Hg-coordination studies of oligopeptides containing cysteine,histidine and tyrosine by 199mHg-TDPAC

In order to study the interaction of histidine- and tyrosine-containing peptide chains with Hg(II), the nuclear quadrupole interaction (NQI) of ^199mHg in the Hg complexes of the oligopeptides Alanyl–Alanyl–Histidyl–Alanyl–Alanine-amid (AAHAA–NH₂) and Alanyl–Alanyl–Tyrosyl–Alanyl–Alanine-amid (AAYAA–NH₂) was determined by time differential perturbed angular correlation and is compared with previous data on Alanyl–Alanyl–Cysteyl–Alanyl–Alanyl (AACAA–OH). The ^199mHg–NQIs depend on the oligopeptide to Hg(II) stoichiometry and indicate that two-fold and four-fold coordinations occur for the bound Hg(II). This revised version was published online in August 2006 with corrections to the Cover Date.     

Heavy metal coordination chemistry in mercaptides and enzymes studied by TDPAC

Time differential perturbed angular correlation (TDPAC) studies of the coordination chemistry of the heavy metal atoms Cd and Hg via the nuclear quadrupole interaction are presented for the following systems; (i) mercury complexes with mercaptides, polymers with thiol groups, and ferrocenethiols. Mercury has a strong tendency to form linear or almost linear bonds with sulfur ligands. Evidence for 1,3-dithia-2-mercura[3]ferrocenophane formation is presented. (ii)^111mCd-derivatives of the small electron transport proteins azurin, including a his 117gly mutant, and stellacyanin. The titration of the his 117gly mutant of azurin with imidazole was monitored in situ. (iii)^111mCd- and^199mHg-derivatives of the multi-Cu enzymes ascorbate oxidase and laccase. Reconstitution probabilities for Hg-reconstitution will be given as well as information on selective depletion and blocking of Cu-sites.     

Orientation of199mHg by optical pumping detected by γ-radiation anisotropy

^199mHg was produced and mass separated at the ISOLDE facility (CERN). Nuclear orientation achieved by optical pumping via the resonance line 6s ^{2 1} S ₀→6s6p ³ P ₁,λ=2537Å was monitored by means of the anisotropy of theγ-radiation emitted in the cascade^199mHg(I=13/2⁺) $${}^{199m}Hg(I = 13/2^ + )\xrightarrow[{M4}]{}{}^{199*}Hg(I = 5/2^ - )\xrightarrow[{E2}]{}{}^{199}Hg(I = 1/2^ - ).$$ ^199*Hg(I=5/2^?)¹⁹⁹Hg(I=1/2^?). Maximum anisotropies of 35% (2,8%) were found in the M4 (E2) transition. A Zeeman scanning of the³ P ₁ state yielded the positions ofF=13/2 and theF=15/2 hfs components relative to the reference isotope²⁰⁴Hg at 15.13 (15) GHz and ?2.86 (15) GHz respectively. Isotopic shift and the quadrupole interaction constant were deduced from these values using the knownA factor.δv ^199m/2O4=v ^2O4?v ^199m=12.20 (16) GHzB=?0.86 (25) GHz. From theB factor the spectroscopic quadrupolment was calculated asQ _s =1.54 (44) barn.     

Electron spin resonance studies of 199HgH, 201HgH, 199HgD and 201HgD isolated in neon and argon matrices at 4K: an electronic structure investigation

Various isotopomers of the mercury hydride radical (HgH) have been generated in a microwave discharge and trapped in neon and argon matrices at 4 K for electron spin resonance (ESR) investigations. Both the dipolar (A_dip) and isotropic (A_iso) components of the nuclear hyperfine interactions have been directly measured for ¹⁹⁹Hg, ²⁰¹Hg, H and D. Electronic structure information for HgH in its X²Σ ground state obtained from the hyperfine data is compared with theoretical results from several different computational methods. The hyperfine interactions in HgH are unusually large with A_iso(¹⁹⁹Hg) = 6859(3), A_dip(¹⁹⁹Hg) = 446(3), A_iso(H) = 730(2) and A_dip(H) = 0(2) MHz. A standard analysis of the hyperfine interactions demonstrates the need for a more in-depth theoretical treatment of HgH that should include relativistic effects. An interesting shift in spin density is observed when deuterium replaces hydrogen in HgH. The decreased spin density on deuterium, which was demonstrated in earlier studies, can now be more fully investigated since these new measurements confirm an associated increase in spin density on mercury     

Nuclear quadrupole interaction of119mHg in mercury(I) and mercury(II) halides

The nuclear quadrupole interactions of^199mHg in the mercury(I) and mercury(II) halides with Cl, Br, I were determined by time differential perturbed angular correlation. The quadrupole moment of theI=5/2 state in¹⁹⁹Hg was redetermined to beQ _5/2=0.674(77) b. The nuclear quadrupole interaction in both mercurous and mercuric halides scales with the electronegativity. Electric field gradients at mercury and halogen sites were calculated by a full-potential linearized augmented plane wave method (WIEN code) and were found in good agreement with experiment. In some cases a total energy minimization for internal parameters was carried out and found to be essential.     

