Studies on the doubly charged cluster ions of sodium and potassium nitrates by electrospray ionization tandem mass spectrometry

Doubly charged cluster ions, besides singly charged cluster ions, from sodium and potassium nitrates were produced evidently under normal source capillary temperature of 200 degrees C in both positive and negative ion electrospray ionization (ESI) ion trap mass spectrometry. The fragmentation pathways for doubly charged cluster ions were studied in detail using ESI tandem mass spectrometry and two pathways were observed depending on the cluster sizes of alkali metal nitrates. In addition, factors that affect the formation of cluster ions were also interrogated.

High-dimensional assembly depending on polyoxoanion templates, metal ion coordination geometries, and a flexible bis(imidazole) ligand

By introducing the flexible 1,1'-(1,4-butanediyl)bis(imidazole) (bbi) ligand into the polyoxovanadate system, five novel polyoxoanion-templated architectures based on [As8V14O42](4-) and [V16O38Cl](6-) building blocks were obtained: [M(bbi)(2)](2)[As8V14O42(H2O)] [M = Co (1), Ni (2), and Zn (3)], [Cu(bbi)](4)[As8V14O42(H2O)] (4), and [Cu(bbi)](6)[V16O38Cl] (5). Compounds 1-3 are isostructural, and they exhibit a binodal (4,6)-connected 2D structure with Schlafli symbol (3(4)center dot 4(2))(3(4)center dot 4(4)center dot 5(4)center dot 6(3))(2), in which the polyoxoanion induces a closed four-membered circuit of M-4(bbi)(4). Compound 4 exhibits an interesting 3D framework constructed from tetradentate [As8V14O42](4-) cluster anions and cationic ladderlike double chains. There exists a bigger M-8(bbi)(6)O-2 circuit in 4. The 3D extended structure of 5 is composed of heptadentate [V16O38Cl](6-) anions and flexural cationic chains; the latter consists of six Cu(bbi) segments arranged alternately. It presents the largest 24-membered circuit of M-24(bbi)(24) so far observed made of bbi molecules and transition-metal cations. Investigation of their structural relations shows the important template role of the polyoxoanions and the synergetic interactions among the polyoxoanions, transition-metal ions, and flexible ligand in the assembly process.

Mercaptoethane sulfonate protected, water-soluble gold and silver nanoparticles: Syntheses, characterization and their building, multilayer films with polyaniline via ion-dipole interactions

Mercaptoethane sulfonate protected, water-soluble gold and silver nanoparticles (Au-MES and Ag-MES) are synthesized by one-phase method and characterized by TEM, TGA and XPS techniques, UV-vis and FTIR spectra. Both Au-MES and Ag-MES nanoparticles are soluble in the water up to 2.0 mg/ml and the stability of AU-MES is much better than that of Ag-MES. When dissolved in the water. they behave like a polyanion and can be used to build multilayer films with polyaniline (PANI) by way of layer-by-layer. A new approach is presented to fabricate the Multilayer films of Au-MES/PANI and Ag-MES/PAN]. The assembly mechanism of these multilayer films is also discussed. We anticipate highly conducting PANI films can be obtained by doping with these nanoparticles.

New typical ionic cluster K+(KNO3)(n) and NO3-(KNO3)(m)

New typical ionic clusters with complex anions could be formed directly from the KNO3 aqueous solution by means of the electrospray ionization mass spectrometry(ESIMS). The difference between the neighboring peaks(m/z), which corresponded to the molecule weight of KNO3 being 101 in the full mass spectrometry of the positive-ion and the negative-ion. The general formula of the ionic clusters belonged to K+(KNO3)(n) and NO3- (KNO3)(m).

