Pulse radiolysis study of ion-species effects on the solvated electron in alkylammonium ionic liquids

The spectra and kinetic behavior of solvated electrons (e_sol⁻) in alkyl ammonium ionic liquids (ILs), i.e. N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMMA-BF₄), N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13-TFSI), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13-TFSI), and N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P14-TFSI) were investigated by the pulse radiolysis method. The e_sol⁻ in each of the ammonium ILs has an absorption peak at 1100 nm, with molar absorption coefficients of 1.5–2.3×10⁴ dm³ mol⁻¹ cm⁻¹. The e_sol⁻ decayed by first order with a rate constant of 1.4–6.4×10⁶ s⁻¹. The reaction rate constant of the solvated electron with pyrene (Py) was 1.5–3.5×10⁸ dm³ mol⁻¹ s⁻¹ in the various ILs. These values were about one order of magnitude higher than the diffusion-controlled limits calculated from measured viscosities. The radiolytic yields (G-value) of the e_sol⁻ were 0.8–1.7×10⁻⁷ mol J⁻¹. The formation rate constant of e_sol⁻ in DEMMA-TFSI was 3.9×10¹⁰ s⁻¹. The dry electron (e_dry⁻) in DEMMA-TFSI reacts with Py with a rate constant of 7.9×10¹¹ dm³ mol⁻¹ s⁻¹, three orders of magnitude higher than that of the e_sol⁻ reactions. The G-value of the e_sol⁻ in the picosecond time region is 1.2×10⁻⁷ mol J⁻¹. The capture of e_dry⁻ by scavengers was found to be very fast in ILs.     

Semibiological molecular machine with an implemented "AND" logic gate for regulation of protein folding

A semibiological molecular machine with an implemented "AND" logic gate was developed, which was capable of controlling the folding process of proteins in response to ATP and light as input stimuli. The molecular design made use of a genetically engineered chaperonin GroEL bearing, at both entrance parts of its cylindrical cavity, cysteine residues, which were functionalized by an azobenzene derivative to construct photoresponsive mechanical gates (azo-GroEL). This engineered chaperonin trapped denatured green fluorescent protein (GFP(denat)) and prohibited its refolding. However, when hosting azo-GroEL detected ATP (input stimulus 1) and UV light (input stimulus 2) at the same time, it quickly released GFP(denat) to allow its refolding. In contrast, reception of either input stimulus 1 or 2 resulted in only very slow or no substantial refolding of GFP(denat). Implementation of such "AND" logic gate mechanisms in mechanically driven biomolecular systems is an important step toward the design of secured drug delivery systems.     

Dispersions of image potential states on surfaces of clean graphite and lead phthalocyanine film

Dispersions of image potential states on a graphite surface (denoted IPS1) and on 1 monolayer (ML) film (denoted IPS2) of lead phthalocyanine (PbPc) are investigated by the micro-spot angle-resolved two-photon photoemission (micro-AR-2PPE) spectroscopy. On the graphite surface, whole dispersions of the two members of IPS1 (n = 1 and 2) are observed. The n = 1 IPS1 peak is weakly visible at energy higher than the vacuum level. The effective mass of an electron in the n = 1 IPS1 becomes slightly light at the high momentum region, suggesting the interaction between the IPS1 and the unoccupied σ-band of graphite. On the PbPc film, the IPS2 band forms a band gap and back-folds at the boundary of the Brillouin zone. A 1-dimensional Kronig-Penny model is used to reproduce the effective mass and the shift of binding energy.     

Japanese version of voice handicap index for subjective evaluation of voice disorder

Recently, the Voice Handicap Index (VHI), developed in the United States, has been highlighted as a means to assess a patient's perceptions of the severity of his or her voice disorder. The VHI is based on a self-administered questionnaire that quantifies the degree of a patient's disability related to his/her voice disorder. The questionnaire was translated into Japanese and applied to Japanese patients with various kinds of disordered voice or dysphonia. The results were analyzed and the usefulness discussed. In this study, 546 patients (281 males and 265 females) were included. Mean VHI scores were 36.2/120 in males and 44.1/120 in females. In the male patients, VHI scores were the highest among teens. However, VHI scores did not vary with age in the female patients. Patients with vocal fold paralysis, functional dysphonia, psychological dysphonia, and spasmodic dysphonia showed relatively high VHI scores, whereas those with laryngeal granuloma and laryngopharyngeal reflux disease showed low scores. In most diseases, functional and physiological scores were higher than emotional scores. In any treated patients, those with vocal nodule, vocal polyp, polypoid vocal fold, and recurrent laryngeal nerve paralysis, VHI scores decreased after therapeutic intervention. These findings suggest that the Japanese VHI is a useful tool for monitoring a patient's psychological status, choosing appropriate treatment, and assessing the therapeutic outcome.     

