Subsurface transport behavior of micro-nano bubbles and potential applications for groundwater remediation.

Micro-nano bubbles (MNBs) are tiny bubbles with diameters on the order of micrometers and nanometers, showing great potential in environmental remediation. However, the application is only in the beginning stages and remains to be intensively studied. In order to explore the possible use of MNBs in groundwater contaminant removal, this study focuses on the transport of MNBs in porous media and dissolution processes. The bubble diameter distribution was obtained under different conditions by a laser particle analyzer. The permeability of MNB water through sand was compared with that of air-free water. Moreover, the mass transfer features of dissolved oxygen in water with MNBs were studied. The results show that the bubble diameter distribution is influenced by the surfactant concentration in the water. The existence of MNBs in pore water has no impact on the hydraulic conductivity of sand. Furthermore, the dissolved oxygen (DO) in water is greatly increased by the MNBs, which will predictably improve the aerobic bioremediation of groundwater. The results are meaningful and instructive in the further study of MNB research and applications in groundwater bioremediation.

Transient flow patterns and bubble slug lengths in parallel microchannels with oxygen gas bubbles produced by catalytic chemical reactions

Transient flow patterns and bubble slug lengths were investigated with oxygen gas (O-2) bubbles produced by catalytic chemical reactions using a high speed camera bonded with a microscope. The microreactor consists of an inlet liquid plenum, nine parallel rectangular microchannels followed by a micronozzle, using the MEMS fabrication technique. The etched surface was deposited by the thin platinum film, which is acted as the catalyst. Experiments were performed with the inlet mass concentration of the hydrogen peroxide from 50% to 90% and the pressure drop across the silicon chip from 2.5 to 20.0 kPa. The silicon chip is directly exposed in the environment thus the heat released via the catalytic chemical reactions is dissipated into the environment and the experiment was performed at the room temperature level. It is found that the two-phase flow with the catalytic chemical reactions display the cyclic behavior. A full cycle consists of a short fresh liquid refilling stage, a liquid decomposition stage followed by the bubble slug flow stage. At the beginning of the bubble slug flow stage, the liquid slug number reaches maximum, while at the end of the bubble slug flow stage the liquid slugs are quickly flushed out of the microchannels. Two or three large bubbles are observed in the inlet liquid plenum, affecting the two-phase distributions in microchannels. The bubble slug lengths, cycle periods as well as the mass flow rates are analyzed with different mass concentrations of hydrogen peroxide and pressure drops. The bubble slug length is helpful for the selection of the future microreactor length ensuring the complete hydrogen peroxide decomposition. Future studies on the temperature effect on the transient two-phase flow with chemical reactions are recommended.

Can the nuclear symmetry potential at supra-saturation densities be negative?

In the framework of an isospin-dependent Boltzmann-Uehling-Uhlenbeck (IBUU) transport model, for the central Au-197 + Au-197 reaction at an incident beam energy of 400 MeV/nucleon, the effect of nuclear symmetry potential at supra-saturation densities on the preequilibrium clusters emission is studied. It is found that for the positive symmetry potential at supra-saturation densities the neutron-to-proton ratio of lighter clusters with mass number A less than or similar to 3 [(n/p)(A less than or similar to 3)] is larger than that of the heavier clusters with mass number A > 3 [(n/p)(A>3)], whereas for the negative symmetry potential at supra-saturation densities the (n/p)(A less than or similar to 3) is smaller than the (n/p)(A>3). This may be considered as a probe of the negative symmetry potential at supra-saturation densities.

Evaluation of flavonoids binding to DNA duplexes by electrospray ionization mass spectrometry

In this study, electrospray ionization mass spectrometry (ESI-MS) was used to investigate the binding interactions of ten flavonoid aglycones and ten flavonoid glycosides with DNA duplexes. Relative binding affinities of the flavonoids toward DNA duplexes were estimated based on the fraction of bound DNA. The results revealed that the 4'-OH group of flavonoid aglycones was essential for their DNA-binding properties. Flavonoid glycosides with sugar chain linked on ring A or ring B showed enhanced binding toward the duplexes over their aglycone counterparts, whereas glycosylation of the flavonol quercetin on ring C exhibited a less pronounced effect.

