Preparation and characterization of cationic corn starch with a high degree of substitution in dioxane-THF-water media

Cationic corn starch derivatives with a high degree of substitution are prepared in alkaline solution or in mixed media of organic solvent and water with different levels of the cationic reagent, 2,3-epoxypropyltrimethylammonium chloride. The starch cationization yield is investigated, and the results indicate that the degree of substitution (DS) of the samples depends on the reaction conditions and reaction media. The maximum DS values are up to 1.37 in 1,4-dioxane alkali ne-aqueous solution. Meanwhile, the structures of the cationic starch derivatives are characterized by elemental analyses, FTIR spectroscopy, X-ray diffraction, and C-13 NMR spectroscopy, as well as by SEM techniques.

Highly Uniform Gd(OH)(3) and Gd2O3:Eu3+ Nanotubes: Facile Synthesis and Luminescence Properties

Uniform Gd(OH)(3) nanotubes have been prepared via a simple wet-chemical route at ambient pressure and low temperature, without any catalysts, templates, or substrates, in which Gd(NO3)(3) was used as the gallium source and ammonia as the alkali. SEM and TEM images indicate that the as-obtained Gd(OH)3 entirely consists of uniform nanotubes in high yield with diameters of about 40 nm and lengths of 200-300 nm. The temperature-dependent morphological evolution and the formation mechanism of the Gd(OH)(3) nanotubes were investigated in detail. Furthermore, the Gd2O3 and Eu3+-doped Gd2O3 nanotubes, which inherit their parents' morphology, were obtained during a direct annealing process in air. The corresponding Gd2O3:Eu3+ nanotubes exhibit the strong red emission corresponding to the D-5(0)-F-7(2), transition of the Eu3+ ions under UV light or low-voltage electron beam excitation, which might find potential applications in the fields such as light-emitting phosphors, advanced flat panel displays, or biological labeling.

Synthesis of Titanate-Based Nanotubes for One-Dimensionally Confined Electrical Properties

Structural tailoring for dimensionally confined electrical properties is fundamentally important for nanodevices and the relevant technologies. Titanate-based nanotubes were taken as a prototype one-dimensional material to study. First, Na0.96H1.04Ti3O7 center dot 3.42H(2)O nanotubes were prepared by a simple hydrothermal condition, which converted into Na0.036H1.964Ti3O7 center dot 3.52H(2)O nanotubes by a subsequent acidic rinsing. Systematic sample characterization using combined techniques of X-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy, electron paramagnetic resonance, Fourier transform infrared spectroscopy, elemental analyses, and alternative current impedance indicated that both nanotubes possessed a scrolled trititanate-type structure with the (200) crystal face predominant on the tube surface. With increasing temperature, both nanotubes underwent a continuous dehydration process, which however imposed different impacts oil the structures and electrical properties, depending on the types of the nanotubes

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.

The relationship between the thermal expansions and structures of ABO(4) oxides

The linear thermal expansion coefficients of ABO(4) compounds are determined and the expansion tendency is analyzed from the chemical bond viewpoint. All chemical bonds contributions are involved. The contributions from different chemical bonds are compared with each other and the origin of the expansion behavior of ABO(4) oxides is revealed that the A-O bonds expansions dominate the compound expansion. The calculated expansion coefficients agree satisfactorily with the experimental data. By analyzing the expansion regularity the range of the expansion coefficients can be qualified. The thermal expansion coefficients of some ABO(4) compounds having not been measured are predicted and discussed.

Facilitated ion-transfer of sodium cation by (anthraquinone-1-yloxy) methane-15-crown-5 across the water/1,2-dichloroethane microinterface

The transfer of sodium cation facilitated by (anthraquinone-1-yloxy) methane-15-crown-5(L) has been investigated at the water/1,2-dichloroethane microinterface supported at the tip of a micropipette. The diffusion coefficient of (anthraquinone-1-yloxy) methane-15-crown-5 obtained was (3.42 +/- 0.20) x 10(-6) cm(2) s(-1). The steady-state voltammograms were observed for forward and backward scans due to sodium ion transfer facilitated by L with 1:1 stoichiometry. The mechanism corresponded to an interfacial complexation (TIC) and interfacial dissociation (TID) process. The association constant was calculated to be log beta(o) = 11.08 +/- 0.03 in the DCE phase. The association constant of other alkali metals (Li+, K+, Rb+) were also obtained.

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.

Mannose-Escherichia coli interaction in the presence of metal cations studied in vitro by colorimetric polydiacetylene/glycolipid liposomes

Supramolecular assemblies of liposomes (vesicles) made of diacetylenic lipids and synthetic mannoside derivative glycolipid receptors were successfully used to mimic the molecular recognition occurring between mannose and Escherichia coli. This specific molecular recognition was translated into visible blue-to-red color transition (biochromism) of the polymerized liposomes, readily quantified by UV-visible spectroscopy. Some transition metal cations (Cd2+, Ag+, Cu2+, Fe3+, Zn2+ and Ni2+) and alkali earth metal cations (Ca2+, Mg2+ and Ba2+) were introduced into the system to analyze their effects on specific biochromism. Results showed that the presence of Cd2+, Ag+, Ca2+, Mg2+ and Ba2+ enhanced biochromisin. A possible enhancement mechanism was proposed in the process of bacterial adhesion to host cells. However, Cu2+, Fe3+, Zn2+ and Ni2+ exhibited inhibitory effects that cooperated with diacetylene lipid with a carboxylic group and increased the rigidity of the liposomal outer leaflet, blocking changes in the side chain conformation and electrical structure of polydiacetylene polymer during biochromism.

