Synthesis of Atom‐Precise Chiral Ag14 Clusters Protected by Penicillamine Ligands

A pair of atom‐precise chiral silver(I) nanocluster enantiomers ( Ag₁₄‐d and Ag₁₄‐l ) protected by d ‐ and l ‐penicillamine ligands is reported. Crystallographic structures reveal that the nanoclusters consist of a S^2? template and a chiral Ag₁₄ core stabilized by 12 penicillamine ligands. The penicillamine ligands show two binding fashions: (i) only thiolate coordination, and (ii) thiolate and carboxylate co‐coordination. Meanwhile, the two enantiomers show strong circular dichroism with opposite signals (mirror image relationship) owing to the chiral metallic core induced by chiral ligands, suggesting that the nanoclusters have well‐defined stereostructures as common chiral molecules do. The proton conductivity is also explored due to the existence of both amino groups and carboxylate groups from the penicillamine ligands, which is beneficial to construct H‐bond network for proton transfer.     

Spectra-Structure Correlations in 2,2′-Bipyridine Mercury(II) Saccharinate: Comparison With Mercury(II) Saccharinate And Chloromercury(II) Saccharinate∗

Abstract

The infrared spectrum of 1:1 complex of mercury(II) saccharinate with 2,2′-bipyridine, [Hg(C₇H₄NO₃S)₂(C₁₀H₈N₂)], was studied in the CO and SO₂stretching regions. The appearance of the spectrum in the region of the carbonyl stretching modes was correlated with the number of non-equivalent CO groups in the structure. The spectral and structural characteristics of the CO groups in the title compound were compared with the corresponding ones in the mercury(II) saccharinate and chloromercury(II) saccharinate. It was found that the frequency of the CO stretchings in the spectrum of Hg(bpy) (sac)₂ is significantly lower (1630 and 1615 cm^?1) than the frequency of the corresponding modes in the spectra of covalently bonded mercury(II) saccharinate (1705 and 1680 cm^?1) and chloromercury saccharinate (1694 cm^?1). An attempt was also made to assign the bands which are mainly due to the symmetric and the antisymmetric SO₂ stretching vibrations.

     

Spectrophotometric Determination of Trace Amounts of Mercury with 3-(2-Thiazolylazo)-2, 6-Diaminopyridine and Gelatine

Abstract

A sensitive method for the determination of trace amounts of mercury by complexation with 3-(2-Thiazolylazo)-2, 6-diaminopyridine (2, 6-TADAP) is described. Hg(II) forms a 1:2 complex with the reagent. Beer's law is obeyed over the range 5–40 μg in the total volume of 10 ml. The molar absorptivity was found to be 1.4 × 10⁴ L mol^?1 cm^?1. This method is simple, rapid and involves no extraction steps whereby the use of gelatine as a solubilizing agent is described.     

A Simple Flow-injection Spectrofluorimetric Method for the Determination of Mercury

A highly sensitive flow-injection spectrofluorimetric method is presented for the rapid and simple determination of Hg (II) in environmental and pharmaceutical samples. Murexide (ammonium purpurate) was used as the fluorescence reagent in the carrier stream. An emission peak of murexide, which is decreased linearly by addition of Hg (II), occurs at 435 nm in aqueous solution with excitation at 335 nm. A linear calibration was obtained for 5–200 ng ml⁻¹ Hg (II) with the relative standard deviation 2.5% (n = 5) for a 20 μl injection volume Hg (II). The limit of the detection was 1 ng ml⁻¹ and the sampling rate was 80 h⁻¹. No significant interference was found by the ions commonly found in the most environmental samples. The proposed method was successfully applied for the determination of trace mercury in real samples and the validation of the proposed methodology is provided.     