Studies on the Biotransformation of Arctigenin Using Electrospray Ionization Mass Spectrometry

To study the biotransformation of arctigenin, arctigenin was anaerobically incubated with Eubacterium sp. ARC-2 of human intestinal bacteria in vitro. Arctigenin formed a molecular ion [M-H](-) in negative ion mode. The arctigenin and its metabolites were investigated directly by the electrospray ionization tandem mass spectrometry ion trap and Fourier transform ion cyclotron resonance. Arctigenin was transformed to 4',4 ''-dihydroxylenterolactone by E sp. ARC-2 through 3 types of demethylation products.

Identification of Phenylethanoid Glycosides in Plant Extract of Plantago asiatica L. by Liquid Chromatography-Electrospray Ionization Mass Spectrometry

The present work describes a liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method for rapid identification of phenylethanoid glycosides in plant extract from Plantago asiatica L. By using a binary mobile phase system consisting of 0.2% acetic acid and acetonitrile under gradient conditions, a good separation was achieved on a reversed-phase C-18 column. The [M-H](-) ions, the molecular weights, and the fragment ions of phenylethanoid glycosides were obtained in the negative ion mode using LC-ESI-MS. The identification of the phenylethanoid glycosides (peaks 1-3) in the extract of P. asiatica L. was based on matching their retention time, the detection of molecular ions, and the fragment ions obtained by collision-induced dissociation (CID) experiments with those of the authentic standards and data reported in the literature.

Analysis on Iridoid Glycosides in Crude and Processed Extracts from Cornus Officinals by Liquid Chromatography-electrospray Ionization Mass Spectrometry

The iridoid glycosides in crude and processed extracts from cornus officinals have been analyzed by high performance liquid chromatography-electrospray ionization mass spectrometry. Samples were analyzed by a reversed-phase C18 column using a binary eluent under gradient conditions. Seven iridoid glycosides could be separated and detected. The [M-H](-) ions of iridoid glycosides in the negative ion mode were observed, which reflect their molecule mass information. An in-source collision induced dissociation (in-source CID) experiment was carried out in order to identify the structures and to measure the contents of iridoid glycosides. The epimers were discovered in the experiment for the first time, namely 7 alpha-O-ethyl-morroniside and 7 beta-O-ethylmorroniside.

Analysis of Saponins from Leaves of Aralia elata by Liquid Chromatography and Multi-stage Tandem Mass Spectrometry

Four saponins were isolated from the leaves of Aralia elata, and established using NMR and other spectroscopic methods, as well as data reported in the literature. Three Aralia saponins from the leaves of Aralia elata sharing the same structures as those isolated from the root bark suggested that the leaves would be a good substitute for the root bark of Aralia elata. These four Aralia saponins were then extensively investigated using complementarily positive and negative electrospray ionization multistage tandem mass spectrometry (ESI-MSn). Two isomers of saponins with different sugar linkages were then successfully differentiated by positive ESI-MSn and verified with different retention times and the collision-induced dissociation (CID) spectra by LC-MS. A simple and effective LC-MS method was thus developed for the rapid identification and screening of these saponins in plant extracts from leaves of Aralia elata.

Investigation of heptakis(2,6-di-O-methyl)-beta-cyclodextrin inclusion complexes with flavonoid glycosides by electrospray ionization mass spectrometry

The non-covalent complexes between three flavonoid glycosides (quercitrin, hyperoside and rutin) and heptakis(2,6-di-O-methyl)-beta-cyclodextrin (DM-beta-CD) were investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The 1:1 complexation of each flavonoid glycoside (guest) to the DM-beta-CD (host) was monitored in the negative ion mode by mixing each guest with an up to 30-fold molar excess of the host. The binding constants for all complexes were calculated by a linear equation in the order: DM-beta-CD:quercitrin > DM-beta-CD:rutin > DM-beta-CD:hyperoside. A binding model for the complexes has also been proposed based on the binding constants and tandem mass spectrometric data of these complexes.

