A velocity map ion-imaging study on C2H5SH and C3H7SH photodissociation at 243 nm

Photodissociation dynamics Of C2H5SH, i-C-3-H7SH and n-C3H7SH at 243.1 nm were investigated using velocity map ion-imaging method. H-atom photolysis products were detected by a (2 + 1) resonance enhanced ionization scheme. Both the angular distribution and translational energy distribution of the H-atom elimination processes were determined from the ion images of the H-atom products. The experimental results indicate that the H-atom eliminations from these molecules are mainly direct and fast dissociation processes from a repulsive potential energy state. And a more statistical dissociation process that likely occurs oil the ground state via internal conversion has also been observed. Dissociation energies of the S-H bonds are also derived from the H-atom product translational energy distributions. (C) 2002 Elsevier Science B.V. All rights reserved.

Calibration of an audio-frequency ion trap mass spectrometer

A method for calibration of an audio-frequency (AF) ion trap mass spectrometer is described. The method is proposed to surmount the obstacle that there is a lack of a proper calibrant for mass spectrometers in the mass-to-charge ratio (m/z) range of 10(6) to 10(10). To calibrate such mass spectra, we determine the point of ejection, q(eject), on the stability diagram of the ion trap operated in a mass-selective axial instability mode. This is accomplished by measuring the radial secular frequencies (and therefore, the m/z value) of a single trapped particle using a light scattering method, followed by monitoring the action of particle ejection in real time to obtain the q(eject). A delayed ejection with q(eject) = 0.949 +/- 0.004 is found at a trap driving frequency of Ohm/2pi = 200-600Hz. Theoretical analysis for the origin of the delayed ejection indicates that the delay is predominantly resulted from the existence of multipole components in the fields due to trap imperfections. Inclusion of -3% of the octopole with respect to the basic quadrupole field can satisfactorily account for our observations. An m/z accuracy approaching 0.1% is attainable after proper calibration of the AF ion trap mass spectrometer. (Int J Mass Spectrom 214 (2002) 63-73) (C) 2002 Elsevier Science B.V. All rights reserved.

Proton transfer reactions within the pyridazine-methanol cluster ion

The multiphoton ionization of the hydrogen-bonding cluster pyridazine-methanol (C4H4N2-CH3OH) was studied using a time-of-flight mass spectrometer at the wavelengths of 355 and 532 nm. At both wavelengths, a series of protonated C4H4N2-(CH3OH)(n)-H+ cluster ions were obtained. Relevant ab initio calculations were performed with HF and B3LYP methods. Equilibrium geometries of both neutral and ionic C4H4N2-CH3OH clusters, and dissociation channels and dissociation energies of ionic clusters, are presented. The results show that when C4H4N2-CH3OH is vertically ionized, C4H4N2H+ and CH3O are the dominant products via proton transfer reaction. A high energy barrier makes another channel corresponding to the production of C4H4N2H+ and CH2OH disfavored. (C) 2002 Elsevier Science B.V. All rights reserved.

Ion recognition: application of symmetric and asymmetric schiff bases and their complexes for the fabrication of cationic and anionic membrane sensors to determine ions in real samples

Schiff base compounds refer to the branch of supra-molecules and can be used as sensing material in the construction of potentiometric ion selective electrodes (ISEs). This relatively modern field has been subject to extensive research in the period of 1999-2007 when more than 100 ISEs employing Schiff bases were constructed. The quantitative high-throughput detection of 29 cations and 7 anions has been demonstrated in various scientific branches, such as biomedicine, pharmacy, biochemistry, pharmacology, environmental chemistry, food technology, and agriculture. This review discusses Schiff base compounds and their applications in the design and development of ion selective sensors and microsensors.

Calibration of a solid-state copper ion-selective electrode in cupric ion buffers containing chloride

It is shown that near-Nernstian calibration slopes can be obtained with a Cu1.8Se electrode in a range of cupric ion buffers in spite of a high chloride content. Best results are obtained with the ligands ethylenediamine, glycine and histidine. The onset of cupric ion toxicity towards marine organisms falls within the pCu calibration range obtained with glycine, and the Cu1.8Se electrode could, therefore, be useful for monitoring cupric ion activity in bioassays in sea-water media.

Mercury(II) ion sensing with PVC-matrix based membrane sensors

Thiosemicarbazone derivatives have been used as ion carriers for the preparation of PVC-matrix based mercury(II)-selective membrane sensors. The electrodes give near-Nernstian responses in the linear concentration range of 1.0×10-1-5.0×10-6 M with detection limits of the order of 10-6 M. The stable potentiometric signals are obtained within a short time period of 20-25s. The effect of different plasticizers has been studied and dioctylsebacate (DOS) found to give a better response in comparison to other plasticizers. Selectivity coefficient values (log KPotHg,M) have been evaluated using fixed interference method. Better selectivity for mercury(II) ions is observed over many of the monovalent (Na+, K+ and NH4+) and divalent ions (Mg2+, Ca2+, Zn2+, Pb2+, Ni2+, Co2+, etc.). The sensors have also been used as indicator electrodes in potentiometric titration of mercury(II) ions with EDTA and its determination in synthetic water samples.

