Use of monoatomic and polyatomic projectiles for the characterisation of polylactic acid by static secondary ion mass spectrometry

The application of polyatomic primary ions is a strongly developing branch of static secondary ion mass spectrometry (S-SIMS), since these projectiles allow a significant increase in the secondary ion yields to be achieved. However, the different limitations and possibilities of certain polyatomic primary ions for use on specific functional classes of samples are still not completely known. This paper compares the use of monoatomic and polyatomic primary ions in S-SIMS for thin layers of polylactic acid (PLA), obtained by spin-coating solutions on silicon wafers. Bombardment with Ga+, Xe+ and SF5+ primary ions allowed the contribution of the projectile mass and number of atoms in the gain in ion yield and molecular specificity (relative importance of high m/z and low m/z signals) to be assessed. Samples obtained by spin-coating solutions with increasing concentration showed that optimal layer thickness depended on the primary ion used. In comparison with the use of Ga+ projectiles, the yield of structural ions increased by a factor of about 1.5 to 2 and by about 7 to 12 when Xe+ and SF5+ primary ion bombardment were applied, respectively. A detailed fragmentation pattern was elaborated to interpret ion signal intensity changes for different projectiles in terms of energy deposition and collective processes in the subsurface, and the internal energy of radical and even-electron precursor ions.     

Improvement of biological time-of-flight-secondary ion mass spectrometry imaging with a bismuth cluster ion source

A new liquid metal ion gun (LMIG) filled with bismuth has been fitted to a time-of-flight-secondary ion mass spectrometer (TOF-SIMS). This source provides beams of Bi(n)q+ clusters with n = 1-7 and q = 1 and 2. The appropriate clusters have much better intensities and efficiencies than the Au3+ gold clusters recently used in TOF-SIMS imaging, and allow better lateral and mass resolution. The different beams delivered by this ion source have been tested for biological imaging of rat brain sections. The results show a great improvement of the imaging capabilities in terms of accessible mass range and useful lateral resolution. Secondary ion yields Y, disappearance cross sections sigma, efficiencies E = Y/sigma , and useful lateral resolutions deltaL have been compared using the different bismuth clusters, directly onto the surface of rat brain sections and for several positive and negative secondary ions with m/z ranging from 23 up to more than 750. The efficiency and the imaging capabilities of the different primary ions are compared by taking into account the primary ion current for reasonable acquisition times. The two best primary ions are Bi3+ and Bi5(2+). The Bi3+ ion beam has a current at least five times larger than Au3+ and therefore is an excellent beam for large-area imaging. Bi5(2+) ions exhibit large secondary ions yields and a reasonable intensity making them suitable for small-area images with an excellent sensitivity and a possible useful lateral resolution <400 nm.     

Comparison of mono- and polyatomic primary ions for the characterization of organic dye overlayers with static secondary ion mass spectrometry

Organic carbocyanine dye coatings have been analyzed by time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) using three types of primary ions: Ga(+) operating at 25 keV, and Xe(+) and SF(5) (+) both operating at 9 keV. Secondary ion yields obtained with these three primary ions have been compared for coatings with different layer thickness, varying from (sub)-monolayer to multilayers, on different substrates (Si, Ag and AgBr cubic microcrystals). For (sub)-monolayers deposited on Ag, Xe(+) and SF(5) (+) primary ions generate similar precursor ion intensities, but with Ga(+) slightly lower precursor ion intensities were obtained. Thick coatings on Ag as well as mono- and multilayers on Si produce the highest precursor and fragment ion intensities with the polyatomic primary ion. The yield difference between SF(5) (+) and Xe(+) can reach a factor of 6. In comparison with Ga(+), yield enhancements by up to a factor of 180 are observed with SF(5) (+). For the mass spectrometric analysis of dye layers on AgBr microcrystals, SF(5) (+) again proves to be the primary ion of choice.     

