Synthesis of Anisotropic Polymer Particles with Soap‐Free Emulsion Polymerization in the Presence of a Reactive Silane Coupling Agent

A novel two step method has been developed for the preparation of anisotropic polymer particles using soap‐free emulsion polymerization in the presence of the reactive silane coupling agent 3‐methacryloxypropyltrimethoxysilane (MPTMS). In the first step, seed polymer particles were prepared in the presence of MPTMS in water. In the second step, another polymerization was conducted in the presence of the seed particles, which induced anisotropic protrusion of polymer from the seed particles. The two step method is applicable to the preparation of anisotropic polymer particles containing inorganic particles such as silica. Silica particles inside the anisotropic polymer particles were dissolved with hydrofluoric acid, which created hollow polymer particles with anisotropy.

     

The Progress of the Gait Impairment and Brain Activation in a Patient with Post-stroke Hemidystonia

Objective: We explore the effects of body weight-supported (BWS) treadmill training, including the change of cortical activation, on a patient with post-stroke hemidystonia. Patient: The patient was a 71-year-old man with left thalamus hemorrhage. His motor symptoms indicated slight impairment. There was no overactive muscle contraction in the supine, sitting, or standing positions. During his gait, the right initial contact was the forefoot, and his right knee showed an extension thrust pattern. These symptoms suggested that he had post-stroke hemidystonia. Methods: The patient performed BWS treadmill training 14 times over 3 weeks. The effects of the BWS training were assessed by a step-length analysis, electromyography and functional magnetic resonance imaging (fMRI). Results: The patient''s nonparetic step length was extended significantly in the Inter-BWS (p<0.001) and Post-BWS (p=0.025) periods compared to the Pre-BWS session. The excessive muscle activity of the right gastrocnemius medialis in the swing phase was decreased at the Inter-BWS, Post-BWS, and follow-up compared to the Pre-BWS session. The peak timing difference of the bilateral tibialis anterior muscle became significant (p<0.05) on the first day of the intervention. The fMRI revealed that the cortical areas activated by the motor task converged through the intervention (p<0.05, family-wise error corrected). Conclusion: These results suggest that there was improvement of the patient''s symptoms of post-stroke hemidystonia due to changes in the brain activity during voluntary movement after BWS intervention. Body weight-supported treadmill training may thus be an effective treatment for patients with poststroke hemidystonia.     

Synthesis of Submicron-Sized Titania-Coated Silica Particles with a Sol-Gel Method and Their Application to Colloidal Photonic Crystals

A previously proposed method for preparing monodispersed titania particles was extended to preparation of titania-coated silica spherical particles. The core silica particles with an average size of 264 nm were prepared with Stöber method. The titania-coating was performed in ethanol/acetonitrile solvent in the presence of silica particles by a sol-gel method with the use of titanium tetraisopropoxide (TTIP) and methylamine (MA) catalyst. Average size of the silica-titania particles decreased from 457 to 292 nm with an increase in concentration of silica particles. Coefficient of variation for the particle size was less than 5%. Colloidal crystals could be fabricated with a dip-coating technique and a sedimentation process, respectively. Measurements of reflectance revealed peaks based on the Bragg diffraction. Those peaks red-shifted with an increase in titania shell thickness because of a high refractive index of titania. Annealing at high temperature transformed crystal structure of titania shell from amorphous to anatase (500°C) and rutile (1000°C), which led to red-shift of reflection peak because of an increase in refractive index of titania due to the crystallization.     

Detection of Polyols by HPLC Coupled with an On‐Line Photochemical Oxidation Reactor and Chemiluminescence Detection

In this paper we propose a new post‐column detection method for polyols containing 1,2‐diol, 1,3‐diol, and saccharides. The polyols are oxidized in a photochemical reactor to yield oxalate with subsequent chemiluminescence detection using [Ru(III)(bpy)₃]³⁺. A mixing solution of eluate and oxidizing reagent is delivered to a reaction coil, which is then irradiated with ultraviolet light to promote the oxidation reaction. The detection limits for 1,2‐ethanediol (ethylene glycol) and 1,3‐propanediol were 38 pmol and 23 pmol, respectively.     

Pd(II)-catalyzed copolymerization of a norbornadiene derivative with substituted phenylacetylenes

Copolymerizations of diethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate (DOHDD) with phenylacetylene (PA) or p-methoxyphenylacetylene (MeOPA) were successfully performed in chloroform using PdBr₂ as catalyst. The products of reactivity ratios r₁ · r₂ for poly(DOHDD-co-PA) and poly(DOHDD-co-MeOPA) are 0.026 and 0.0077, respectively. These values suggest a maximum degree of alternating sequences of 86 and 92% in the two systems, hence a high alternating tendency. It is interesting to note that the present copolymerizations occur by combination of different types of monomer, alkene and alkyne.     