Hg ION implantation in silicon: Lattice disorder created and hg atom lattice location

Abstract

The lattice disorder produced by 42-keV and 75-keV Hg ions implanted in Silicon at room temperature and the lattice location of the Hg atoms were studied by means of the channeling technique with a 2.0 MeV ⁴He⁺ beam. The damage produced was found to increase linearly with ion dose until a saturation value, connected to the ion range, is reached. The number of Si atoms displaced for Hg ion implanted was evaluated and compared with the theoretical expectation. The substitutional Hg fraction is connected to the disorder produced: the replacement mechanism is discussed.     

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.     

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.     

Coexistence and mixing of spherical and deformed states in the region of light Hg-isotopes

The low-energy spectra of¹⁸⁶Hg and¹⁸⁴Hg are interpreted by a mixing of spherical and deformed states for angular momentum I=2, 4. In order to establish agreement between experimental results on¹⁸⁶Hg and¹⁸⁴Hg and potential calculations, a stronger isospin dependence of the pairing interaction is introduced. The existence of shape-isomeric states for¹⁸⁶Hg,¹⁸⁴Hg with a life-time ≈10^?8 sec is concluded from the model. The particle-vibration coupling is discussed as the probable origin for the odd-even staggering of the ground-state deformation.     

Investigation of203, 205Hg with the (d,pγ) reaction — Identification of thei 13/2 neutron hole state in205Hg

Low lying levels in²⁰³Hg and²⁰⁵Hg were studied with the (d, p) deuteron break-up reaction atE _d=14 and 18 MeV. Gamma-rays and conversion-electrons were measured in coincidence with protons. In addition delayed spectra were recorded with us and ms beam pulsing. Thei _13/2 neutron hole state was identified in²⁰⁵Hg and confirmed in²⁰³Hg. The known level structure of²⁰⁵Hg below 2 MeV is confirmed and extended. For²⁰³Hg we observe theγ-decay of several levels below 1.5 MeV, which were previously known from transfer reactions.     

Ground state shaoe and crossing of near spherical and deformed bands in 182Hg

The energy levels of ¹⁸²Hg have been identified for the first time through comparison of in-beam studies of the reactions ^156,154Gd(³²S, 4n)^184,182Hg and γ-X-ray coincidences. Levels up to 12⁺ in ¹⁸²Hg were established from γ-γ coincidences and singles measurements. The data establish that the ground state shape is near spherical, and that the ground band is crossed by a well-deformed band at 4⁺. In contrast to IBA model predictions that the deformed band will rise in energy in ¹⁸²Hg compared to ¹⁸⁴Hg, the energies of the deformed levels in ¹⁸²Hg continue to drop.     

Damage and lattice location studies in Hg implanted Hg1–xCdxTe

Abstract

Rutherford backscattering (RBS) and ion induced X-ray (PIXE) channeling experiments have been used to study the damage accompanying Hg and Al implantations into Hg_0.8Cd_0.2 Te and its annealing as well as to determine the location of Hg in the crystal.

The damage induced by the implantation of 300 keV Hg and 250 keV Al ions at room temperature was found from RBS channeling studies to reach a saturation level at doses of 1 × 10¹⁴ cm^?2 and 3 × 10¹⁴ cm^?2 respectively. The damage resembles that characteristic for extended defects and it anneals at ≈ 300°C.

The location of the constituents of Hg implanted Hg_0.8 Cd_0.2 Te was studied by PIXE channeling observing the characteristic X-rays for each element. Angular scans indicate that the channels are mostly blocked by Hg atoms for both unannealed and, to a lesser extent, annealed crystals. This observation supports the suggestion that interstitial Hg atoms may be responsible for the conductivity of Hg implanted Hg_1–x Cd_g Te.     