Comparison of primary monoatomic with primary polyatomic ions for the characterisation of polyesters with static secondary ion mass spectrometry

Static secondary ion mass spectrometry (S-SIMS) emerges as one of the most adequate methods for the surface characterisation of polymers with an information depth of essentially one monolayer. The continuing search for increased analytical sensitivity and specificity has led to exploring the use of polyatomic primary ions as an alternative to the traditionally applied monoatomic projectiles. As part of a systematic investigation on polyatomic bombardment of organic and inorganic solids, this paper focuses on selected polyesters. Mass spectra and ion yields are compared for layers deposited on silicon wafers by spincoating solutions with different concentrations of poly(epsilon-caprolactone) (PCL), poly(butylene adipate) (PBA) and poly(ethylene adipate) (PEA). Accurate mass measurements have been used to support the assignment of the ions and link the composition of the detected ions to the analyte structure. Use of polyatomic projectiles increases the yield of structural ions with a factor of +/-15, +/-30 and +/-10 for PCL, PBA and PEA, respectively, in comparison to bombardment with Ga+ primary ions, while the molecular specificity is improved by the detection of additional high m/z ions.     

An investigation of secondary ion yield enhancement using Bi n 2+ (n=1, 3, 5) primary ions

We have investigated secondary ion yield enhancement using Bin2+ (n=1, 3, 5) primary ions impacting phenylalanine, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE), cholesterol, Irganox 1010, and polymer films adsorbed on silicon and aluminum. Secondary ion yields are increased using Bi2+and Bi3(2+) primary ions for the molecular layers and polymers that can undergo allyl cation rearrangements. For Irganox 1010, the deprotonated molecular ion yields (m/z 1175; [M-H]-) are one to two times larger for Bi2+ and Bi(3)2+ primary ions than for Bi+ and Bi3+ at the same primary ion velocities. In the positive ion mode, the largest fragment ion yield (m/z 899) is 1.5 times larger for Bi2+ ions than for Bi+. For Bi3(2+) the largest fragment ion yield is only 70% of the ion yield using Bi3+, but the secondary ion yields of the fragment ions at m/z 57 and 219 are enhanced. For polymers that can undergo allyl cation rearrangement reactions the secondary ion yield enhancements of the monomer ions range from 1.3 to 4.3. For Bi(5)2+ primary ions, secondary ion yields were the same or slightly larger than for Bi5+ in the negative ion mass spectra for Irganox 1010, but lower in the positive ion mode. No secondary ion yield enhancements were measured on polymer samples for Bi5(2+). For all polymer films studied, secondary ion intensities from the oligomer regions are substantially decreased using Bin2+ (n=1, 3, 5). We discuss differences in the ionization mechanisms for doubly and singly-charged Bi primary ion bombardment.     

Energetic ion bombardment of Ag surfaces by C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> and Ga<Superscript>+</Superscript> projectiles

The ion bombardment-induced release of particles from a metal surface is investigated using energetic fullerene cluster ions as projectiles. The total sputter yield as well as partial yields of neutral and charged monomers and clusters leaving the surface are measured and compared with corresponding data obtained with atomic projectile ions of similar impact kinetic energy. It is found that all yields are enhanced by about one order of magnitude under bombardment with the C60+ cluster projectiles compared with Ga+ ions. In contrast, the electronic excitation processes determining the secondary ion formation probability are unaffected. The kinetic energy spectra of sputtered particles exhibit characteristic differences which reflect the largely different nature of the sputtering process for both types of projectiles. In particular, it is found that under C60+ impact (1) the energy spectrum of sputtered atoms peaks at significantly lower kinetic energies than for Ga+ bombardment and (2) the velocity spectra of monomers and dimers are virtually identical, a finding which is in pronounced contrast to all published data obtained for atomic projectiles. The experimental findings are in reasonable agreement with recent molecular dynamics simulations.     

Is proton cationization promoted by polyatomic primary ion bombardment during time-of-flight secondary ion mass spectrometry analysis of frozen aqueous solutions?

Ion bombardment of pure water ice by Au+ monoatomic and Au3 + and C60 + polyatomic projectiles results in the emission of two series of water cluster ions-(H2O)n + and (H2O)nH+-with n ranging from 1 to >40. The cluster ion yields are very significantly higher under polyatomic ion bombardment than when using an Au+ primary ion. The yield of the protonated water species (H2O)nH+ is found to be enhanced by increasing ion fluence. C60 + bombardment results in a very dramatic increase in the (H2O)nH+ yield and decrease in the yield of (H2O)n +. Au3 + also significantly increased the yield of protonated species relative to the non-protonated but to a lesser extent than C60 +. Bombardment by Au+ also increased the yield of protonated species but to a very much smaller extent. The hypothesis that the protonated species may enhance the yield of [M+H]+ from solute molecules in solution has been investigated using two amino acids, alanine and arginine, and a nucleic base, adenine. The data suggest that the protons produced by the sputtering of water ice are depleted in the presence of these solutes and concurrently the yields of solute-related [M+H]+ and immonium secondary ions are greatly enhanced. These yield enhancements are analysed in the light of other possible contributors such as increased rates of sputtering under polyatomic beams and increased secondary ion yields as a consequence of solute dispersion. It is concluded that enhanced proton attachment is occurring in polyatomic sputtered frozen aqueous solutions.     

