Synthesis of a novel polymeric carbohydrate via regio‐ and stereoselective cyclopolymerization of 1,2:5,6‐dianhydrohexitol

The selective cyclopolymerization of 1,2:5,6‐dianhydrohexitols corresponding to diepoxides was a new synthetic strategy for polycarbohydrates, though the polymer is a lack of the anomeric linkage which is found in the naturally occurring polysaccharides. 1,2:5,6‐Dianhydro‐3,4‐di‐O‐methyl‐D‐mannitol, L‐iditol, and D‐glucitol were polymerized using t‐BuOK and BF₃·Oet₂ to produce the polymers consisting of five‐membered rings. On the other hand, the polymers consisting of six‐membered rings were obtained by the cationic and anionic polymerizations of meso allitol and galactitol monomers, respectively.     

Synthesis of end-functionalized (1 → 6)-2,5-anhydro-D-glucitols via anionic cyclopolymerization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol for preparing graft copolymers

End-functionalized (1→6)-2,5-anhydro-3,4-di-O-methyl-D-glucitols ( 3a–c ) were synthesized by the anionic cyclopolymerization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol ( 1 ), followed by treatment with a terminating agent such as 4-vinylbenzyl ( 2a ), oxetanyl ( 2b ), and methacryloyl group ( 2c ). The end-functionalization proceeded in a high efficiency at 73–98%. The radical copolymerization of styrene with 3a yielded a polymer ( 5a ) whose GPC trace exhibited a unimodal peak. 5a was polystyrene with (1→6)-2,5-anhydro-3,4-di-O-methyl-D -glucitol as pendant groups whose structure was confirmed by the ¹H NMR spectrum.     

Nondestructive real-time radioisotope imaging system for visualizing 14C-labeled chemicals supplied as CO2 in plants using Arabidopsis thaliana

We have developed a real-time radioisotope imaging system (RRIS) that can nondestructively trace ¹⁴C-labeled chemicals in plants. In an experiment, after feeding ¹⁴CO₂ to a plant, the plant was fixed inside a box where lighting was regulated, and beta rays emitted from the ¹⁴C in the plant were intermittently imaged using the developed system. As a first step, using a series of standard sources of ¹⁴C, the data depth and detection limits of the ¹⁴C images captured by the RRIS were evaluated for various integral times. As a result, the linearity between the ¹⁴C activity and signal intensity was determined for the range 10³. Next, the linearity was validated using plant (Arabidopsis thaliana) organs, resulting that the linearity was shown in the case of young leaf, but was not maintained in the thick organs, such as a flower, mature leaf, siliques, and stem. Considering the good correlation between the intensity by RRIS and the PSL value by an imaging plate (IP) as well as the relative low energy of beta rays emitted from ¹⁴C, the thickness of the organs would easily affect the quantitativity of the RRIS as well as an IP. Our findings prove that sequential images of ¹⁴C in a living plant sample in a regulated light and air environment can be nondestructively analyzed using the developed system, whose quantitativity is similar to that of an IP.     

Diffusional kurtosis imaging of cingulate fibers in Parkinson disease: Comparison with conventional diffusion tensor imaging

Objective

The pathological changes in Parkinson disease begin in the brainstem; reach the limbic system and ultimately spread to the cerebral cortex. In Parkinson disease (PD) patients, we evaluated the alteration of cingulate fibers, which comprise part of the limbic system, by using diffusional kurtosis imaging (DKI).

Methods

Seventeen patients with PD and 15 age-matched healthy controls underwent DKI with a 3-T MR imager. Diffusion tensor tractography images of the anterior and posterior cingulum were generated. The mean kurtosis (MK) and conventional diffusion tensor parameters measured along the images in the anterior and posterior cingulum were compared between the groups. Receiver operating characteristic (ROC) analysis was also performed to compare the diagnostic abilities of the MK and conventional diffusion tensor parameters.

Results

The MK and fractional anisotropy (FA) in the anterior cingulum were significantly lower in PD patients than in healthy controls. The area under the ROC curve was 0.912 for MK and 0.747 for FA in the anterior cingulum. MK in the anterior cingulum had the best diagnostic performance (mean cutoff, 0.967; sensitivity, 0.87; specificity, 0.94).

