Preparation of monodispersed vinylpyridine–divinylbenzene porous copolymer resins and their application to high-performance liquid chromatographic separation of aromatic amines

For the separation of aromatic amines, two types of monodispersed porous polymer resins were prepared by the copolymerization of 2-vinylpyridine and 4-vinylpyridine with divinylbenzene in the presence of template silica gel particles (particle size 5 μm), followed by dissolution of the template silica gel in an alkaline solution. The transmission electron micrographs and the scanning electron micrograph revealed that these templated polymer resins have a spherical morphology with a good monodispersity and porous structure. Using these monodispersed polymer resins, the high-performance liquid chromatographic separation of aromatic amines in the mobile phases of pHs 2.0, 2.9, 4.1, 7.2 and 11.7 were carried out. The 2-vinylpyridine–divinylbenzene copolymer resins showed slightly stronger retentions for aromatic amines than the 4-vinylpyridine–divinylbenzene copolymer resins. Under acidic conditions (around pH 2.0), aniline and the toluidines showed no retention on these copolymer resins due to the repulsion between the cationic forms of these amines and pyridinium cations in the stationary phase, whereas less basic aromatic amines or non-basic acetanilide showed slight retentions. Above pH 4.1, the separation of aromatic amines with these polymer resins showed a typical reversed-phase mode separation. Therefore, the separation patterns of aromatic amines are effectively tunable by changing the pH value of the mobile phases. A good separation of eight aromatic amines was achieved at pH 2.9 using the 2-vinylpyridine–divinylbenzene copolymer resins.     

Large molecules in high-intensity laser fields

New research fields have opened up that are related to the interactions between molecules and high-intensity optical fields where the laser intensity ranges from 10¹²–10¹⁷ W cm⁻². A broad outline of this area will be described from the perspective of products and new techniques for beam generation. Studies of large molecules have begun and some examples are introduced herein. Parent ions with little fragmentation are found to form in the intensity region below 10¹⁶ W cm⁻². The formation of intact ions can be used in femtosecond laser mass spectrometry. In the intensity region above 10¹⁶ W cm⁻², electrons are stripped from the molecules by optical field ionization and the highly charged ions can undergo a Coulomb explosion. Coulomb explosions of benzene and C₆₀ have been demonstrated, and the mechanism can be analyzed by means of molecular dynamics simulations. A high intensity femtosecond laser beam can be converted to radiation sources of coherent VUV light, X-rays etc. and some possibilities for new chemical applications will be discussed.     

Enhanced skin permeation of salicylate by ion-pair formation in non-aqueous vehicle and further enhancement by ethanol and l-menthol

Enhancement of skin permeability of salicylate from non-aqueous vehicle by ion-pair formation with either alkylamines or benzylamine as model cationic ions was examined in excised guinea pig dorsal skin. Solubility of salicylate in isopropyl myristate (IPM) was increased by the addition of either alkylamines or benzylamine as counter ions. The increase was more significant in the presence of amines with longer alkyl chains. Flux of salicylate increased in the presence of these amines due to the increase in the solubility. Maximum flux was observed in the presence of n-hexylamine, which induced an 11-fold increase due to 137-fold increase in solubility. Flux and permeability coefficients of salicylate in the presence of n-butylamine, n-hexylamine, iso-octylamine and benzylamine as counter ions in IPM were larger than those of the non-ionic form of salicylic acid. Flux of 3-methylsalicylate (3-CH3 substituent) and that of 5-hydroxysalicylate (5-OH substituent) were smaller than that of salicylate in the presence of n-hexylamine. After partition to the skin surface, the ion-pair is suggested to dissociate and permeate separately according to the study using lidocaine as the counter ion. Flux of salicylate increased in the presence of benzylamine as the counter ion by the addition of 15% ethanol and 15% ethanol plus 1% l-menthol due to further improvement in the solubility as well as an increase in the permeability coefficient.     