Theoretical investigation on the electronic and geometric structure of GaN2+ and GaN4+

The electronic and geometric structures of gallium dinitride cation, GaN2+ and gallium tetranitride cation, GaN4+ were systematically studied by employing density functional theory (DFT-B3LYP) and perturbation theory (MP2, MP4) in conjunction with large basis sets, (aug-)cc-pVxZ, x = T, Q. A total of 7 structures for GaN2+ and 24 for GaN4+ were identified, corresponding to minima, transition states, and saddle points. We report geometries and dissociation energies for all the above structures as well as potential energy profiles, potential energy surfaces, and bonding mechanisms for some low-lying electronic states. The calculated dissociation energy (De) of the ground state of GaN2+, X1Sigma+, is 5.6 kcal/mol with respect to Ga+(1S) + N2(X1Sigmag+) and that of the excited state, ?3Pi, is 24.8 kcal/mol with respect to Ga+(3P) + N2(X1Sigmag+). The ground state and the first excited minimum of GaN4+ are of 1A1(C2v) and 3B1(C2v) symmetry with corresponding De of 11.0 and 43.7 kcal/mol with respect to Ga+(1S) + 2N2(X1Sigmag+) for X1A1 and Ga+(3P) + 2N2(X1Sigmag+) for 3B1.     

Time-of-flight secondary ion mass spectrometry of matrix-diluted oligo- and polypeptides bombarded with slow and fast projectiles: Positive and negative matrix and analyte ion yields, background signals, and sample aging

Human angiotensin II, chain B of bovine insulin, and porcine insulin were determined by time-of-flight secondary ion mass spectrometry under impact of approximately 25 keV Xe+ and SF5+ ion beams and approximately 100 MeV 252Cf fission fragments. Matrix-embedded samples, dissolved in a large surplus of alpha-cyano-4-hydroxycinnamic acid, were prepared by nebulizer spray deposition, neat samples by the droplet technique. It is shown that the status of the sample can be assessed by evaluating the matrix-specific features of the mass spectra. The beneficial effect of matrix isolation was small for angiotensin but large for the insulin samples, which did not show parent peaks from neat material. Negative ion yields under SF5+ impact were up to a factor of 50 higher than with Xe+. For positive secondary ions, the enhancement was much smaller. The mass spectra produced by slow ion beams or fast fission fragments were qualitatively similar. Quantitative differences include the following: with fast projectiles the yields were about 10-30 times higher than with slow ions, but similar for negative ion emission under SF5+ bombardment; the analyte-to-matrix yield ratios were higher with slow ions and up to 250 times higher than the molar analyte concentration; for analyte ions the peak-to-background ratios were higher using slow projectiles; the fraction of carbon-rich collisionally formed molecular ions was much higher with fast projectiles. Sample aging in vacuum for up to five weeks strongly reduced the yield of protonated analyte molecules ejected by slow ion impact, but not of deprotonated species. Hence protonation seems to correlate with sample "wetness" or the presence of volatile proton-donating additives.     

Reactions of radicals with hydrolyzed Bi(III) ions: a pulse radiolysis study

Radiolytic reduction of BiOClO4 in aqueous solutions leads to the formation of bismuth clusters and larger nanoparticles. The mechanisms of redox reactions of the polycationic Bi(III) species that exist in the solution were investigated with pulse radiolysis. The kinetic and spectral properties of the transients formed by the reaction of these species with the primary radicals from water radiolysis are reported. The single-electron reduction product, Bi9(OH)224+, absorbs at lambdamax = 273 nm, while the OH adduct, Bi9(OH)235+, has a broad absorption spectrum with a maximum at 280 nm and a shoulder at 420 nm. Several rate constants were measured: k (e-aq + Bi9(OH)225+) = 1.2 x 1010 M-1 s-1 and k (OH + Bi9(OH)225+) = 1.5 x 109 M-1 s-1. The reduced species, Bi9(OH)224+ further reacts with (CH3)2COH radicals, but not with CH2C(CH3)2OH radicals from t-butanol, to produce a doubly reduced polynuclear species. A few reactions of the reduction of the Bi salt in the presence of poly(acrylic acid) are also described. In the presence of the polymer, a metal-polymer complex is formed prior to the irradiation, and the reduction reactions are significantly slowed down.     

