Observation and implications of high mass-to-charge ratio ions from electrospray ionization mass spectrometry

High mass-to-charge ratio ions (> 4000) from electrospray ionization (ESI) have been observed for several proteins, including bovine cytochrome c (M _r 12,231) and porcine pepsin (M _r 34,584), by using a quadrupole mass spectrometer with an m/z 45,000 range. The ESI mass spectrum for cytochrome c in an aqueous solution gives a charge state distribution that ranges from 12 + to 2 +, with a broad, low-intensity peak in the mass-to-charge ratio region corresponding to the [M + H]⁺ ion. the negative ion ESI mass spectrum for pepsin in 1% acetic acid solution shows a charge state distribution ranging from 7? to 2?. To observe the [M - H]^? ion, harsher desolvation and interface conditions were required. Also observed was the abundant aggregation of the protens with average charge states substantially lower than observed for their monomeric counterparts. The negative ion ESI mass spectrum for cytochrome c in 1–100 mM NH₄OAc solutions showed greater relative abundances for the higher mass-to-charge ratio ions than in acuidic solutions, with an [M - H]^? ion relative abundance approximately 50% that of the most abundant charge state peak. The observation that protein aggregates are formed with charge states comparable to monomeric species (at fower mass-to-charge ratios) suggests that the high mass-to-charge ratio monomers may be formed by the dissociation of aggregate species. The observation of low charge state and aggregate molecular ions concurrently with highly charged species may serve to support a variation of the charged residue model, originally described by Dole and co-workers (Dole, M., et al. J. Chem. Phys. 1968, 49, 2240; Mack, L. L., et al. J. Chem. Phys. 1970, 52, 4977) which involves the Coulombically driven formation of either very highly solvated molecular ions or lower ananometer-diameter droplets.     

A universal algorithm for fast and automated charge state deconvolution of electrospray mass-to-charge ratio spectra

This article describes a new algorithm for charge state determination and deconvolution of electrospray ionization (ESI) mass-to-charge ratio spectra. The algorithm (Zscore) is based on a charge scoring scheme that incorporates all above-threshold members of a family of charge states or isotopic components, and deconvolves both low- and high-resolution mass-to-charge ratio spectra, with or without a peak list (stick plot). A scoring weight factor, log (I/I ₀), in which I is the signal magnitude at a calculated mass-to-charge ratio, and I ₀ is the signal threshold near that mass-to-charge ratio, was used in most cases. For high-resolution mass-to-charge ratio spectra in which all isotopic peaks are resolved, the algorithm can deconvolve overlapped isotopic multiplets of the same or different charge state. Compared to other deconvolution techniques, the algorithm is robust, rapid, and fully automated (i. e., no user input during the deconvolution process). It eliminates artifact peaks without introducing peak distortions. Its performance is demonstrated for experimental ESI Fourier transform ion cyclotron resonance mass-to-charge ratio spectra (both low and high resolution). Charge state deconvolution to yield a “zero-charge” mass spectrum should prove particularly useful for interpreting spectra of complex mixtures, identifying contaminants, noncovalent adducts, fragments (N-terminal, C-terminal, internal), and chemical modifications of electrosprayed biomacromolecules.     

Proton transfer reaction studies of multiply charged proteins in a high mass-to-charge ratio quadrupole mass spectrometer

Proton transfer reaction of multiply charged ions at high mass-to-charge ratios were explored with a low frequency quadrupole mass spectrometer. This instrument enabled a qualitative comparison of proton transfer reaction rates at low charge states for ions generated by electrospray ionization (ESI) from different solution conformations and for disulfide-linked versus disulfide-reduced protein ions. Proton transfer reactions that efficiently reduced the number of charges for ESI-generated ions to approximately the number of arginines in the polypeptide sequence were observed. No significant differences in gas-phase reaction rates were noted between different solution conformers. Differences in reaction rates between “native” and disulfide-reduced proteins were much smaller than those observed below m/z 2000 with lower proton affinity reagents or by using lower reagent concentrations. These smaller differences in reaction rates are thought to reflect the reduced electrostatic contributions from widely spaced charge sites and thus, the reduced sensitivity to an ion's three-dimensional structure or “compactness.”     

Effect of dispersion on the relaxation-retardation time scale ratio

A simple relation between relaxation (modulus) and retardation (permittivity and compliance) times is determined for cases of dispersive instead of purely exponential response functions. An analytical solution for the Cole-Cole case and numerical treatments of the Cole-Davidson function reveal that the ratio of the relaxation- to retardation time constant is given by the ratio of the high- to low-frequency dielectric constant raised to the power of 1x, where x is the exponent that gauges the deviation from exponentiality.     