卟啉铜接枝SiO2有机-无机复合材料及强的非线性折射率

通过卟啉配合物Meso-四(4-羧基苯基)卟啉铜(简称Cu(Ⅱ)-TCPP)中的羧基与γ-氨基丙基三乙氧基硅烷(NH₂(CH₂)₃Si(OC₂H₅)₃,KH550)中的氨基的相互化学作用,成功地把卟啉配合物接枝到KH550中,随着KH550中乙氧基的水解与聚合反应的进行,卟啉铜连接到固体介质中,从而大幅度提高了卟啉在无机固体介质中的掺杂浓度. 将反应产物与γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(CH₂CHCH₂O(CH₂)₃Si(OCH₃)₃,KH560) 相杂化,形成物化性能良好、连接卟啉的有机-无机复合材料. 用红外光谱表征了Cu(Ⅱ)-TCPP与KH550的化学反应产物,用紫外—可见吸收光谱研究Cu(Ⅱ)-TCPP的分子状态. 应用Z扫描技术研究不同Cu(Ⅱ)-TCPP掺杂浓度的复合材料的非线性光学性质,其三介非线性折射率n₂达-1.1161×10^-16 m²/W. 关键词： 非线性折射率 有机-无机复合材料 接枝 Meso-四(4-羧基苯基)卟啉铜     

Photochemical production of the 204Hg isotope

Technologies for photochemical separation of highly enriched mercury isotopes are being developed and an appropriate experimental setup has been designed at the National Research Centre ??Kurchatov Institute.?? The process is based on the reaction of oxidation of selectively excited mercury atoms in the presence of 1.3-butadiene. Along with the ¹⁹⁶Hg, ¹⁹⁸Hg, ¹⁹⁹Hg, ²⁰⁰Hg, and ²⁰²Hg isotopes with concentrations from 90 to 99%, the ²⁰⁴Hg isotope with a concentration of 98% has been separated for the first time.     

Multiple coulomb excitation of202Hg and204Hg

Multiple Coulomb excitation measurements on^{202, 204}Hg have been performed with 5 MeV/u²⁰⁸Pb projectiles. The ground bands are excited up to the newly discovered 6⁺ states and B(E2) values are derived for the 4⁺→2⁺ and 6⁺→4⁺ transitions. Whereas the 2⁺ and 4⁺ levels in the Hg isotopes with 196≦A≦204 have an almost constant energy, the 6⁺ levels increase in²⁰²Hg and²⁰⁴Hg, compared to the lighter isotopes, by approximately 100 and 300 keV, respectively. The relative B(E2) values in both nuclei show that the collectivity in the neutron rich Hg nuclei is of more complex origin than expected from the few proton and neutron holes with respect to the 82 and 126 major shells.     

Preconcentration of mercury on polyaniline expands the horizon for energy dispersive X‐ray fluorescence determination

Hg(II) was sorbed on polyaniline from aqueous solutions, followed by determination using energy dispersive X‐ray fluorescence spectrometry. Distribution coefficient of Hg(II) on polyaniline was about 4 × 10³ in water, whereas distribution coefficient was 1.2 × 10⁴ at 0.1 M HCl and decreased drastically with increase in HCl concentration. Rapid kinetics of sorption was evinced by the 80% uptake within the initial 1 min and quantitative sorption within 5 min of equilibration. The sorption was found to follow Langmuir isotherm model, and the Langmuir capacity was calculated as 19.7 mg g^?1. The ability of polyaniline to form stable and homogeneous pellets facilitated the energy dispersive X‐ray fluorescence determination without recourse to elution. Detection limit of Hg was found to be 22 ng, considering 100 mg pellet of polyaniline. The apparent detection limit was 6 pg, as the preconcentration factor of Hg(II) on polyaniline was 4 × 10³. The developed method is at par with the established method for mercury determination, namely, cold vapor atomic absorption spectrometry. Accuracy of the method was established by the analysis of the International Atomic Energy Agency reference materials, namely, hair and lichen, for Hg(II). Copyright © 2016 John Wiley & Sons, Ltd.     