Characteristic Fragmentation of Polysiloxane Monolayer Films by Bombardment with Monatomic and Polyatomic Primary Ions in TOF-SIMS

This study reports the characteristic fragmentation patterns from two polysiloxane polymers that form ordered overlayer on silver substrates. Results are compared for the bombardment of various monatomic and polyatomic projectiles of Cs⁺, C₆₀⁺ (10 keV), Bi₁⁺, and Bi₃⁺ (25 keV) in the high mass range time-of-flight secondary ion mass spectrometry (TOF-SIMS) spectra. Results are reported from sub-monolayer (solution cast) coverages of poly(dimethylsiloxane)s with the number average molecular weights (M_n) of 2200 and 6140 Da, respectively, and Langmuir-Blodgett monolayers of poly(methylphenylsiloxane) with molecular weights (MW) from 600 and 1000 Da. For each film, Bi projectiles resulted in the emission of positive silver cluster ions from the substrate under the polymer overlayer and peaks corresponding to silver cluster ions with larger mass were observed by impact of polyatomic 25 keV Bi₃⁺ projectiles. In addition, depending on the change of energy of Bi₃⁺, a different pattern of fragments was observed. With Cs⁺ and C₆₀⁺ impact, however, the emission of silver cluster ions was not detected. In the case of C₆₀⁺ impact for PDMS-6140, peaks corresponding to silver-cationized intact oligomers were not observed. In this paper, these results are explained by the possible bombardment mechanism for each projectile, based on its mass, energy, and split trajectories of the component atoms under the polyatomic impact.     

A new SIMS paradigm for 2D and 3D molecular imaging of bio-systems

With the implementation of focused primary ion beams, secondary ion mass spectrometry (SIMS) has become a significant technique in the rapidly emerging field of mass spectral imaging in the biological sciences. Liquid metal ion guns (LMIG) offered the prospect of sub-100 nm spatial resolution, however this aspiration has yet to be reached for molecular imaging. This brief review shows that using LMIG the limitations of the static limit and low ionization probability will restrict useful imaging to around 2 μm spatial resolution with high-yield molecules. The only prospect of going beyond this in the absence of factors of 100 increase in ionization probability is to use polyatomic ion beams such as C₆₀⁺, for which bombardment induced damage is low. In these cases sub-micron imaging becomes possible, using voxels together with molecular depth profiling and 3D imaging. The discussion shows that conventional ToF-SIMS instrumentation then becomes a limitation in that the pulsed ion beam has a very low duty cycle which results in inordinately long analysis times, and pulsing the beam means that high-mass resolution and high spatial resolution are mutually incompatible. New instrumental configurations are described that allow the use of a dc ion beam and separate the mass spectrometry for the ion formation process. Early results from these instruments suggest that sub-micron analysis and imaging with high mass resolution and good ion yields are now realizable, although the low ion yield issue still needs to be solved.     

Gibbs energies of transfer of alkali metal cations between mutually saturated water-solvent systems determined from extraction experiments with radiotracer 137Cs

Thermodynamic standard Gibbs energies of transfer of alkali metal cations related to Cs+ cation [DeltatG degrees*,(Cs+)-[DeltatG degrees*,(M+)] between several mutually saturated solvents of the type water-solvent were calculated from determined extraction exchange constants Kexch degrees,*(Cs+/M+). The used liquid-liquid extraction method with radioactive tracing by 137Cs permits attaining higher precision of the values as compared to the methods used up to now. The data for o-nitrophenyloctyl ether, 1,2-dichloroethane, and 1-octanol were compared with literature sources and recommended absolute values of DeltatG degrees,*M+) are reported. For dissociating solvents, the dependences of [DeltatG degrees,*(Cs+) - [DeltatG degrees,*(M+)] on Gibbs energy of hydration of an ion, DeltaGhydr degrees are straight lines either for four cations Cs+, Rb+, K+, and Na+ (nitrosolvents) or for three cations Cs+, Rb+, and K+ (1,2-dichloroethane and 1-octanol). The hydration of Na+ and still more of Li+ in the water-saturated organic phase is apparent from the results. This manifests for high-water-content equilibrium 1-octanol even in a reversal of the values [i.e., DeltatG degrees*,(Li+) being more negative than DeltatG degrees,*(Na+)], although for Cs+, Rb+, and K+, the general trend is conserved. Water-saturated 1-octanol is thus slightly less basic than water, but the overall selectivity is very low. For one studied nondissociating solvent, dioctyl sebacate, the trend of the dependences of log Kexch degrees,*(CsB/M+) on DeltaGhydr degrees is similar to that of Kexch degrees,*(Cs+/M+) for polar solvents, but different for different anions B, thus reflecting ion association in the organic phase.     