Trapping of wide range mass-to-charge ions and dependence on matrix amount in internal source MALDI-FTMS

Internal ionization source MALDI-FTMS shows clear variation of number average molecular weight (M(n)) for an equimolar mixture of four PEG polymers (PEG 2000, PEG 4000, PEG 6000, PEG 8000) when the 2,5-dihydroxy benzoic acid (DHB) matrix to PEG ratio is varied or the laser power is changed. As the matrix to analyte ratio is increased, the analyte signal of higher molecular mass ions increases and the signal of lower mass ions decreases. Laser power dependence studies show a similar trend. Possible explanations for these observations are discussed.     

The Prigogine-Defay ratio revisited

One of the basic characteristics of the glass transition, the Prigogine-Defay ratio, connecting jumps of the thermal expansion coefficient, isothermal compressibility, and isobaric specific heat capacity in vitrification is rederived in the framework of the thermodynamics of irreversible processes employing the order-parameter concept introduced by de Donder and van Rysselberghe [Thermodynamic Theory of Affinity (Stanford University Press, Stanford, 1936)]. In our analysis, glass-forming liquids and glasses are described by only one structural order parameter. However, in contrast to previous approaches to the derivation of this ratio, the process of vitrification is treated not in terms of Simon's simplified model [Z. Anorg. Allg. Chem. 203, 219 (1931)] as a freezing-in process proceeding at some sharp temperature, the glass transition temperature T(g), but in some finite temperature interval accounting appropriately for the nonequilibrium character of vitrifying systems in this temperature range. As the result of the theoretical analysis, we find, in particular, that the Prigogine-Defay ratio generally has to have values larger than 1 for vitrification in cooling processes. Quantitative estimates of the Prigogine-Defay ratio are given utilizing a mean-field lattice-hole model of glass-forming melts. Some further consequences are derived concerning the behavior of thermodynamic coefficients, in particular, of Young's modulus in vitrification. The theoretical results are found to be in good agreement with experimental data.     

The diiodine basicity scale: toward a general halogen-bond basicity scale

The new diiodine basicity scale pK_BI2 is quasi‐orthogonal to most known Lewis basicity scales (hydrogen‐bond, dative‐bond and cation basicity scales). The diiodine basicity falls in the sequence N>P≈Se>S>I≈O>Br>Cl>F for the iodine‐bond acceptor atomic site and SbO≈NO≈AsO>SeO>PO>SO>C?O>? O? >SO₂ or PS?? S? >C?S?N?C?S for the functionality of oxygen or sulfur bases. Substituent effects are quantified through linear free energy relationships, which allow the calculation of individual complexation constants for each site of polybases and thus the classification of aromatic ethers as carbon π bases and of aromatic amines, thioethers and selenoethers as N, S and Se bases, respectively. The pK_BI2 values of nBu₃N⁺‐N^?C≡N, 2‐aminopyridine and 1,10‐phenanthroline reveal a superbasic nitrile, a hydrogen‐bond‐assisted iodine bond and a two‐centre iodine bond, respectively. The diiodine basicity scale is a general inorganic but family‐dependent organic halogen‐bond basicity scale because organic halogen‐bond donors such as IC≡N and ICF₃ have a stronger electrostatic character than I₂. The family independence can be restored by the addition of an electrostatic parameter, either the experimental pK_BHX hydrogen‐bond basicity scale or the computed minimum electrostatic potential.     

The landau-placzek ratio for multicomponent fluids

Abstract

Under the assumption that the coupling between the sound modes and modes associated with heat and mass diffusion can be neglected, an expression for the Landau-Placzek ratio for multicomponent fluids is derived using thermodynamic fluctuation theory. Applications of the general formula to ternary systems are discussed briefly     

The amino acid ratio on thin layer chromatography

A procedure for the use of the amino acid ratio on thin layer chromatography is described. Its use in developing countries is emphasized. The advantages of the amino acid ratio on thin layer chromatography versus paper chromatography are presented.     

Comparison of particle-in-cell simulations with experimentally observed frequency shifts between ions of the same mass-to-charge in fourier transform ion cyclotron resonance mass spectrometry

It has been previously observed that the measured frequency of ions in a Fourier transform mass spectrometry experiment depend upon the number of trapped ions, even for populations consisting exclusively of a single mass-to-charge. Since ions of the same mass-to-charge are thought not to exert a space-charge effect among themselves, the experimental observation of such frequency shifts raises questions about their origin. To determine the source of such experimentally observed frequency shifts, multiparticle ion trajectory simulations have been conducted on monoisotopic populations of Cs⁺ ranging from 10² ions to 10⁶ ions. A close match to experimental behavior is observed. By probing the effect of ion number and orbital radius on the shift in the cyclotron frequency, it is shown that for a monoisotopic population of ions, the frequency shift is caused by the interaction of ions with their image-charge. The addition of ions of a second mass-to-charge to the simulation allows the comparison of the magnitude of the frequency shift resulting from space-charge (ion-ion) effects versus ion interactions with their image charge.     