Synthesis and Metal-ion Binding Properties of New N2S4O2- and N2S5O2-Donor Macrocycles

Synthetic procedures for new mixed-donor macrocycle compounds were reported. The macrocyclic compounds were used in solvent extraction metal picrates such as Ag+, Hg2+, Cd2+, Zn2+, Cu2+, Ni2+, Mn2+, Pb2+, and Co2+. The metal picrate extractions were investigated at 25±0.1°C with the aid of UV-visible spectrometry. It was found that 6,7,9,10,12,13,23,24-octahydro-19H,26Hdibenzo[h,t](1,4,7,13,16,22,10,19) dioxatetrathiadiazasiclotetracosine-20,27(21H,28H)-dione showed selectivity towards Ag+, Hg2+, and Cd2+ among the other metals. The extraction constants (Log Kex) and complex compositions were determined for the Ag+ and Hg2+ complexes for this compound and 9,10,12,13,23,24,26,27,29,30-decahydro-5H,15H-dibenzo-[h,w][1,4,7,13,16,19,25-,10,22] dioxapentathiadiazacycloheptacosine-6,16(7H,17H)-dione.

Synthesis and characterization of a novel two-component organogelator based on ion-bonded discotic complex

A novel ion-bonded discotic complex was prepared from 2,3,6,7,10,11-hexakis(N,N-dimethylaminopropylaminocarbonylmethoxy)triphenylene (HDTP) and 4'-dodecyloxybiphenyl-4-carboxylic acid (DBC) by ionic self-assembly (ISA) route and characterized by Fourier transform infrared (FTIR) spectrum. We found that the complex can self-assemble into stable gels in aromatic hydrocarbons. Nanofibers with diameters of 50-130 nm were observed in the gels by transmission electron micrograph (TEM).

A strategy for synthesis of ion-bonded supramolecular star polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization

We have developed a novel strategy for the preparation of ion-bonded supramolecular star polymers by RAFT polymerization. An ion-bonded star supramolecule with six functional groups was prepared from a triphenylene derivative containing tertiary amino groups and trithiocarbonate carboxylic acid, and used as the RAFT agent in polymerizations of tert-butyl acrylate (tBA) and styrene (St). Molecular weights and structures of the polymers were characterized by H-1 NMR and GPC. The results show that the polymerization possesses the character of living free-radical polymerization and the ion-bonded supramolecular star polymers PSt, PtBA, and PSt-b-PtBA, with six well-defined arms, were successfully synthesized.

A strategy for synthesis of ion-bonded amphiphilic miktoarm star copolymers via supramolecular macro-RAFT agent

Amphiphilic supramolecular miktoarm star copolymers linked by ionic bonds with controlled molecular weight and low polydispersity have been successfully synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization using an ion-bonded macromolecular RAFT agent (macro-RAFT agent). Firstly, a new tetrafunctional initiator, dimethyl 4,6-bis(bromomethyl)-isophthalate, was synthesized and used as an initiator for atom transfer radical polymerization (ATRP) of styrene to form polystyrene (PSt) containing two ester groups at the middle of polymer chain. Then, the ester groups were converted into tertiary amino groups and the ion-bonded supramolecular macro-RAFT agent was obtained through the interaction between the tertiary amino group and 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid (DMP). Finally, ion-bonded amphiphilic miktoarm star copolymer, (PSt)(2)-poly(N-isopropyl-acrylamide)(2), was prepared by RAFT polymerization of N-isopropylacrylamide (NIPAM) in the presence of the supramolecular macro-RAFT agent. The polymerization kinetics was investigated and the molecular weight and the architecture of the resulting star polymers were characterized by means of H-1-NMR, FTIR, and GPC techniques. (c) 2008 Wiley Periodicals, Inc.

Structural characterization and identification of dibenzocyclooctadiene lignans in Fructus Schisandrae using electrospray ionization ion trap multiple-stage tandem mass spectrometry and electrospray ionization Fourier transform ion cyclotron resonance multiple-stage tandem mass spectrometry

The electrospray ionization ion trap multiple-stage tandem mass spectrometry (ESI-MSn) and electrospray ionization Fourier transform ion cyclotron resonance multiple-stage tandem mass spectrometry (ESI-FT-ICR-MSn) have been applied successfully to the direct investigation of a number of dibenzocyclooctadiene lignan constituents from the methanol extracts of the Fructus Schisandrae in the positive ion mode. The detailed structural characterization of the same skeleton and different peripheral substituents had been studied and the precise elemental compositions of ions at high mass resolution had been obtained. So the fragmentation mechanisms could be clarified.

Studies on alkaloids binding to GC-rich human survivin promoter DNA using positive and negative ion electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI-MS) was used to investigate the binding of 13 alkaloids to two GC-rich DNA duplexes which are critical sequences in human survivin promoter. Negative ion ESI-MS was first applied to screen the binding of the alkaloids to the duplexes. Six alkaloids (including berberine, jatrorrhizine, palmatine, reserpine, berbamine, and tetrandrine) show complexation with the target DNA sequences. Relative binding affinities were estimated from the negative ion ESI data, and the alkaloids show a binding preference to the duplex with higher GC content. Positive ion ESI mass spectra of the complexes were also recorded and compared with those obtained in negative ion mode.

Studies of the intermolecular DNA triplexes of C+center dot GC and T center dot AT triplets by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry

Formation and stabilities of four 14-mer intermolecular DNA triplexes, consisting of third strands with repeating sequence CTCT, CCTT, CTT, or TTT, were studied by electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in the gas phase. The gas-phase stabilities of the triplexes were compared with their CD spectra and melting behaviors in solution, and parallel correlation between two phases were obtained. In the presence of 20 mm NH4+ (pH 5.5), the formation of the TTT triplex was not detected in both solution and the gas phase.