Halochromism of N-phenoxide betaine dye in salt-containing poly(ethylene oxide) oligomers

The polarity of poly(ethylene oxide) (PEO) oligomers and PEO/salt mixed system was analyzed as the negative solvatochromism and halochromism of betaine dye, 2,6-diphenyl-4-(2,4,6-triphenylpyridinio) phenolate ( 1 ). The polarity of PEO oligomers, detected as the shift of the absorption maximum of the dye ( 1 ), decreased with increasing PEO chain length, reflecting the terminal hydroxyl group fraction. The polarity of the PEO matrix was the function of both lattice energy and cation radius of the added salt under the same salt concentration. There is a clear relation between the absorption maximum and the lattice energy of a series of salts having the same cation. The lattice energy of most salts was suggested to be estimated empirically by this relation.     

Bioactive constituents from Chinese natural medicines. XXVIII. Chemical structures of acyclic alcohol glycosides from the roots of Rhodiola crenulata

Five new glycosides, creosides I, II, III, IV, and V, were isolated from the methanolic extract of the roots of Rhodiola crenulata, together with 21 known compounds. The chemical structures of new constituents were elucidated on the basis of chemical and physicochemical evidence.     

Three-dimensional metal–organic frameworks: Two Ag(I) coordination polymers of TTF derivatives with axially chiral helical motifs

Two novel 3D coordination polymeric networks based on Ag(I) and TTF derivatives, [Ag₄(tces-TTF)₂(CF₃SO₃)₂](CF₃SO₃)₂ (tces = 2,3,6,7-tetra(cyanoethylsulfanyl)) (1) and [Ag₂(bmdt)₂](SbF₆)₂ · acetone (bmdt = 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione) (2), were synthesized and crystallographically characterized. Both 1 and 2 have axially chiral helical motifs and these helices were assembled in a similar way: spiral up along b axis infinitely. In addition, complex 2 forms a “cds” network with a topology of 6⁵.8. The conductivity of complex 1 was measured at RT with a σ value of 3.47 × 10⁻⁶S cm⁻¹ due to the S?S contacts in the molecules, while 2 is an insulator at RT.     

Preferential destruction of metallic single-walled carbon nanotubes by laser irradiation

Upon laser irradiation in air, metallic single-walled carbon nanotubes (SWNTs) in carbon nanotube thin film can be destroyed in preference to their semiconducting counterparts when the wavelength and power intensity of the irradiation are appropriate and the carbon nanotubes are not heavily bundled. Our method takes advantage of these two species' different rates of photolysis-assisted oxidation, creating the possibility of defining the semiconducting portions of carbon nanotube (CNT) networks using optical lithography, particularly when constructing all-CNT FETs (without metal electrodes) in the future.     

Rapid methylation on carbon frameworks useful for the synthesis of 11CH3-incorporated PET tracers: Pd(0)-mediated rapid coupling of methyl iodide with an alkenyltributylstannane leading to a 1-methylalkene

The Pd(0)-mediated rapid coupling of methyl iodide with an excess of alkenyltributylstannane was examined with the aim of incorporating a short-lived 11C-labeled methyl group into a biologically significant organic compound with a 1-methylalkene unit for the synthesis of a PET tracer. Four sets of reaction conditions (A-D) were used, all performed in DMF at 60 degrees C for 5 min. Condition B, using CH3I/stannane/Pd2(dba)3/P(o-tolyl)3/CuCl/K2CO3 (1:40:0.5:4-6:2:5), works well in almost all cases. Condition D, using CH3I/stannane/Pd2(dba)3/P(o-tolyl)3/CuX (X = Br, Cl, or I)/CsF (1:40:0.5-5:2-20:2-20:5-50), shows the best results with regard to general applicability to tin substrates, affording the corresponding methylated product in >90% yield based on consumption of methyl iodide. P(t-Bu)2Me was less effective than P(o-tolyl)3, particularly for alpha,beta-unsaturated carbonyl substrates. No regio- or stereoisomerization occurred under these reaction conditions. The efficiency of the protocol was demonstrated by synthesis of an 11C-methylated compound.     

Ionization condition of lithium ionic liquid electrolytes under the solvation effect of liquid and solid solvents

Ionization condition and ionic structures of the lithium ionic liquid electrolytes, LiTFSI/EMI-TFSI/(PEG or silica), were investigated through the measurements of ionic conductivity and diffusion coefficient. The size of the hydrodynamic lithium species (rLi) evaluated from the Stokes-Einstein equation was 0.90 nm before gelation with the PEG or silica. This reveals that the TFSI- anions from the solvent are coordinated on Li+ for solvation, forming, for example, Li(TFSI)4(3-) and Li(TFSI)2- in the electrolyte solution. By the dispersion of PEG for gelation, rLi increased up to 1.8 nm with the 10 wt % of PEG. This indicates that the lithium species is directly interacted with the oxygen sites on the polymer chains and the lithium species migrate, reflecting the polymer by hopping from site to site. In case of the silica dispersion, rLi decreased to 0.7 nm at 10 wt % silica. Although the silica surface with silanol groups fundamentally attracts Li+, the lithium does not migrate from site to site on the silica surface as in the gel of the polymer and follows random walk behavior in the network of the liquid-phase pathways in the two-phase gel. In the process, that solvated TFSI- anions are partially removed may be due to the attractive effect of H+, which was dissociated from the silanol group. It is concluded that the dispersed silica is effective to modify the hydrodynamic lithium species to be appropriate for charge transport as reducing the size and anionic charge of Li(TFSI)4(3-) by removing one or two TFSI- anions.     