199Hg and63,65Cu NMR studies of mercury based high-T c superconductors

Hg-oxide ceramic high temperature superconductors were studied by¹⁹⁹Hg and^63,65Cu NMR spectroscopy. Room temperature spectra, spin-spin and spin-lattice relaxation times of samples with different superconducting transition temperatures are presented. A spin-lattice relaxation time ofT ₁=35 msec and a spin-spin relaxation time ofT ₂=1.6 msec were found for the¹⁹⁹Hg NMR. All samples exhibit similar characteristic powder spectra caused by an axially symmetric¹⁹⁹Hg spin interaction. The isotropic value and the anisotropy of the tensor relative to solid HgCl₂ as a standard substance is estimated. Furthermore, results of^63,65Cu NMR measurements at a temperature of 4.2 K which exhibit a typical powder line shape (forI=3/2) are presented.     

199Hg Mössbauer measurements on mercury alloys and Hg-fluorides

The Mössbauer effect on the 158 keV 5/2^??1/2^? transition in¹⁹⁹Hg, of the order of 10 ppm, has been studied using the current integration technique. The isomer shift between the Hg(I)- and Hg(II)-fluorides as well as the quadrupole splitting in Hg₂Pt and Hg₂F₂ are interpreted in terms of relativistic Hartree-Fock-Slater and Molecular Orbital calculations. The following nuclear parameters could be derived: δ2<=(3.2± l.l)10^?3fm² andQ(5/2^?)=(-0.8±0.4)b. Evidence for an oblate triaxially deformed¹⁹⁹Hg nucleus is derived from particle plus rotor calculations.     

Production ofH(2s) andH(2p) by electron detachment fromH − in collisions with nitrogen and oxygen

¹⁹⁹Hg Fourier Transform NMR studies of various solutions of diverse mercury salts in H₂O and D₂O or in the appropriate protonated and deuterated acids are reported for both Hg ₂ ⁺⁺ and Hg⁺⁺. In the different solutions investigated the¹⁹⁹Hg line positions depend on the concentration of the solution, on the solvents and their isotopic composition and on the temperature of the sample. A ratio of the Larmor frequency of¹⁹⁹Hg and of²H in a Hg(NO₃)₂ solution in dilute DNO₃ is given. Using this ratio and the measured chemical shifts, a ratio of the Larmor frequencies of¹⁹⁹Hg for infinite dilution relative to²H in pure D₂O is given. From this a g_I-factor for¹⁹⁹Hg is derived and compared with the g_I-factor of an optical pumping experiment. The resulting shielding constant is σ^* (hydrated¹⁹⁹Hg⁺⁺ versus¹⁹⁹Hg atom)=?24.32(5) · 10^?4. This yields an atomic reference scale for all measured NMR line shifts of mercury.     

The magnetic moments and halflives of the 5/2− states in199Hg and197Hg and the discrepancies in the experimental hyperfine fields at Hg in Fe

The Larmor-precession frequencies for¹⁹⁷Hg in Fe have been determined to beω _L = 1291 ±25 MHz at 293 K andω _L = 1334±25 MHz at 105 K. For¹⁹⁹Hg in Feω _L =1372±50 MHz has been measured at 293 K. The half-lives of the 5/2^? states in¹⁹⁷Hg and¹⁹⁹Hg have been remeasured asT _1/2(¹⁹⁷Hg)=8.1±0.16 nsec andT _1/2(¹⁹⁹Hg)=2.45±0.05 ns, respectively. The magnetic moment of the 5/2^? 158keV state in¹⁹⁹Hg was redetermined by the integral perturbed angular correlation method in an external magnetic field of 47kG asμ(5/2 ^? ) = 0.905±0.091 nm. With this new value consistency for the magnetic hyperfine fields at Hg in Fe measured with the TDPAC-method and with the NMR/ON-method is obtained. This fact is used to determine theg-factors of the 5/2^? states in¹⁹⁷Hg and¹⁹⁹Hg more precisely fromω _L -values given above:g(¹⁹⁷Hg)=0.342(6);g(¹⁹⁹Hg)=0.352(13). The magnetic moments of the first excited 2⁺ states in^198–204Hg isotopes which rely on calibrations with the¹⁹⁹Hg-g-factor, are revised.     