Conclusions

DKI can detect alterations of the anterior cingulum in PD patients more sensitively than can conventional diffusion tensor imaging. Use of DKI can be expected to improve the ability to diagnose PD.     

Polarization and intensity of Compton scattering

X-ray spectra scattered at 90° by acrylic resin plates of various thicknesses are measured. The intensity and polarization of Compton-scattered X-rays are estimated from the spectra. As the thickness of the slab increases, the intensity increases but the polarization decreases. The optimal thickness for a polarized X-ray fluorescence spectrometer is determined, which provides both high intensity and high polarization.     

End‐functionalization of polystyrene by malto‐oligosaccharide generating aggregation‐tunable polymeric reverse micelle

This article describes that glucose, maltose, maltotriose, maltotetraose, maltopentaose, and maltohexaose ( a , b , c , d , e , and f , respectively) were introduced into the initiating chain‐end of polystyrene (PSt) through the 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO)‐mediated radical polymerization. A series of glycoconjuaged TEMPO‐adducts, 1a–f , was synthesized and used as the initiators for the polymerization of styrene (St) for 6 h at 120 °C to afford the end‐functionalized PSt's with the acetyl saccharides, 2a–f , in the yields of 37–43%. For 2a–f obtained by the polymerizations using the [St]/[ 1 ] of 125, 250, and 500, the number‐average molecular weights determined by size exclusion chromatography (SEC), M_n,SEC's, were 4800–6300, 8800–10,600, and 18,400–25,200, respectively, which fairly agreed with the predicted values. The end‐functionalized PSt's with saccharides, 3a–f , which were obtained from the deacetylation of 2a–f using sodium methoxide in dry THF, formed the polymeric reverse micelles consisting of a saccharide‐core and a PSt‐shell in chloroform and toluene. The static laser light scattering (SLS) measurements provided the average molar mass of the aggregates in toluene, M_w,SLS's, which ranged from 7.50 × 10⁴ to 1.77 × 10⁵ for 3a , from 1.90 × 10⁵ to 4.93 × 10⁵ for 3b , from 4.41 × 10⁵ to 7.21 × 10⁵ for 3c , from 5.85 × 10⁵ to 8.51 × 10⁵ for 3d , from 7.55 × 10⁵ to 8.53 × 10⁵ for 3e , and from 8.54 × 10⁵ to 9.26 × 10⁵ for 3f . The aggregation numbers, N_agg's, which were calculated from the M_w,SLS's, were from 7 to 24 for 3a , from 20 to 37 for 3b , from 34 to 89 for 3c , from 39 to 116 for 3d , from 41 to 145 for 3e , and from 31 to 146 for 3f . It was confirmed that the aggregation property, such as the M_w,SLS or N_agg values, was strongly related to the polymerization degrees of St (DP's) or the number of the glucose residues (n's) for 3a–f . © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4864–4879, 2006     

Copolymerization of ethylene and norbornene using cyclopentadienylzirconium trichloride activated by isobutyl‐modified methylaluminoxane

The copolymerization of ethylene (E) and norbornene (NB) was investigated using the commercially available and inexpensive catalyst system, cyclopentadienylzirconium trichloride (CpZrCl₃)/isobutyl‐modified methylaluminoxane (MMAO), at a moderate polymerization temperature in toluene. For the CpZrCl₃ catalyst system activated by aluminoxane with a 40 mol % methyl group and a 60 mol % isobutyl group (MMAO), the quantities of the charged NB and the polymerization temperature significantly affected the molecular weights, polydispersities, and NB contents of the obtained copolymers and the copolymerization activities in all the experiments. As the charged NB increased and thereby the NB/E molar ratio increased, the NB content in the copolymer increased and reached a maximum value of 71 mol %. The CpZrCl₃/MMAO ([Al]/[Zr] = 1000) catalyst system with the [NB] of 2.77 mol L^?1 and ethylene of 0.70 MPa at 50 °C showed the highest activity of 1690 kg mol_Zr^?1 h^?1 and molecular weight of 21,100 g mol^?1. The ¹³C NMR analysis showed that the CpZrCl₃/MMAO catalyst system produced the E‐NB random copolymer with a number of NB homosequences such as the NN dyad and NNN triad. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7411–7418, 2008