Effect of Ga2O3 on the spectroscopic properties of erbium-doped boro-bismuth glasses

The spectroscopic properties and thermal stability of Er3+-doped Bi2O3-B2O3-Ga2O3 glasses are investigated experimentally. The effect of Ga2O3 content on absorption spectra, the Judd-Ofelt parameters Omega t (t=2, 4, 6), fluorescence spectra and the lifetimes of Er3+:4I 13/2 level are also investigated, and the stimulated emission cross-section is calculated from McCumber theory. With the increasing of Ga2O3 content in the glass composition, the Omega t (t=2, 4, 6) parameters, fluorescence full width at half maximum (FWHM) and the 4I 13/2 lifetimes of Er3+ first increase, reach its maximum at Ga2O3=8 mol.%, and then decrease. The results show that Er3+-doped 50Bi2O3-42B2O3-8Ga2O3 glass has the broadest FWHM (81nm) and large stimulated emission cross-section (1.03 x1 0(-20)cm2) in these glass samples. Compared with other glass hosts, the gain bandwidth properties of Er+3-doped Bi2O3-B2O3-Ga2O3 glass is better than tellurite, silicate, phosphate and germante glasses. In addition, the lifetime of 4I 13/2 level of Er(3+) in bismuth-based glass, compared with those in other glasses, is relative low due to the high-phonon energy of the B-O bond, the large refractive index of the host and the existence of OH* in the glass. At the same time, the glass thermal stability is improved in which the substitution of Ga2O3 for B2O3 strengthens the network structure. The suitability of bismuth-based glass as a host for a Er3+-doped broadband amplifier and its advantages over other glass hosts are also discussed.     

OFF-OFF-ON switching of fluorescence and electron transfer depending on stepwise complex formation of a host ligand with guest metal ions

Stepwise complex formation is observed between 2,3,5,6-tetrakis(2-pyridyl)pyrazine (TPPZ) and a series of metal ions (M(n+) = Sc3+, Y3+, Ho3+, Eu3+, Lu3+, Nd3+, Zn2+, Mg2+, Ca2+, Ba2+, Sr2+, Li+), where TPPZ forms a 2:1 complex [(TPPZ)2-M(n+)] and a 1:1 complex [TPPZ-M(n+)] with Mn+ at low and high concentrations of metal ions, respectively. The fluorescence intensity of TPPZ begins to increase at high concentrations of metal ions, when the 2:1 (TPPZ)2-M(n+) complex is converted to the fluorescent 1:1 TPPZ-M(n+) complex. This is regarded as an "OFF-OFF-ON" fluorescence sensor for metal ions depending on the stepwise complex formation between TPPZ and metal ions. The fluorescence quantum yields of the TPPZ-M(n+) complex vary depending on the metal valence state, in which the fluorescence quantum yields of the divalent metal complexes (TPPZ-M2+) are much larger than those of the trivalent metal complexes (TPPZ-M3+). On the other hand, the binding constants of (TPPZ)2-M(n+) (K1) and TPPZ-M(n+) (K2) vary depending on the Lewis acidity of metal ions (i.e., both K1 and K2 values increase with increasing Lewis acidity of metal ions). Sc3+, which acts as the strongest Lewis acid, forms the (TPPZ)2-Sc3+ and TPPZ-Sc3+ complexes stoichiometrically with TPPZ. In such a case, "OFF-OFF-ON" switching of electron transfer from cobalt(II) tetraphenylporphyrin (CoTPP) to O2 is observed in the presence of Sc3+ and TPPZ depending on the ratio of Sc3+ to TPPZ. Electron transfer from CoTPP to O2 occurs at Sc3+ concentrations above the 1:2 ratio ([Sc3+]/[TPPZ]0 > 0.5), when the (TPPZ)2-Sc3+ complex is converted to the TPPZ-Sc3+ complex and TPPZ-(Sc3+)2, which act as promoters of electron transfer (ON) by the strong binding of O2*- with Sc3+. In sharp contrast, no electron transfer occurs without metal ion (OFF) or in the presence at Sc3+ concentrations below the 1:2 ratio (OFF), when the (TPPZ)2-Sc3+ complex has no binding site available for O2*-.     