Structural changes of TiO2 gel using Eu3+ ion as the fluorescence probe

Because of the extremely sensitivity to the local environment of the D-5(0) --> F-7(2) transition of Eu3+ ion, the fluorescence of Eu3+ ions was Studied by introducing Eu3+ ions to TiO2 gel by the sol-gel method, from which the structural changes of TiO2 gel were characterized. The results showed that the intensity of D-5(0) --> F-7(2) transition increased with the increasement of heat treatment temperature, which indicated the evaporation of molecular water and the completeness of the condensation reaction. Because of the quenching of the fluorescence induced by the cluster of Eu3+ ions, the addition of Al3+ ions greatly enhanced the emission intensity of Eu3+ ion.

Behavior of silver cluster on laser desorption/ionization time-of-flight mass spectrometry

A successful analysis of silver was reported utilizing laser desorption/ionization time-of-flight mass spectrometry (LDI/TOF-MS) in this paper, The silver cluster ions Ag-n(+) and AgnO+ (n=2 similar to 5) were formed during laser desorption/ionization. In the presence of I-, K+ and Na+, the peaks corresponding, to the cluster ions [AgnIn-1](+) (n=2 similar to 6) and the adduct ions [AgI](+), [AgI]Na+ and [AgI]K+ were observed in the positive ion spectrum; the peaks corresponding to [AgnIn+1](-) (n=1 similar to 3) were found in the negative ion spectrum, all of which accompanied by sliver isotope distribution, The formation of silver cluster ions was accomplished through two-stage reaction: the first step was the generation of clusters, which was followed by the processes of photoionization and ion/molecule reaction.

Ionography of nanostructures with the use of a laser plasma of cluster targets

It has been shown that a femtosecond plasma of cluster targets is an almost isotropic source of fast ions and, hence, can be used to obtain ionographic images with a wide field of view. The spatial resolution of the resulting ionographic images is no worse than 600 nm, which corresponds to a uniquely high value of about 105 of the ratio of the field of view to the resolution. The use of 100–300-keV ion fluxes ensures the sensitivity of the method to the sample thickness of no worse than 100 nm even for samples consisting of light chemical elements (C, H). The proposed method can be used to obtain images of low-contrast biological objects, thin films, membranes, and other nanostructured objects.

Electron-induced hydrogen loss in uracil in a water cluster environment

Low-energy electron-impact hydrogen loss due to dissociative electron attachment (DEA) to the uracil and thymine molecules in a water cluster environment is investigated theoretically. Only the A'-resonance contribution, describing the near-threshold behavior of DEA, is incorporated. Calculations are based on the nonlocal complex potential theory and the multiple scattering theory, and are performed for a model target with basic properties of uracil and thymine, surrounded by five water molecules. The DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster. This growth is due to two effects: the increase of the resonance lifetime and the negative shift in the resonance position due to interaction of the intermediate negative ion with the surrounding water molecules. A similar effect was earlier found in DEA to chlorofluorocarbons. 

Studies on the optical band gap and cluster size of the polyaniline thin films irradiated with swift heavy Si ions

Polyaniline thin films prepared by RF plasma polymerisation were irradiated with 92MeV Si ions for various fluences of 1 1011, 1 1012 and 1 1013 ions/cm2. FTIR and UV–vis–NIR measurements were carried out on the pristine and Si ion irradiated polyaniline thin films for structural evaluation and optical band gap determination. The effect of swift heavy ions on the structural and optical properties of plasma-polymerised aniline thin film is investigated. Their properties are compared with that of the pristine sample. The FTIR spectrum indicates that the structure of the irradiated sample is altered. The optical studies show that the band gap of irradiated thin film has been considerably modified. This has been attributed to the rearrangement in the ring structure and the formation of CRC terminals. This results in extended conjugated structure causing reduction in optical band gap

Femtosecond dynamics of molecular and cluster ionization and fragmentation

The real-time dynamics of molecular (Na_2 . Na_3) and cluster Na_n (n=4-2l) multiphoton ionization and -fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Wave packet motion in the dimer Na_2 reveals two independent multiphoton ionization processes while the higher dimensional motion in the trimer Na_3 reflects the chaotic vibrational motion in this floppy system. The first studies of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na^*_n) ) with femtosecond laser pulses give a striking illustration of the transition from "molecule-like" excitations to "surfaceplasma"-like resonances for increasing cluster sizes. Time-resolved fragmentation of cluster ions Na_n^* indicate that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.