The Effect of Toe-grasping Exercises on Balance Ability in Home-based Rehabilitation: A Randomized Controlled Trial by Block Randomization

Objective: The purpose of the study was to clarify the causal effect of toe-grasping exercises on the improvement of static or dynamic balance ability in home-based rehabilitation users. Method: Our study included 34 subjects who met the criteria and were evaluable out of 98 rehabilitation service users at home nursing stations. This study was a randomized controlled trial. The intervention group performed towel gathering exercises in addition to the regular home-based rehabilitation program. The primary outcome was one-leg standing time, and the secondary outcomes were two-step test and toe grip strength. Results: Seventeen subjects were assigned to the intervention group and seventeen to the control group by block randomization. Data from 15 and 12 subjects in the intervention group and control group, respectively, who were able to complete the initial evaluation and the evaluation after 3 months, were analyzed. We compared the amount of change after 3 months of evaluation in the intervention group with the change in the control group. The results showed that the left/right mean value of oneleg standing time in the intervention group was significantly greater than that in the control group. In terms of the amount of change in the intervention period (T2-T1) within each assessment, there were significant improvements in both the toe-grip strength and the two-step values in the intervention group. Conclusion: We found that toe-grasping exercises could improve the balance ability of home-based rehabilitation users. This suggests the clinical significance of toe function in rehabilitation programs.     

Magnetic properties of DNA-templated Co/Cu naonoparticle chains

<正>According to ultraviolet(UV)-vis absorption spectra recorded in the DNA metallization process,DNA-templated Co/Cu binary nanoparticle chains are fabricated by incubating genome DNA of paralichthys olivaceus muscle in CoCl_2 and CuCl_2 mixture solution for 20 hours and reducing the complex for 2 hours.Transmission electron microscopy observation indicates that Co and Cu nanoparticles with 20 nm in diameter were randomly dispersed on the DNA template. The superconducting quantum interference device(SQUID) measurements display that the magnetic interaction between cobalt particles is greatly decreased by the copper particle.With increasing copper content,the coercivity of the systems enhance from 9 Oe to 100 Oe(1 Oe=79.5775 A/m).     

Cationic N,N-Dimethylglycine Ester Prodrug of 2R-α-Tocotrienol Promotes Intestinal Absorption via Efficient Self-Micellization with Intrinsic Bile Acid Anion

The intestinal absorption of hydrophobic compounds is severely influenced by their transportation rate through the unstirred water layer in the intestinal lumen. A member of the vitamin E family, α-Tocotrienol (α-T3) has remarkable pharmacological effects, but its intestinal absorption is hampered due to its hydrophobicity. Here, we prepared three ester derivatives of 2R-α-T3, and we selected a suitable prodrug compound using rat plasma and liver microsomes. The micellization profile of the selected compound in the presence of taurocholic acid (TCA) was evaluated. After gastrostomy administration of the prodrug candidate or α-T3 solution containing TCA, AUC values were determined for α-T3 in plasma obtained from bile duct-ligated rats. Among the three types in the efficiency of the reconversion to the parent drug, α-T3 N,N-dimethylglycinate (α-T3DMG) was the best prodrug; α-T3DMG formed mixed micelles via ion pairs with anionic TCA. The solubility of α-T3DMG in n-octanol/water depended on its ratio to TCA. The AUC after α-T3DMG administration to ligated rats was 2-fold higher than that after α-T3 administration, suggesting a smooth interaction with intrinsic bile acids. In conclusion, utilization of the prodrug synthesized using N,N-dimethylglycine ester may be a beneficial approach to promote intestinal absorption of α-T3 via self-micellization with intrinsic bile acid.     

Enantioseparation of 3-Hydroxycarboxylic Acids via Diastereomeric Salt Formation by 2-Amino-1,2-diphenylethanol (ADPE) and Cinchonidine

Enantioseparation of 3-hydroxycarboxylic acids via diastereomeric salt formation was demonstrated using 2-amino-1,2-diphenylethanol (ADPE) and cinchonidine as the resolving agents. Racemic 3-hydroxy-4-phenylbutanoic acid (rac-1), 3-hydroxy-4-(4-chlorophenyl)butanoic acid (rac-2), and 3-hydroxy-5-phenylpentanoic acid (rac-3) were efficiently resolved using these resolving agents. Moreover, the successive crystallization of the less-soluble diastereomeric salt of 1 and cinchonidine using EtOH yielded pure (R)-1 · cinchonidine salt in a high yield. The crystal structures of less-soluble diastereomeric salts were elucidated and it was revealed that hydrogen bonding and CH/π interactions play an important role in reinforcing the structure of the less-soluble diastereomeric salts.