation; III, porphyrins undergo pi-stacking. The calculations primarily utilized the classical polarizability theory of DeVoe, but were supplemented by the quantum mechanical matrix method. Class I was represented by three isomers of the diester of 5alpha-cholestane-3,17-diol with 5-(4'-carboxyphenyl)-10,15,20-triphenylporphin (2-alphabeta, 2-betaalpha, 2-betabeta). Careful analysis of the torsional degrees of freedom led to two to four minimum-energy conformers for each isomer, in each of which the phenyl-porphyrin bonds had torsional angles near 90 degrees. Libration about these bonds is relatively unrestricted over a range of +/-45 degrees. CD spectra in the Soret region were calculated as Boltzmann-weighted averages over the low-energy conformers for each isomer. Three models were used: the effective transition moment model, in which only one of the degenerate Soret components is considered, along the 5-15 direction; the circular oscillator model, in which both Soret components are given equal weight; and the hybrid model, in which the 10-20 oscillator is given half the weight of the 5-15 oscillator, to mimic the effect of extensive librational averaging about the 5-15 direction. All three models predict Soret exciton couplets with signs in agreement with experiment. Quantitatively, the best results are given by the hybrid and circular oscillator models. These results validate the widely used effective transition moment model for qualitative assignments of bis-porphyrin chirality and thus permit application of the exciton chirality model. However, for quantitative studies, the circular oscillator or hybrid models should be used. The simplified effective transition moment and hybrid models are justified by the librational averaging in the class I bis-porphyrins and should only be used with such systems. Two class II bis-porphyrins were also studied by DeVoe method calculations in the circular oscillator model, which yielded good agreement with experiment. Class III bis-porphyrins were represented by 2-alphaalpha, for which the calculations gave qualitative agreement. However, limitations in the conformational analysis with the close contacts and dynamic effects in these pi-stacked systems preclude quantitative results.     

Kekulé structure counts for some classes of all-benzenoid and all-coronoid hydrocarbons

Summary A general formula for the Kekulé structure count (K) is deduced for the class of catacondensed all-benzenoids with unbranched backbones. The formula is extended to thin pericondensed all-benzenoids, where allowance is made for pyrene units. In this treatment the fragmentation matrices are employed. A generalization of these matrices is furnished. Next some generalK formulas for classes of catacondensed and thin pericondensed all-coronoids are deduced. Again the fragmentation matrices are employed, but the problem is also studied in terms of certain polynomials.Dedicated to the memory of Professor Oskar E. Polansky, who died in January 1989. He was the one who coined the term all-benzenoid.     

Cobalt Chalcogenide Clusters. Synthesis,Characterization and DFT Calculations of [Co4Se2(CO)10] and [Co4Te2(CO)11]. Crystal Structure of [Co8Se4(CO)16(μ‐dppa)2]

The reactions of [Co₂(CO)₈] with E(SiMe₃)₂ (E = Se, Te) in CH₂Cl₂ result in the formation of the compounds [Co₄Se₂(CO)₁₀]> ( 1 ) and [Co₄Te₂(CO)₁₁] ( 2 ), respectively. Both cluster complexes have similar molecular structures in which the cobalt atoms form four‐membered rings with μ₄‐bridging chalcogen atoms (Se and Te) above and below the plane of the metal atoms and the carbonyl ligands as either terminal or μ₂‐bridging ligands. DFT‐calculations for both compounds have been carried out in order to obtain some more information about their electronic distribution. In the presence of the phosphine Ph₂PC≡CPPh₂ (dppa), the reaction of [Co₂(CO)₈] with Se(SiMe₃)₂ leads to the formation of [Co₈Se₄(CO)₁₆(μ‐dppa)₂] ( 3 ). During the reaction two molecules of [Co₂(CO)₈] have been added to the acetylene groups of the dppa ligands, whilst the remaining cobalt atoms coordinate to the phosphorus atoms of the phosphine. In this compounds the selenium atoms act as μ₃‐ligands, bridging the metal atoms bonded to the phosphorus with those bonded to the acetylene groups.     

Shake-up and multiplet structure of ESCA satellites of Cu compounds

The ESCA inner shell spectra of Cu compounds are investigated theoretically. It is shown that the large satellites appearing for Cu(II) compounds correspond to shake-up states which are close to the configuration p⁵d⁹ and have the characteristic multiplet splitting of this configuration.