The importance of aspect ratio in profile analysis tensiometry

The latest developments in profile analysis tensiometry (PAT) for determining surface tension and interfacial viscoelastic parameters involve the determination of a digital interface profile and its best fit with the Young–Laplace equation. In this short communication, we show that the results for surface tension and other interfacial parameters determined by PAT are extremely sensitive to the (aspect) ratio of length to width of a pixel. Fine calibration (to five decimal digits) for the aspect ratio required to obtain physically consistent results is not always achieved with conventional numerical procedures due to nanometer resolution limit of optical imaging devices but can be manually adjusted using the known surface tension of pure water and/or surfactant solutions at reference temperature.     

The scale of non-homogeneity as defined by diffusion measurements

The asymptotic behaviour of the permeation rate in non-homogeneous laminar slabs of increasing width l is studied. We show rigorously that for a wide class of slabs with nonhomogeneities distributed in a statistically homogeneous manner, the permeation rate approaches that of a homogeneous slab as 1/l². The result is compared with previous studies of this subject.     

The acidity scale of HCl solutions in N,N-dimethylformamide

The scale of the thermodynamic acidity of HCl solutions in DMF has been measured at 25 and 39.5 °C up to 15 mol L^–1 acid concentration by the indicator method. It is shown that in the HCl-DMF system the ionization of the nitroaniline-derived indicators occurs by the ion pair mechanism. Within the temperature range studied acidity is independent of temperature. Indicators of the nitroaniline series are used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1025–1028, June, 1994.     

The intensity ratio of corresponding symmetric and antisymmetric stretching modes

The intensity ratio of corresponding symmetric and antisymmetric stretching modes is derived for C_2v and C_3v molecules, using the zero-order approximation of bond moment theory. The validity of the final relations is discussed with respect to the assumptions made. The relations could be helpful in the estimation of individual intensities in cases in which the frequencies of corresponding symmetric and antisymmetric modes nearly coincide.     

Molecular scale bioelectrochemistry

Our ability to interface with biological macromolecules continues to advance at a significant pace and brings with it potential applications that are as broad as they are powerful. Running alongside this evolution has been the refinement of methods by which interfaces can be probed at scales approaching (or being at) the molecular. Through combinations of experimental design, proximal probe technology and high sensitivity optical imaging, one can truly probe the bioelectronic interface at levels that are both startling and associated with unprecedented levels of detail.     

The EACN scale for oil classification revisited thanks to fish diagrams

The phase behavior of C(10)E(4)-oil-water systems at constant o/w ratio and variable temperature (fish diagram) has been investigated for several homologous oil families. The temperature T( *) and surfactant concentration C( *) at the critical point were determined for 10 n-alkanes varying from C(6) to C(28) as well as for a series of alkylcyclohexanes and alkylbenzenes. On the basis of T( *), equivalent alkane carbon numbers (EACN) were assigned to nonlinear alkanes, alkylbenzenes, and alkylcyclohexanes. The consistency of the method was shown by corroborating that the EACN values of oils previously investigated with other C(i)E(j) (dibutyl ether, squalane, isopropyl myristate, and dodecylbenzene) are the same when determined with C(10)E(4). The fact that two oils of different nature but with the same EACN (i.e., the same T( *)) do not exhibit the same C( *) is discussed in terms of monomeric solubility of the surfactant in the oil (CMC(oil)).     

The isomeric cross-section ratio in double neutron capture of 93Nb

The yields of ⁹⁵Nb isomers were investigated by means of the double neutron capture of ⁹³Nb target. The effective cross section of ⁹⁴Nb(n,γ)^95mNb and ⁹⁴Nb(n,γ)^95gNb reactions were found, by the activation method, to be 0.61 ± 0.03 barn and 14.6 ± 0.3 barn, respectively, with the choice of Wescott's epithermal index r√(T/T₀) = 0.022. The observed isomeric cross section ratio of the reaction was compared with the theoretical prediction on the basis of the statistical model. As a result, the spin of the compound nucleus was assigned and the contribution of the quadrupole transition was deduced in the gamma cascade process.