Determination of spin,magnetic moment and isotopic shift of neutron rich205Hg by optical pumping

Neutron rich²⁰⁵Hg (T _1/2=5.2 min) was produced and on-line mass separated at the ISOLDE facility at CERN. The polarization achieved by optical pumping via the atomic line (6s ²¹ S ₀?6s6p ³ P ₁,λ=2 537Å) was monitored by theβ decay asymmetry. Hyperfine structure and isotopic shift of the²⁰⁵Hg absorption line was determined by Zeeman scanning. In addition a magnetic resonance was performed on the polarized²⁰⁵Hg nuclei in the atomic ground state. The results are: \(I(^{205} Hg) = \tfrac{1}{2}\) (confirmed);μ _I (²⁰⁵Hg)=0.5915 (1)μ _N (uncorrected for diamagnetism); isotopic shiftδv^204/205=v(²⁰⁵Hg)-v(204Hg)=?1.8 (1) GHz.μ _I and IS are discussed briefly in the frame of current literature.     

Magneto-optical trapping of neutral mercury

We report on the cooling of neutral mercury in a magneto-optical trap utilizing the spin forbidden ¹S₀ → ³P₁ transition at 253.7 nm. We trapped two Hg isotopes, i.e. the bosonic ²⁰²Hg and the fermionic ¹⁹⁹Hg isotope, respectively. The temperature of the cold atom cloud was determined to be approximately 300 μK using a modified TOF-method. It is currently limited by the quality of the laser lock. Trapped neutral Hg has many interesting avenues such as a time standard and high precision measurements. Here, we discuss the possibilities of photo-association spectroscopy and the generation of ultra-cold Hg₂ dimers.     

Ultrasensitive and selective spectrofluorimetric determination of Hg(II) using a dimercaptothiadiazole fluorophore

The present work describes the ultrasensitive and selective spectrofluorimetric determination of Hg(II) using 2,5-dimercaptothiadiazole (DMT) as a fluorophore. DMT shows an emission maximum at 435 nm while exciting at 330 nm. The colorless solution of DMT changes into a highly emittive yellow color immediately after the addition of 0.5 μM Hg(II) and nearly 245-fold increase in emission intensity at 435 nm was observed. These changes were ascribed to the complex formation between Hg(II) and DMT. Based on the fluorescence enhancement, the concentration of Hg(II) was determined. The binding constant value (K_A=1.8620×10⁴ mol⁻¹ L) suggests that there is a strong binding force between Hg(II) and DMT. The fluorescence quantum yield of DMT-Hg(II) complex was found to be 4-fold higher than that of DMT, indicating that the DMT-Hg(II) complex was highly emittive than the DMT. Interestingly, the emission intensity was increased even in the presence of 0.1 pM Hg(II). The fluorophore showed an extreme selectivity towards 100 nM Hg(II) in the presence of 50,000-fold higher concentrations of Na⁺, K⁺, Ca²⁺, Mg²⁺, Fe²⁺, Fe³⁺, Cd²⁺, Cr³⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺, Cl⁻, SO₄²⁻, NO₃⁻ ions and 1000-, 500- and 200-fold higher concentrations of Cu²⁺, Pb²⁺ and Ag⁺ ions, respectively, as interferences. The lowest detection of 18 pg L⁻¹ Hg(II) (LOD=3S/m) was achieved for the first time using DMT by fluorimetry. The proposed method was successfully utilized for the determination of Hg(II) in tap water, river water and industrial waste water samples.     

Oblate shapes of200, 202, 204Hg

Measurements of the reorientation effect for the first excited 2⁺ states in^{200, 202, 204}Hg were performed by exploiting the dependence of theγ-ray yield on Q₂+ for different projectiles. For²⁰⁰Hg, a positive quadrupole moment of Q₂=0.96±0.11 eb (for negative interference) or Q₂=1.11±0.11 eb (for positive interference) was determined indicating an oblate shape. Small positive Q₂ values were also found for²⁰²Hg and²⁰⁴Hg. Nine B(E2) values for excitation of the 2⁺, 2⁺′ and 4⁺ states in^196–204Hg measured.