Can H2 inside C60 communicate with the outside world?

The quenching rate constants of singlet oxygen by C60, H2@C60, D2@C6o, H2, and D2 in solution were measured. The presence of a hydrogen (H2@C60) or deuterium (D2@C60) molecule inside the fullerene did not produce any observable effect based on triplet lifetime or EPR measurements. However, a remarkable effect was found for the 1O2 quenching by C60, H2@C60, D2@C6o, H2, and D2. Singlet oxygen was generated by photosensitization or by thermal decomposition of naphthalene endoperoxide derivatives. Comparison of the rate constants for quenching of 1O2 by H2@C60 and D2@C60 demonstrates a significant vibrational interaction between oxygen and H2 inside the fullerene. The quenching rate constant for H2 is 1 order of magnitude higher than that of D2, in agreement with the results observed for the quenching of 1O2 with H2@C60 or D2@C60.     

Cyclodehydration of cis-2-butene-1,4-diol with active methylene compounds catalyzed by a diphosphinidenecyclobutene-coordinated palladium complex

(π-Allyl)palladium triflate coordinated with 1,2-bis(4-methoxyphenyl)-3,4-bis(2,4,6-tri-t-butylphenylphosphinidene)cyclobutene (DPCB-OMe), [Pd(η³-C₃H₅)(DPCB-OMe)]OTf, efficiently catalyzes cyclodehydration of cis-2-butene-1,4-diol with active methylene compounds such as acetylacetone and ethyl acetoacetate in toluene in the presence of pyridine. The reactions can be performed in air, giving 2-vinyl-2,3-dihydrofurans in good to high yields.     

A new assignment technique of 2D‐NMR spectra by spin‐lock sequence to a tripeptide containing tryptophan in water

We developed a new assignment technique of tryptophan residues using pulsed field gradient TOCSY–ROESY (PFG‐TORO) and pulsed field gradient TOCSY–ROESY–TOCSY (PFG‐TOROTO) techniques in water. Connectivity from βH to ζ2H (H‐7) via ε1H (H‐1) and δ1H (H‐2) in the TORO spectrum and from βH to ζ3H (H‐5) and η2H (H‐6) via ε1H (H‐1) and δ1H (H‐2) in the TOROTO spectrum could be able to assign each of the protons of the indole rings. Copyright © 2010 John Wiley & Sons, Ltd.     

Non-uniformity correction of human brain imaging at high field by RF field mapping of B1+ and B1-

A new method of non-uniform image correction is proposed. Image non-uniformity is originated from the spatial distribution of RF transmission and reception fields, represented as B(1)(+) and B(1)(-), respectively. In our method, B(1)(+) mapping was performed invivo by a phase method. In B(1)(-) mapping, images with multiple TEs were acquired with a multi-echo adiabatic spin echo (MASE) sequence which enables homogeneous excitation. By T(2) fitting of these images an M(0) map (M(0)(MASE)) was obtained, in which signal intensity was expressed as the product of B(1)(-) and M?(1-e?(TR/T1)) . The ratio of this M(0)(MASE) map to the B(1)(+) map showed a similar spatial pattern in different human brains. These ratios of M(0)(MASE) to B(1)(+) in 24 subjects were averaged and then fitted with a spatially polynomial function to obtain a ratio map of B(1)(-)/B(1)(+)(α). Uniform image was achieved in spin echo (SE), MASE and inversion recovery turboFLASH (IRTF) images using measured B(1)(+) and calculated B(1)(-) by αB(1)(+). Water fractions in gray and white matters obtained from the M(0) images corrected by this method were in good agreement with previously reported values. From these experimental results, the proposed method of non-uniformity correction is validated at 4.7 T imaging.     

Double lactonization in triarylamine-conjugated dimethyl diethynylfumarate: formation of intensely colored and luminescent quadrupolar molecules including a missing structural isomer of Pechmann dyes

Acid-induced double lactonization in triarylamine-conjugated dimethyl diethynylfumarate E-1 opens up a new synthetic route to Pechmann dyes. This one-pot reaction affords three donor-acceptor-donor quadrupolar molecules (P(55)-1, P(66)-1, and P(56)-1); P(56)-1 comprises a missing structural isomer of Pechmann dyes. They are intensely colored and brightly luminescent. An organic field-effect transistor device fabricated with P(66)-1 functions as a p-type semiconductor.     

Matrix-isolation infrared studies of 1:1 molecular complexes containing chloroform (CHCl3) and Lewis bases: seamless transition from blue-shifted to red-shifted hydrogen bonds

The infrared spectra of molecular complexes containing chloroform (CHCl(3)) and Lewis bases (N(2), CO, H(2)O, and CH(3)CN) have been observed in an Ar matrix, and vibrational peaks for the 1:1 complexes have been assigned. The C-H stretching band of chloroform in the complexes showed a seamless transition from a blue shift (for N(2) and CO) to a red shift (H(2)O and CH(3)CN), in accord with the proton affinity of the base molecules. Density functional calculations predicted that the C-H··(σ-type lone pair) isomer is the most stable, which is consistent with the observed vibrational peak shift upon complex formation. The underlying mechanisms of the C-H hydrogen bond were explored using the topological properties of the electronic charge density and natural orbital analyses.     

Paeoniflorigenone,a new monoterpene from paeony roots

Paeoniflorigenone (1), a new monoterpene which produces a neuromuscular-blocking effect in mice, was isolated from paeony roots and its structure was elucidated.     

Configurational studies on amylose. II. Moments and distribution functions

Statistical mechanical averages of vectors and tensors characterizing the configuration of amylose chains have been calculated. These quantities are expressed in the reference frame affixed to the first glucose unit, the x axis being situated along the O(4)—O(1) virtual bond vector, and the Y axis in the plane of the virtual bond and the O(4)—C(4) bond. The persistence vector a as defined by the average of the end-to-end vector r converges slowly to the limiting persistence vector a _∞ with increasing chain length. Configurational averages of the Cartesian tensors formed from the displacement vector ρ = r ? a have been computed up to seventh rank according to the generator matrix method. The density distribution functions W_α (ρ) evaluated for x_u = 40 by using the three-dimensional Hermite polynomial expansion truncated at the term involving the tensor of seventh rank are approximately cylindrically symmetric about one of the principal axes of the second-moment tensor <ρ^×2. The density distribution function W_α(ρ) is slightly asymmetric even for x_u = 80.     

Two new monoterpene glycosides and trypanocidal terpenoids from Dracocephalum kotschyi

From the whole plant of Dracocephalum kotschyi BOISS., two new monoterpene glycosides (9, 10), together with seven known terpenoids and a phytosterol (1-8), were isolated. Their structures were determined to be limonen-10-al (1), geranial (2), neral (3), beta-sitosterol (4), oleanolic acid (5), ursolic acid (6), p-mentha-8-en-1,2-diol (7), colosolic acid (8), limonen-10-ol 10-O-beta-D-glucopyranoside (9), and limonen-10-ol 10-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside (10). Compounds 1 (3.1 microM), 2 (3.1 microM), 3 (3.1 microM), 5 (6.2 microM), 6 (6.2 microM), and 8 (6.2 microM) were effective against epimastigotes of Trypanosoma cruzi.