g-factor measurements in stable Hg isotopes

The g-factor of the first 2⁺ state in¹⁹⁸Hg,²⁰⁰Hg and²⁰²Hg has been measured using the thin foil Transient Field technique. The values were calibrated to the known g-factor of the first 5/2⁻ state in¹⁹⁹Hg. The levels were Coulomb excited by 217 MeV nickel ions with gadolinium acting as ferromagnetic medium. The obtained values are rather constant and contradict a previously observed dip at²⁰⁰Hg. Two other g-factors have been remeasured in¹⁹⁹Hg.     

Sudden change of quadrupole moment between the first 52− states of 197Hg and 199Hg

Low-temperature time differential perturbed angular correlation experiments with the 164 keV-134 keV cascade of ^197mHg in a zinc matrix give evidence that the hitherto accepted value of the quadrupole moment of the first $\text{5}\text{2}{}^{\mathrm{?}}$ state of ¹⁹⁷Hg is erroneous. A new value is derived from a time differential perturbed angular correlation experiment with the 374 keV?158 keV cascade of ^199mHg implanted into a Be single crystal and comparison with an analogous experiment for ^197mHg. Taking $\text{Q(}\text{5}\text{2}{}^{\mathrm{?}}\text{,}{}^{199}\text{Hg) = +0.95(7)}\text{b}$ we derive $\text{|Q(}\text{5}\text{2}{}^{\mathrm{?}}\text{,}{}^{197}\text{Hg)¦= 0.081(6)}\text{b}$. This change of quadrupole moment is discussed in the framework of the shell model.     

NMR of mercury in porous carbon and silica gel

The temperature dependences of the integrated intensity and of the Knight shift of ¹⁹⁹Hg NMR signals are measured for liquid and solid mercury introduced into porous carbon and silica gel. A decrease in the temperature of completion of crystallization and a small temperature hysteresis (from 4 to 9 K) between melting and crystallization are observed. The melting temperature of mercury in pores coincides with that in the bulk. The ¹⁹⁹Hg NMR signal from crystalline mercury under the condition of restricted geometry is observed for the first time. It is established that the Knight shift for liquid and crystalline mercury in pores is smaller than in the bulk.     

The magnetic hyperfine field at Hg impurities in ferromagnetic Gd

The magnetic hyperfine field at dilute Hg impurities in Gd has been investigated by the conversion electron (e ^–)--time differential perturbed angular correlation (TDPAC) technique. The radioactivities^197m Hg and¹⁹⁹Tl were implanted into Gd foils by means of an isotope separator. TDPAC measurements were performed with the 165 keV-L-conversion electron—134 keV--cascade of¹⁹⁷Hg at different temperatures and with the 334 keV--158 keV-K-conversion electron cascade of¹⁹⁹Hg at 200 K.The regular site occupation probabilities were found to be 15(3)% for an annealed^197m HgGd sample and 29(5)% in unannealed¹⁹⁹TlGd samples.From the magnetic hyperfine interaction frequencies measured for the regular sites at 200 K the magnetic hyperfine fields |H _hf(¹⁹⁷HgGd; 200 K)|=256(13) kG and |H _hf(¹⁹⁹HgGd; 200 K)|=267(7) kG were deduced.On leave from the University of Lisboa, Portugal     

Radiative capture of deuterons in Ba and Au

¹³⁸Ba(d,γ)¹⁴⁰La and¹⁹⁷Au(d,γ)^199mHg cross sections were measured for deuteron energies ranging from 5 to 26 MeV. A survey of existing experimental (p,γ), (d,γ) and (α,γ) cross sections is given. A comparison of all the experimental data with calculated compound nucleus cross sections is performed. An increase in the ratio of experimental cross sections and calculated compound nuclear cross sections with increasing mass numberA is observed for all capture processes.     

The electric field gradients for Hg at different lattice sites in Be

¹⁹⁹Tl ions were implanted into a Be single crystal. From time differential perturbed e^– angular correlation experiments with the 5/2^– state of¹⁹⁹Hg the effective electric field gradientV _zz ^eff =±15.2(1.8)×10¹⁷ V · cm^–2 was deduced for Hg on an octahedral interstitial site in Be. From a nuclear orientation experiment, the sign ofV _zz ^eff for^197mHg implanted in Be is determined. In time differential perturbed angular correlation experiments with the 5/2 state of¹⁹⁹Hg populated in the -decay of¹⁹⁹Au implanted into Be, the effective electric field gradient for Hg on a substitutional site in Be was determined asV _zz ^eff =–1.2(2)×10¹⁷V · cm^–2. The dependence of the site population of Tl implanted in Be on annealing was investigated by use of the channeling technique. In a comparison of the derived effective field gradients with the corresponding lattice field gradient contributions different electronic enhancement factors are derived for different sites of Hg in Be.     