Coordinated ground-based, low altitude satellite and Cluster observations on global and local scales during a transient post-noon sector excursion of the magnetospheric cusp

On 14 January 2001, the four Cluster spacecraft passed through the northern magnetospheric mantle in close conjunction to the EISCAT Svalbard Radar (ESR) and approached the post-noon dayside magnetopause over Greenland between 13:00 and 14:00 UT During that interval, a sudden reorganisation of the high-latitude dayside convection pattern accurred after 13:20 UT most likely caused by a direction change of the Solar wind magnetic field. The result was an eastward and poleward directed flow-channel, as monitored by the SuperDARN radar network and also by arrays of ground-based magnetometers in Canada, Greenland and Scandinavia. After an initial eastward and later poleward expansion of the flow-channel between 13:20 and 13:40 UT, the four Cluster spacecraft, and the field line footprints covered by the eastward looking scan cycle of the Sondre Stromfjord incoherent scatter radar were engulfed by cusp-like precipitation with transient magnetic and electric field signatures. In addition, the EISCAT Svalbard Radar detected strong transient effects of the convection reorganisation, a poleward moving precipitation, and a fast ion flow-channel in association with the auroral structures that suddenly formed to the west and north of the radar. From a detailed analysis of the coordinated Cluster and ground-based data, it was found that this extraordinary transient convection pattern, indeed, had moved the cusp precipitation from its former pre-noon position into the late post-noon sector, allowing for the first and quite unexpected encounter of the cusp by the Cluster spacecraft. Our findings illustrate the large amplitude of cusp dynamics even in response to moderate solar wind forcing. The global ground-based data proves to be an invaluable tool to monitor the dynamics and width of the affected magnetospheric regions.

Coordinated Cluster and ground-based instrument observations of transient changes in the magnetopause boundary layer during an interval of predominantly northward IMF: relation to reconnection pulses and FTE signatures

We study a series of transient entries into the low-latitude boundary layer (LLBL) of all four Cluster spacecraft during an outbound pass through the mid-afternoon magnetopause ([X(GSM), Y(GSM), Z(GSM)] approximate to [2, 7, 9] R(E)). The events take place during an interval of northward IMF, as seen in the data from the ACE satellite and lagged by a propagation delay of 75 min that is well-defined by two separate studies: (1) the magnetospheric variations prior to the northward turning (Lockwood et al., 2001, this issue) and (2) the field clock angle seen by Cluster after it had emerged into the magnetosheath (Opgenoorth et al., 2001, this issue). With an additional lag of 16.5 min, the transient LLBL events cor-relate well with swings of the IMF clock angle (in GSM) to near 90degrees. Most of this additional lag is explained by ground-based observations, which reveal signatures of transient reconnection in the pre-noon sector that then take 10-15 min to propagate eastward to 15 MLT, where they are observed by Cluster. The eastward phase speed of these signatures agrees very well with the motion deduced by the cross-correlation of the signatures seen on the four Cluster spacecraft. The evidence that these events are reconnection pulses includes: transient erosion of the noon 630 nm (cusp/cleft) aurora to lower latitudes; transient and travelling enhancements of the flow into the polar cap, imaged by the AMIE technique; and poleward-moving events moving into the polar cap, seen by the EISCAT Svalbard Radar (ESR). A pass of the DMSP-F15 satellite reveals that the open field lines near noon have been opened for some time: the more recently opened field lines were found closer to dusk where the flow transient and the poleward-moving event intersected the satellite pass. The events at Cluster have ion and electron characteristics predicted and observed by Lockwood and Hapgood (1998) for a Flux Transfer Event (FTE), with allowance for magnetospheric ion reflection at Alfvenic disturbances in the magnetopause reconnection layer. Like FTEs, the events are about 1 R(E) in their direction of motion and show a rise in the magnetic field strength, but unlike FTEs, in general, they show no pressure excess in their core and hence, no characteristic bipolar signature in the boundary-normal component. However, most of the events were observed when the magnetic field was southward, i.e. on the edge of the interior magnetic cusp, or when the field was parallel to the magnetic equatorial plane. Only when the satellite begins to emerge from the exterior boundary (when the field was northward), do the events start to show a pressure excess in their core and the consequent bipolar signature. We identify the events as the first observations of FTEs at middle altitudes.