Formation of flat, homogeneous surfaces of organized molecular films of three-armed polymerizable amphiphiles with metal-scavenging properties

Surface complexing (i.e., metal-bridged polymerization in this study) of a three-armed amphiphilic compound with metal-scavenging properties has been investigated using the surface pressure-area (π-A) isotherms of a Langmuir monolayer from the subphase. Inductively coupled plasma mass spectrometry (ICP-MS) was also carried out on eluted solutions from corresponding multilayers of the solid. Furthermore, the molecular arrangement and surface morphology of organized molecular films of the resultant comb polymer were estimated by in-plane and out-of-plane X-ray diffraction (XRD) and by atomic force microscopy. From an analysis of the wide-angle X-ray diffraction of the corresponding monomer in the bulk, the long hydrocarbon chains are observed to pack hexagonally in the solid state. Compared to their monolayer on distilled water as the subphase, a polymerized monolayer on a buffer solution containing Cd(2+) ions is remarkably expanded at 15 °C. From ICP-MS and IR measurements, it is found that this monolayer stoichiometrically contains Cd(2+) ions on the -SH group. It is found by XRD that highly ordered layer structures and regular 2D lattices are constructed in the organized molecular films of the Cd-bridged comb polymer. Furthermore, the surface morphology of Langmuir-Blodgett films fabricated from the monolayers on a buffer solution containing Cd(2+) and Pd(2+) shows flat and smooth domains upon metal scavenging and polymerization.     

Nano-biphasic ionic liquid systems composed of hydrophobic phosphonium salts and a hydrophilic ammonium salt

A combination of a phosphonium-type-zwitterions-lithium bis(trifluoromethanesulfonyl)imide complex and a hydrophilic ammonium salt provides a nanosegregated liquid-crystalline matrix consisting of hydrophilic ionic liquid (IL) domains and hydrophobic IL domains.     

Organic acid induced olefination reaction of lactones

(Z)-Selective olefination of several lactones with ketene silyl acetals was achieved by the catalysis of carbon acids (C-H acids) having a bis(triflyl)methyl group as an acidic functionality; in particular, the triple carbon acid having three bis(triflyl)methyl groups in phloroglucinol shows an excellent catalytic performance.     

Characterization of magnetic nanoparticles modified with thiol functionalized PAMAM dendron for DNA recovery

Magnetic nanoparticles (MNPs) modified with the thiol functionalized polyamidoamine (PAMAM) dendron were synthesized to estimate their DNA recovery capabilities. Aminosilane-modified MNPs and MNPs surrounded by a phospholipid (distearoylphosphatidylethanolamine (DSPE)) bilayer were used as core particles. Cystamine-core PAMAM dendrimers were reduced by dithiothreitol to dendron thiols and chemically conjugated to the core particles. Characterization of the synthesis revealed an increase of the surface amine charge from generation 1 (G1) to G6, starting with an aminosilane initiator. Particle size distribution analysis indicated that G6 PAMAM-modified MNPs exhibited monodispersity in an aqueous solution. G6 PAMAM-MNPs and G6 PAMAM-PE-MNPs synthesized by the proposed method have equivalent DNA recovery abilities to PAMAM-MNPs prepared by the conventional divergent synthesis method. In optimized conditions, 96% of λDNA was recovered using G6 PAMAM-PE-MNPs. Therefore, the method for preparing PAMAM-MNPs and PAMAM-PE-MNPs proposed in this study will be a novel approach for producing DNA carriers for efficient DNA purification by magnetic separation.     

Preparation of (Z)-1-fluoro-1-alkenyl carboxylates,carbonates and carbamates through chromium mediated transformation of dibromofluoromethylcarbinyl esters and the reactivity as double acyl group donors

CrCl₂/Mn-mediated transformation of various dibromofluoromethylcarbinyl esters including carboxylates, carbonates and carbamates provided 1-fluoro-1-alkenyl esters via [2,3]-sigmatropic rearrangement of ester group. Reaction proceeded by using CrCl₂/Mn system under mild conditions (in THF at room temperature) to give 1-fluoro-1-alkenyl esters in good yield with an excellent Z selective manner. 1-Fluoro-1-alkenyl ester thus obtained acts as a double acyl donor in the reaction with necleophiles such as amine, thiol, alcohol as well as bifunctional necleophiles such as ethylene diamine derivative.     

Microgravity experiments on colloidal crystallization of silica spheres in the presence of sodium chloride

 Rate coefficients (k) in the colloidal crystallization of monodispersed silica spheres in the presence of sodium chloride are studied in microgravity achieved by parabolic flights of an aircraft. Time-resolved reflection spectroscopy is made with a continuous circulating-type stopped-flow cell system. The k values decrease as the salt concentration increases both at 0 and 1 G and those in microgravity are smaller than those in normal gravity by 16% (maximum), especially in water and in the presence of a small amount of the salt lower than 2 × 10⁻⁶ mol/l. The rates in flight at 1 G are larger by 15% (maximum) compared with those at 1 G on the ground. The k values obtained at 0 G, 1 G in flight and 1 G on the ground agree excellently with each other for the suspensions with 3 × 10⁻⁶ and 4 × 10⁻⁶ mol/l sodium chloride. Disappearance of the downward diffusion of spheres and no convection of the suspensions are important for retardation in microgravity. Received: 20 January 2000 Accepted: 9 March 2000