Fluorescence sensor for water in organic solvents prepared from covalent immobilization of 4-morpholinyl-1, 8-naphthalimide

A new fluorescent dye, N-allyl-4-morpholinyl-1,8-naphthalimide (AMN), was synthesized as a fluorescence indicator in the fabrication of a sensor for determining water content in organic solvents. To prevent leakage of the fluorophore, AMN was photo-copolymerized with acrylamide, (2-hydroxyethyl)methacrylate, and triethylene glycol dimethacrylate on a glass surface treated with a silanizing agent. The sensing mechanism is based on the solvatochromic feature of the covalently immobilized AMN. The fluorescence intensity of AMN decreased with increasing water contents when it was excited at 400 nm. In the range of ca. 0.00–4.40% (v/v), the fluorescence intensity of AMN changed as a linear function of water content. The sensor exhibited satisfactory reproducibility, reversibility, and a response time (t ₉₉) of the order of 50 s. The detection limit was solvent-dependent, when acetonitrile was used as the solvent, and the detection limit could be as low as 0.006% (v/v) of water. Additionally, the prepared sensor is pH-insensitive and possesses a relatively long lifetime of at least one month.     

Adsorption of 1,10-phenanthroline within a dodecanethiol monolayer: an approach to a switchable electrode surface

A simple method was used to prepare a "switchable" electrode surface by using self-assembled monolayers of dodecanethiol on a gold electrode. The dodecane-modified electrode was electrochemically inactive until the monolayer was soaked in solutions of 1,10-phenanthroline or 2,2'-bipyridine. The electroactive form of the electrode could be reverted back to the nonelectroactive form by rinsing the electrode. Surface IR results showed that both dodecanethiol and 1,10-phenanthroline exist in the mixed monolayer.     

A facile synthesis to Zn(2)SiO(4):Mn(2+) phosphor with controllable size and morphology at low temperature

Sphere- and rod-shaped Zn(2)SiO(4):Mn(2+) phosphor nanocrystals were synthesized at 230 degrees C. The process consists of tuning the surfactant concentration in the oil/surfactant/ethanol system. Powder X-ray (XRD) and transmission electron microscopy (TEM) were used to characterize the phase purity, size and morphology. Photoluminescent (PL) spectra were collected and analyzed. Fourier transform infrared (FT-IR) spectra of the samples indicate the removal of surfactant in the phosphor nanoparticles. As a result, the sphere-shaped phosphor nanoparticles of 100 nm in size can be redispersed in ethanol ultrasonically. The suspension maintain stable for over 48 h.     

First insights into the electronic properties of a Cu(II) center embedded in the PN3 cap of a calix[6]arene-based ligand

The first metal complex based on the calix[6]PN3 cryptand is described. The solid-state and solution studies show a 5-coordinate Cu(II) center due to its coordination to the PN3 cap and to an exchangeable guest molecule. Spectroscopic and electrochemical studies evidence surprising properties of the metal ion, which are tentatively assigned to the unusual P-Cu(II) bond enforced by the cryptand.     

Steady surface modification of polydimethylsiloxane microchannel and its application in simultaneous analysis of homocysteine and glutathione in human serum

A novel polydimethylsiloxane (PDMS) surface modification method for microchip electrophoresis has been developed to make a stable and sufficient electroosmotic flow (EOF). Poly(l-glutamic acid) (PGA) which had ionizable carboxyl groups at a high pH-range was immobilized on the surface of microchannel fabricated with PDMS. The surface modification involved surface oxidation by plasma, the silanization of 3-aminopropyldimethylethoxysilane (APDMES) and immobilization of PGA via amide bond. The modified channel was extremely stable against consecutive electric power supply over 5h, and its long-term stability was demonstrated by the efficient separation of four amino acid derivatives reproducibly after a week. Additionally, homocysteine (Hcy), important risk factor of cardiovascular disease, osteoporosis and problems in pregnancy, was successfully measured in human serum in modified PDMS channel with the other thio amino acid simultaneously.     