DFT calculations of 57Fe Mössbauer isomer shifts and quadrupole splittings for iron complexes in polar dielectric media: applications to methane monooxygenase and ribonucleotide reductase

To predict the isomer shifts of Fe complexes in different oxidation and spin states more accurately, we have performed linear regression between the measured isomer shifts (delta(exp)) and DFT (PW91 potential with all-electron triple-zeta plus polarization basis sets) calculated electron densities at Fe nuclei [rho(0)] for the Fe(2+,2.5+) and Fe(2.5+,3+,3.5+,4+) complexes separately. The geometries and electronic structures of all complexes in the training sets are optimized within the conductor like screening (COSMO) solvation model. Based on the linear correlation equation delta(exp) = alpha[rho(0) - 11884.0] + C, the best fitting for 17 Fe(2+,2.5+) complexes (totally 31 Fe sites) yields alpha = -0.405 +/- 0.042 and C = 0.735 +/- 0.047 mm s(-1). The correlation coefficient is r = -0.876 with a standard deviation of SD = 0.075 mm s(-1). In contrast, the linear fitting for 19 Fe(2.5+,3+,3.5+,4+) complexes (totally 30 Fe sites) yields alpha = -0.393 +/- 0.030 and C = 0.435 +/- 0.014 mm s(-1), with the correlation coefficient r = -0.929 and a standard deviation SD = 0.077 mm s(-1). We provide a physical rationale for separating the Fe(2+,2.5+) fit from the Fe(2.5+,3+,3.5+,4+) fit, which also is clearly justified on a statistical empirical basis. Quadrupole splittings have also been calculated for these systems. The correlation between the calculated (DeltaE(Q(cal))) and experimental (DeltaE(Q(exp))) quadrupole splittings based on |DeltaE(Q(exp))| = A |DeltaE(Q(cal))| + B yields slope A, which is almost the ideal value 1.0 (A = 1.002 +/- 0.030) and intercept B almost zero (B = 0.033 +/- 0.068 mm s(-1)). Further calculations on the reduced diferrous and oxidized diferric active sites of class-I ribonucleotide reductase (RNR) and the hydroxylase component of methane monooxygenase (MMOH), and on a mixed-valent [(tpb)Fe3+(mu-O)(mu-CH3CO2)Fe4+(Me3[9]aneN3)]2+ (S = 3/2) complex and its corresponding diferric state have been performed. Calculated results are in very good agreement with the experimental data.     

固体高辨核磁共振技术对改性金属离子在HZSM-5分子筛中的行为研究

使用固体高分辨核样共振技术研究Zn^2+, Ga^3+,等离子在HZSM-5分子筛中的行为。结果表明, Ga^3+离子主要定位于HZSM-5外表面, 不能抑制骨架脱铝; Zn^2+离子进入了HZSM-5内孔道, 取代了桥羟基上部分质子位, 能稳定沸石骨架。Ga^3+,Zn^2+离子均未进入沸石骨架位。骨架脱铝顺序为: GaHZSM-5>ZnHZSM-5》BaHZSM-5≌CaHZSM-5。     