Increased luminance of MEH-PPV and PFO based PLEDs by using salmon DNA as an electron blocking layer

The effect of salmon DNA-CTMA as an electron blocking layer (EBL) has been examined on the performance of MEH-PPV and PFO-based light emitting diodes. Though the turn-on voltage increases with incorporation of EBL, a significant increase in luminance and luminous efficiency for both the devices is observed. The EBL improves the device performance by blocking electrons at the EBL-polymer interface, thereby increasing the recombination probability of electrons and holes. The luminance of the MEH-PPV based Bio-LED increases to 100 cd/m² from 30 cd/m² while a corresponding increase for the PFO based LED is to 160 cd/m² from 80 cd/m² with and without EBL, respectively.     

Study of orientation transfer by collisions of the second kind between 198Hg and 199Hg atoms

A double resonance experiment is used to detect the collisional transfer of orientation from an optically oriented ¹⁹⁸Hg (6³P₁) atom to the hyperfine levels $\text{(6}{}^3\text{P}{}_1\text{; F =}\text{1}\text{2}\text{, F =}\text{3}\text{2}\text{)}$ of a ¹⁹⁹Hg atom. The reaction of transfer is assumed to be ¹⁹⁸Hg (6³P₁) + ¹⁹⁹Hg (6¹S₀) → ¹⁹⁸Hg (6¹S₀) + ¹⁹⁹Hg (6³P₁).The theory of such a process is summarized, the experimental set-up described and the double resonance signals compared with those predicted by the theory.     

Quadrupole interaction studies of Hg in Zn and lattice location of Hg and Au in Zn

¹⁹⁷Hg,¹⁹⁹Tl and¹⁹⁹Au ions were implanted into Zn single crystals. From time differential perturbed e^–- and - angular correlation experiments with the 5^–/2 states in¹⁹⁷Hg and¹⁹⁹Hg, respectively, the quadrupole interaction for Hg in Zn is reinvestigated. Only the data for the¹⁹⁹Au sample exhibit a single unique quadrupole precession pattern in agreement with the result of the lattice location studies by use of the channeling technique, which show Hg to occupy random lattice sites in Zn while Au is substitutional.From the measured interaction frequency, sign and magnitude of the effective electric field gradient for Hg on the substitutional site in Zn is determined asV _zz ^eff = +15.2(1.8)×10¹⁷V·cm^–2. By comparison of this value to the corresponding lattice field gradient contribution an electronic enhancement factor ofK(HgZn)=2.6 is deduced in disagreement with a previous derivation of this quantity, but which supports the proposal that the electronic field gradient depends linearly upon the valence of the impurity probe atom.     

Interpretation of level-anticrossing phenomena in phosphorescence and optical nuclear polarization in organic crystals

Level-anticrossing (LAC) phenomena in electronic states of molecules in organic crystals are described with a density matrix formalism. A condition for the observability of LAC signals in phosphorescence and ONP is derived. The validity of these predictions is tested at quadrupole satellite positions in the LAC spectra. As a consequence of the full density matrix treatment, off-diagonal damping terms Γ _mn = T ₂ ^-1(mn) are introduced. These turned out to be essential for the interpretation of the vanishing of experimentally observed LAC signals at higher order satellite positions. If T ₂ equals the lifetime τ of the triplet state, earlier predictions based on kinetic arguments evolve as a limiting case of the present theory. The quadrupole satellite signals can be described properly by the density matrix formalism and there is no need for the introduction of an additional cross-relaxation mechanism.     

Saturated absorption spectroscopy in the ultra-violet with a continuous-wave,frequency-doubled,ring dye laser; even isotope shifts on the 6d3D1-6p3P0 transition of HgI

A novel, single-frequency, continuous-wave, ring, dye laser with intra-cavity frequency-doubling has been developed, and used to carry out saturated absorption spectroscopy on the 6s6d³D₁-6s6p³P₀ transition of Hg I at 296.7 nm. Even isotope shifts have been measured by this technique on this transition and are: Hg204-202, 350 ± 10 MHz; Hg202-200, 345 ± 10 MHz; Hg200-198, 310 ± 10 MHz. The shift on transitions from the hyperfine state 6s6d³D₁ ($\text{F =}\text{3}\text{2}$) between Hg199 and Hg201 has also been measured, and is 225 ± 10 MHz.