Highly efficient syntheses of [methyl-11C]thymidine and its analogue 4'-[methyl-11C]thiothymidine as nucleoside PET probes for cancer cell proliferation by Pd(0)-mediated rapid C-[11C]methylation

Pd(0)-mediated rapid couplings of CH(3)I (and then [(11)C]CH(3)I) with excess 5-tributylstannyl-2'-deoxyuridine and -4'-thio-2'-deoxyuridine were investigated for the syntheses of [methyl-(11)C]thymidine and its stable analogue, 4'-[methyl-(11)C]thiothymidine as PET probes for cancer diagnosis. The previously reported conditions were attempted using Pd(2)(dba)(3)/P(o-CH(3)C(6)H(4))(3) (1?:?4 in molar ratio) at 130 °C for 5 min in DMF, giving desired products only in 32 and 30% yields. Therefore, we adapted the current reaction conditions developed in our laboratory for heteroaromatic compounds. The reaction using CH(3)I/stannane/Pd(2)(dba)(3)/P(o-CH(3)C(6)H(4))(3)/CuCl/K(2)CO(3) (1?:?25?:?1?:?32?:?2?:?5) at 80 °C gave thymidine in 85% yield. Whereas, CH(3)I/stannane/Pd(2)(dba)(3)/P(o-CH(3)C(6)H(4))(3)/CuBr/CsF (1?:?25?:?1?:?32?:?2?:?5) including another CuBr/CsF system promoted the reaction at a milder temperature (60 °C), giving thymidine in 100% yield. Chemo-response of thiothymidine-precursor was different from thymidine system. Thus, the above optimized conditions including CuBr/CsF system gave 4'-thiothymidine only in 40% yield. The reaction using 5-fold amount of CuBr/CsF at 80 °C gave much higher yield (83%), but unexpectedly, the reaction was accompanied by a considerable amount of undesired destannylated product. Such destannylation was greatly suppressed by changing to a CuCl/K(2)CO(3) system using CH(3)I/stannane/Pd(2)(dba)(3)/P(o-CH(3)C(6)H(4))(3)/CuCl/K(2)CO(3) (1?:?25?:?1?:?32?:?2?:?5) at 80 °C, giving the 4'-thiothymidine in 98% yield. The each optimized conditions were successfully applied to the syntheses of the corresponding PET probes in 87 and 93% HPLC analytical yields. [(11)C]Compounds were isolated by preparative HPLC after the reaction conducted under slightly improved conditions, exhibiting sufficient radioactivity of 3.7-3.8 GBq and specific radioactivity of 89-200 GBq μmol(-1) with radiochemical purity of ≥99.5% for animal and human PET studies.     

Improving peptide fragmentation by N-terminal derivatization with high proton affinity

An improved method of de novo peptide sequencing based on mass spectrometry using novel N-terminal derivatization reagents with high proton affinity has been developed. The introduction of a positively charged group into the N-terminal amino group of a peptide is known to enhance the relative intensity of b-ions in product ion spectra, allowing the easy interpretation of the spectra. However, the physicochemical properties of charge derivatization reagents required for efficient fragmentation remain unclear. In this study, we prepared several derivatization reagents with high proton affinity, which are thought to be appropriate for peptide fragmentation under low-energy collision-induced dissociation (CID) conditions, and examined their usefulness in de novo peptide sequencing. Comparison of the effects on fragmentation among three derivatization reagents having a guanidino or an amidino moiety, which differ in proton affinity, clearly indicated that there was an optimal proton affinity for efficient fragmentation of peptides. Among reagents tested in this study, derivatization with 4-amidinobenzoic acid brought about the most effective fragmentation. This derivatization approach will offer a novel de novo peptide sequencing method under low-energy CID conditions.     

Defects in electron-irradiated 3C-SiC epilayers observed by positron annihilation

Positron annihilation has been used to study defects induced by 1 MeV electron irradiation in cubic silicon carbide (3C-SiC) epitaxially grown on Si substrates by chemical vapor deposition. Narrowing of the Doppler-broadened energy spectrum of annihilation gamma-rays by the electron irradiation was observed in the fluence range above 5 × 10¹⁶ e/cm². The electron fluence dependence of the narrowing is accounted for by the introduction of monovacancies and divacancies in 3C-SiC by the irradiation.     

Matrix effect on the analysis of oligonucleotides by using a mass spectrometer with a sonic spray ionization source.

Matrix or impurities remaining in a DNA sample solution after various sample treatment procedures may influence a subsequent DNA analysis. In this work, several matrices were investigated concerning their effects on the analysis of oligonucleotide by using an ion-trap mass spectrometer equipped with a sonic spray ionization source. Inorganic salts of sodium chloride and magnesium chloride depressed the signal intensity by about 50% when the content of the salts was about 10 microM. dNTPs and Taq showed more severe depression on the oligonucleotide. However, Tris, or (hydroxymethyl)aminomethane, intensified the signal intensity, if its content was within an appropriate range. When the content of Tris was about 500 microM, the signal intensity was enhanced by factors of 3 and 5 for the 6-mer and the 20-mer oligonucleotides, respectively. With the existence of Tris, matrix effects from the inorganic salts, dNTPs and Taq were reduced.