Oxygen activation by cytochrome p450: a thermodynamic analysis

Electrode potentials for every intermediate in the cytochrome P450 cycle were estimated and evaluated by means of an oxidation state diagram. By this approach, and within the uncertainties of the approximations, the superoxide complex of cytochrome P450 at pH 7 is oxidizing: E degrees ' (P450FeO(2)2+, H+/P450FeOOH2+) = +0.93 V, and the Gibbs energy for the reaction of the hydroperoxo complex of cytochrome P450 to form compound I and water, P450FeOOH2+ + H+ = P450FeO2+ por(*+) + H2O, is 0 kJ/mol. Although cytochrome P450FeOOH2+ and cytochrome P450FeO2+ por(*+) are approximately isoenergetic, they are likely to react at different rates with substrates and may yield different products. Homolysis of the hydroperoxo complex of cytochrome P450 to compound II and the hydroxyl radical, P450FeOOH2+ = P450FeO2+ + HO(*), is unfavorable (DeltaG degrees ' = +92 kJ/mol), as is the dissociation into HOO- and cytochrome P450Fe3+ (+73 kJ/mol). It is shown that the sum of the Gibbs energy of association for cytochrome P450Fe3+ with the hydroperoxo anion and the Gibbs energy for the one-electron reduction of cytochrome P450FeOOH2+, relative to NHE, is constant (-203 kJ/mol). While the estimated E degrees ' (P450FeO(2)2+, H+/P450FeOOH2+) = +0.93 V at pH 7 is larger than necessary to effect reduction of cytochrome P450FeO(2)2+, the magnitude of this electrode potential implies that the binding constant for cytochrome P450Fe3+ with hydrogen peroxide is ca. 3 x 106 M(-1) at pH 7. An association constant of this magnitude ensures that a fraction of cytochrome P450FeOOH2+ is available to form compound I or to react with substrates directly, while a larger one would imply that compound I is too weak an oxidant. In general, the energetics of the reduction of dioxygen to water determines the energetics of catalysis of hydroxylations by cytochrome P450. These results enable calibration of energy levels obtained for intermediates in the cytochrome P450 reaction cycle obtained by ab initio calculations and provide insights into the catalytic efficiency of cytochrome P450 and guidelines for the development of competent hydroxylation catalysts.     

Vacuum Ultraviolet Excited Photoluminescence Properties of Y202S:Eu3+,Bi3+ Phosphor

As an Hg-free lamp using phosphor,the Bi3+ and Eu3+ co-doped Y2O2S phosphors were prepared and their luminescence properties under vacuum uitraviolet(VUV) excitation were investigated.The VUV photolumineseent intensity of Y2O2S:Eu3+ was weak,however,considerably stronger red emission at 626 nm with good color purity was observed in Y2O2S:Eu3+,Bi3+ systems.Investigation on the photoluminescence reveals that the strong VUV luminescence of Y2O2S:Eu3+,Bi3+ at 147 nm is mainly because the Bi3+ acts as a medium and effectively performs the energy transfer process: Y3+-O2→Bi3+→Eu3+,while the intense emission band at 172 nm is attributed to the absorption of the characteristic 1So-1P1 transition of Bi3+ and the direct energy transfer from Bi3+ to Eu3+.The Y2O2S:Eu3+,Bi3+ shows excellent VUV optical properties compared with the commercial (Y,Gd)BO3:Eu3+.Thus,the Y2O2S:Eu3+,Bi3+ can be a potential red VUV-excited candidate applied in Hg-free lamps for backlight of liquid crystal display.     

Speciation of cyclo(Pro-Gly)<Subscript>3</Subscript> and its divalent metal-ion complexes by electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI-MS) was used to study the binding of selected group II and divalent transition-metal ions by cyclo(Pro-Gly)3 (CPG3), a model ion carrier peptide. Metal salts (CatXn) were combined with the peptide (M) at a molar ratio of 1:10 M/Cat in aqueous solvents containing 50% vol/vol acetonitrile or methanol and 1 or 10 mM ammonium acetate (NH4Ac). Species detected include [M+H]+, [M+Cat-H]+, [M2+Cat]2+, [M+Cat+Ac]+, and [M+Cat+X]+. The relative stabilities of complexes formed with different cations (Mg2+, Ca2+, Sr2+, Mn2+, Co2+, Ni2+, Cu2+, and Zn2+) were determined from the abundance of 1:1 and 2:1 M/Cat species relative to that of the unbound peptide. The largest metal ions (Ca2+, Sr2+, and Mn2+) formed the most stable complexes. Reducing the buffer concentration increased the overall extent of metal binding. Results show that the binding specificity of CPG3 depends upon the size of the metal ion and its propensity for electrostatic interaction with oxygen atoms. Product ion tandem mass spectrometry of [M+H]+ and [M+Cu-H]+ confirmed the cyclic structure of the peptide, although the initial site(s) of metal attachment could not be determined.