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.

Structural analysis of selected characteristic flavones by electrospray tandem mass spectrometry

Seven structure analogical flavonoid aglycones have been analyzed using electrospray ionization tandem mass spectrometry (ESI-MSn) in the negative-ion mode. The spectra obtained ESI-MSn allowed us to propose plausible schemes for their fragmentation mechanism. By analyzing the product ions spectra of deprotonated molecule ions [M-H](-), some neutral diagnostic losses and specific retro Diels-Alder fragments were obtained. By using all of these characteristic fragment ions we can specially differentiate the flavone isomer.

Characterization of non-covalent complexes of rutin with cyclodextrins by electrospray ionization tandem mass spectrometry

Electrospray ionization tandem mass spectrometry (ESI-MSn) and the phase solubility method were used to characterize the gas-phase and solution-phase non-covalent complexes between rutin (R) and alpha-, beta- and gamma-cyclodextrins (CDs). The direct correlation between mass spectrometric results and solution-phase behavior is thus revealed. The order of the 1:1 association constants (K-c) of the complexes between R and the three CDs in solution calculated from solubility diagrams is in good agreement with the order of their relative peak intensities and relative collision-induced dissociation (CID) energies of the complexes under the same ESI-MSn condition in both the positive and negative ion modes. Not only the binding stoichiometry but also the relative stabilities and even binding sites of the CD-R complexes can be elucidated by ESI-MSn. The diagnostic fragmentation of CD-R complexes, with a significant contribution of covalent fragmentation of rutin leaving the quercetin (Q) moiety attached to the CDs, provides convincing evidence for the formation of inclusion complexes between R and CDs. The diagnostic fragment ions can be partly confirmed by the complexes between Q and CDs. The gas-phase stability order of the deprotonated CD-R complexes is beta-CD-R > alpha-CD-R > gamma-CD/R; beta-CD seems to bind R more strongly than the other CDs.

Structural analysis of saponins from medicinal herbs using electrospray ionization tandem mass spectrometry

The underivatized saponins from Tribulus terrestris and Panax ginseng have been investigated by electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn). In ESI-MS spectra, a predominant [M + Na](+) ion in positive mode and [M - H](-) ion in negative mode were observed for molecular mass information. Multi-stage tandem mass spectrometry of the molecular ions was used for detailed structural analysis. Fragment ions from glycoside cleavage can provide information on the mass of aglycone and the primary sequence and branching of oligosaccharide chains in terms of classes of monosaccharides. Fragment ions from cross-ring cleavages of sugar residues can give some information about the linkages between sugar residues. It was found that different alkali metal-cationized adducts with saponins have different degrees of fragmentation, which may originate from the different affinity of a saponin with each alkali metal in the gas phase. ESI-MSn has been proven to be an effective tool for rapid determination of native saponins in extract mixtures, thus avoiding tedious derivatization and separation steps.

Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip.

Mass spectrometric studies of metallofullerene

The endrohel metallofullerene, Gd@C-82, Gd@C-80, Gd-2@C-80 were synthesized by using K-H method. The technique of two-step of high pressure and high temperature extraction with 1, 3, 5-trimethylbenzene (first step) and pyridine(second step) has been successfully utilized to extract metallofullerene of Gd@C-82 The gas-phase negative ions of fullerenes C-n(n= 60, 70, 78, 82, 84...) and metallofullerene (Gd@C-82) have been studied by the ESI-MS, REC-MS and MALDI-TOF-MS. The differences among the mass spectra of ESI-MS, REC-MS and MALDI-TOF-MS have been observed and explained. In contrast to the empty fullerene C-82 , the metallofullerene Gd@C-82 should have a larger HOMO-LUMO gap. Experimental results suggest that Gd@C-82 is polarized and Gd3+ located in the off-center position of C-82 cage after Gd3+ is trapped into C-82 cage.