Synthesis, crystal structure, and photoluminescent property of a novel heterobimetallic Zn(II)-Ag(I) cyano-bridged coordination polymer incorporating,a pentameric unit [Ag(CN)(2-)](5) assembled by argentophilic interaction

A new photoluminescent heterobimetallic Zn(II)-Ag(I) cyano-bridged coordination polymer, [Ag5Zn2(tren)(2)(CN)(9)] (tren = tris(2-aminoethyl)amine) (1), has been synthesized and structurally characterized. It features rare linear pentameric unit of dicyanoargentate(I) ions assembled by d(10)-d(10) interaction as building blocks. Solid state emission spectrum of I shows strong ultraviolet luminescence with emission peak in the range of 376 nm.

Estimation thermal expansion coefficient from lattice energy for inorganic crystals

By using the study of the lattice energy and the structural parameters of binary inorganic crystals, a new parameter reflecting the thermal expansion property has been found, the relation between the linear expansion coefficient and new parameter has been established. A semiempirical method for evaluation of linear expansion coefficient from the lattice energy is presented, and developed to the complex crystals. The estimated values of the linear expansion coefficients of both simple and complex crystals are in good agreement with the experimental values.

Systematic study of the transfer of amino acids across the water/1,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Facilitated ion transfer reactions of 20 amino acids with di.benzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, Ile, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (beta(0)), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization.

Investigation of ion transfer across the micro-water/nitrobenzene interface facilitated by a fullerene derivative

A functionalized fullerene derivative containing a monoaza-18-crown-6 moiety was investigated by facilitated ion (such as Li+, Na+, K+, NH4+, Mg2+, and Ca2+) transfer across the micro-water/nitrobenzene interface supported at the tip of a micropipet. The current responses were detected by cyclic voltammetry and Osteryoung square wave voltammetry, which demonstrated that the facilitated ion transfer does occur by an interfacial complexation-dissociation process. The diffusion coefficient of this compound in nitrobenzene was approximately (5.90 +/- 0.04) x 10(-7) cm(2) s(-1), which is 1 order of magnitude less than other common ionophores due to the large size of the molecule. The selectivity of this molecule toward the metal ions followed the sequence Na+ > Li+ > K+ > NH4+ > Ca2+ similar to Mg2+. In addition, this compound was also easy to form film at the water/nitrobenzene interface to inhibit the simple ion transfer of tetramethylammonium ion. However, the adsorption of this ionophore has less influence on the facilitated metal ion transfer.

Cleavage of nucleotides by Ce4+ and the lanthanide metal complexes

The cleavage of adenosine-5'-monophosphate (5'-AMP) and guanosine-5'-monophosphate (S-GMP) by Ce4+ and lanthanide complex of 2-carboxyethylgermanium sesquioxide (Ge-132) in acidic and near neutral conditions was investigated by NMR, HPLC and measuring the liberated inorganic phosphate at 37 degrees C and 50 degrees C, The results showed that 5'-GMP and 5'-AMP was converted to guanine (G), 5'-monophosphate (depurination of 5'-GMP), ribose (depurination and dephosphorylation of 5'-GMP), phosphate and adenine (A), 5'-monophosphate (depurination of 5'-AMP), ribose (depurination and dephosphorylation of 5'-AMP), phosphate respectively by Ce4+. In presence of lanthanide complexes, 5'-GMP and 5'-AMP were converted to guanosine (Guo) and phosphate and adenosine (Ado) and phosphate respectively. The mechanism of cleaving 5'-GMP and 5'-AMP is hydrolytic scission.

Electrospray ionization multiple-stage tandem mass spectrometric analysis of diglycosyldiacylglycerol glycolipids from the bacteria Bacillus pumilus

Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MSn) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C-14-C-19 fatty acids, some of which were monounsaturated, Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type, The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations, The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MSn spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS2 spectra of[M + K](+) ions, it was established that all components have a C-15:0 fatty acid at the sn-2 position of the glycerol backbone and C-14-C-19 acids at the sn-1 position of the glycerol backbone. Copyright (C) 1999 John Wiley & Sons, Ltd.

Cleavage of nucleotides by lanthanide metal complexes

The present work revealed that the praseodymium( II ) complex of 2-carboxyethylgermanium sesquioxide (Ge-132) promotes the hydrolysis of the phosphodiester linkages of 3',5'-cyclic adenosine monophosphate (cAMP), 3' , 5'-cyclic deoxyadenosine monophosphate (dcAMP), 5'-adenosine monophosphate(5'-AMP) and 5'-deoxyadenosine monophosphate (5'-dAMP) under mild conditions. Both cAMP and dcAMP were hydrolyzed site-specifically, yielding predominantly 3'-monophosphates, the main products of the cleavage of 5'-AMP and 5'-dAMP included adenosine (Ado). deoxyadenosine (dAdo) and free phosphates respectively. A hydrolytic mechanism was proposed for cAMP, dcAMP, 5'-AMP and 5'-dAMP.