Titanium-capped carbon chains as promising new hydrogen storage media

The capacity of Ti-capped sp carbon atomic chains for use as hydrogen storage media is studied using first-principles density functional theory. The Ti atom is strongly attached at one end of the carbon chains via d-p hybridization, forming stable TiC(n) complexes. We demonstrate that the number of adsorbed H(2) molecules on Ti through Kubas interactions depends upon the chain types. For polyyne (n even) or cumulene (n odd) structures, each Ti atom can hold up to five or six H(2) molecules, respectively. Furthermore, the TiC(5) chain effectively terminated on a C(20) fullerene can store hydrogen with an optimal binding energy of 0.52 eV per H(2) molecule. Our results reveal a possible way to explore high-capacity hydrogen storage materials in truly one-dimensional carbon structures.     

Calix[4] open-chain crown ether-modified, vinyl-functionalized hybrid silica monolith for capillary electrochromatography

A novel calix[4] open-chain crown ether (p-tert-butylcalix[4]arene-1,3-bis(allyloxyethy) ether)-modified, organic-inorganic hybrid silica-based monolithic column possessing vinyl ligands for CEC is described. The monolithic silica matrix containing a vinyl functionality was synthesized by in situ cocondensation of tetramethoxysilane (TMOS) and vinyltrimethoxysilane (VTMS) via sol-gel process and chemically modified with calix[4] open-chain crown ether by free radical polymerization procedure using alpha, alpha'-azobisisobutyronitrile (AIBN) as an initiator. Morphology of the monolithic column was examined by SEM and the successful incorporation of calix[4] open-chain crown ether to the vinyl-hybrid monolith was characterized by infrared (IR) spectra. Compared with an unmodified vinyl-hybrid monolithic column, slightly stronger EOF at pH >7.5 was observed for this monolithic column due to the ionization of phenolic hydroxyls on the lower rim of calix[4]arene. VTMS/TMOS ratios in the reaction mixture were varied and 1:4 was found to be optimum to obtain homogeneous monolith with good permeability. The performance of the column was evaluated by nucleotides, beta-blockers, neurotransmitters, and PAHs as test solutes and compared with that of unmodified vinyl-hybrid monolithic column. Greatly improved column performance was obtained due to the host-guest interaction and intermolecular hydrogen bonding provided by the calix[4] open-chain crown ether moiety. The column efficiencies for neurotransmitters and nucleotides are up to 120 000 and 110 000 plates/m, respectively. Migration time and theoretical plate number reproducibilities were reasonable with RSDs less than 1.0 and 1.8% each for within column runs and not more than 7.2 and 8.6% each for column-to-column measurements, using four nucleotides as test solutes.     

Charge-transfer effect at the interface of phthalocyanine-electrode contact studied by scanning tunneling spectroscopy

Scanning tunneling microscopy (STM) and spectroscopy (STS) are used in this work to investigate the charge-transfer effect at the molecule-substrate interface of substituted metal phthalocyanines. STS results revealed that the apparent energy gaps for both fluorinated phthalocyanines and unsubstituted phthalocyanines are essentially the same, which agree with the hybrid density functional calculations. More interestingly, there is a systematic shift of the energy level of valence bands, possibly as the result of charge-transfer effect at the molecule-substrate interface.     

Nonstandard decision methods for the solvability of real polynomial equations

For a multivariate polynomial equation with coefficients in a computable ordered field, two criteria of this equation having real solutions are given. Based on the criteria, decision methods for the existence of real zeros and the semidefiniteness of binaly polynomials are provided. With the aid of computers, these methods are used to solve several examples. The technique is to extend the original field involved in the question to a computable non-Archimedean ordered field containing infinitesimal elements. Project supported by the National Natural Science Foundation of China (Grant No. 19661002) and the Climbing Project.     

Time-variable Method for Studying Reaction Rates in a Calorimeter

A novel method for the determination of rate constants of reactions, the time-variable method, is proposed in this paper. The method needs only three time points (t), peak heights () and pre-peak areas (), obtained from the measured thermoanalytical curve. It does not require the thermokinetic reaction to be completed. It utilizes data-processing on a computer to give the rate constants. Four reaction systems, including a first-order reaction, second-order reactions (with equal concentrations and with unequal concentrations) and a third-order reaction, were studied with this method. The method was validated and its theoretical basis was verified by the experimental results.This revised version was published online in November 2005 with corrections to the Cover Date.