Coordinated Cluster, ground-based instrumentation and low-altitude satellite observations of transient poleward-moving events in the ionosphere and in the tail lobe

During the interval between 8:00-9:30 on 14 January 2001, the four Cluster spacecraft were moving from the central magnetospheric lobe, through the dusk sector mantle, on their way towards intersecting the magnetopause near 15:00 MLT and 15:00 UT. Throughout this interval, the EIS-CAT Svalbard Radar (ESR) at Longyearbyen observed a series of poleward-moving transient events of enhanced F-region plasma concentration ("polar cap patches"), with a repetition period of the order of 10 min. Allowing for the estimated solar wind propagation delay of 75 ( 5) min, the interplanetary magnetic field (IMF) had a southward component during most of the interval. The magnetic footprint of the Cluster spacecraft, mapped to the ionosphere using the Tsyganenko T96 model (with input conditions prevailing during this event), was to the east of the ESR beams. Around 09:05 UT, the DMSP-F12 satellite flew over the ESR and showed a sawtooth cusp ion dispersion signature that also extended into the electrons on the equatorward edge of the cusp, revealing a pulsed magnetopause reconnection. The consequent enhanced ionospheric flow events were imaged by the SuperDARN HF backscatter radars. The average convection patterns (derived using the AMIE technique on data from the magnetometers, the EISCAT and SuperDARN radars, and the DMSP satellites) show that the associated poleward-moving events also convected over the predicted footprint of the Cluster spacecraft. Cluster observed enhancements in the fluxes of both electrons and ions. These events were found to be essentially identical at all four spacecraft, indicating that they had a much larger spatial scale than the satellite separation of the order of 600 km. Some of the events show a correspondence between the lowest energy magnetosheath electrons detected by the PEACE instrument on Cluster (10-20 eV) and the topside ionospheric enhancements seen by the ESR (at 400-700 km). We suggest that a potential barrier at the magnetopause, which prevents the lowest energy electrons from entering the magnetosphere, is reduced when and where the boundary-normal magnetic field is enhanced and that the observed polar cap patches are produced by the consequent enhanced precipitation of the lowest energy electrons, making them and the low energy electron precipitation fossil remnants of the magnetopause reconnection rate pulses.

Structural role of fluoride in the ion-conducting glass system B(2)O(3)-PbO-LiF studied by single- and double-resonance NMR

The local structure of an ion-conducting glass with nominal composition 50B(2)O(3)-10PbO-40LiF has been investigated by complementary (7)Li, (11)B, (19)F, and (207)Pb single- and double-resonance experiments. The results give insight into the structural role of the lithium fluoride additive in borate glasses: (1) LiF is seen to actively participate in the network transformation process contributing to the conversion of three- into four-coordinate boron units, as shown by (11)B single-resonance as well as by (11)B{(19)F} and (19)F{(11)B} double-resonance experiments. (2) (19)F signal quantification experiments suggest substantial fluoride loss, presumably caused by formation of volatile BF(3). A part of the fluoride remains in the dopant role, possibly in the form of small LiF-like cluster domains, which serve as a mobile ion supply. (3) The extent of lithium-fluorine and lead-fluorine interactions has been characterized by (7)Li{(19)F} and (207)Pb{(19)F} REDOR and SEDOR experiments. On the basis of these results, a quantitative structural description of this system has been developed.

Supramolecular Approach to Gold Nanoparticle/Triruthenium Cluster Hybrid Materials and Interfaces

A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.