Mechanism of enantioseparation of DL-pantothenic acid in ligand exchange capillary electrophoresis using a diol-borate system

Borate complexes formed in the ternary system at pH 9.2 containing borate, (S)-3-amino-1,2-propanediol (SAP), and DL-pantothenic acid (DL-PTA) were identified by 13C and 11B NMR, and it is confirmed that the binary complexes, [B(OH)2(SAP)], [B(SAP)2]+ [B(OH)2(D- or L-PTA)]2-, and [B(D- or L-PTA)2]3- (including [B(D-PTA)(L-PTA)]3-), and the ternary complexes, [B(SAP)(D- or L-PTA)]-, coexist at equilibrium in the ternary system. Thermodynamic experiments by variable-temperature 11B NMR revealed that the ternary complex, [B(SAP)(D-PTA)]-, is entropically more stable than [B(SAP)(L-PTA)]-. Because two geometrical isomers are possible for the respective ternary complexes, semi-empirical molecular orbital calculations were performed by PM5, PM3, and AM1 methods in order to obtain the optimized structures. It is indicated from the calculated heats of formation and experimentally obtained thermodynamic parameters that the (S)-isomer is more probable for the respective ternary complexes with D- and L-PTA. In the optimized structure of (S)-[B(SAP)(D-PTA)]- in water, the SAP and D-PTA ligands were oppositely oriented to form a rather linear structure, while the diastereomer, (S)-[B(SAP)(L-PTA)]-, had a folded structure. Because such a difference in the solvated structure of the ternary complexes can give a different electrophoretic velocity in CE, the enantioseparation of DL-PTA in CE is reasonably attributed to a difference in the observed electrophoretic mobility for the equilibrated ternary systems containing the respective ternary complexes.     

Chiral resolution of monosaccharides as 1-phenyl-3-methyl-5-pyrazolone derivatives by ligand-exchange CE using borate anion as a central ion of the chiral selector

Six reducing monosaccharides (mannose, galactose, fucose, glucose, xylose, and arabinose) were derivatized with 1-phenyl-3-methyl-5-pyrazolone (PMP) and chiral resolution of these racemic PMP-monosaccharides was studied by ligand-exchange CE using borate anion as a central ion of the chiral selector and (S)-3-amino-1,2-propanediol (SAP) as a chiral selector ligand. PMP-mannose, PMP-galactose and PMP-fucose were successfully enantioseparated. Lowering the capillary temperature increased the resolution of PMP-mannose system, but decreased that of PMP-galactose and PMP-fucose systems. Whereas the maximum resolution was obtained at pH 8.9 in the PMP-mannose system, resolution increased gradually with pH in the PMP-galactose and PMP-fucose systems. Expecting the formation of the ternary borate complexes with SAP and PMP-monosaccharide in the CE experiments, the optimized structures of the borate diastereomers were obtained by semiempirical molecular orbital calculations to discuss the structural difference of the diastereomers in connection with the enantioseparation behaviors.     

Sonoporation-mediated transduction of siRNA ameliorated experimental arthritis using 3 MHz pulsed ultrasound

The goal of this feasibility study was to examine whether sonoporation assisted transduction of siRNA could be used to ameliorate arthritis locally. If successful, such approach could provide an alternative treatment for the patients that have or gradually develop adverse response to chemical drugs. Tumor necrosis factor alpha (TNF-α) produced by synovial fibroblasts has an important role in the pathology of rheumatoid arthritis, inducing inflammation and bone destruction. In this study, we injected a mixture of microbubbles and siRNA targeting TNF-α (siTNF) into the articular joints of rats, and transduced siTNF into synovial tissue by exposure to a collimated ultrasound beam, applied through a probe 6 mm in diameter with an input frequency of 3.0 MHz, an output intensity of 2.0 W/cm² (spatial average temporary peak; SATP), a pulse duty ratio of 50%, and a duration of 1 min. Sonoporation increased skin temperature from 26.8 °C to 27.3 °C, but there were no adverse effect such as burns. The mean level of TNF-α expression in siTNF-treated knee joints was 55% of those in controls. Delivery of siTNF into the knee joints every 3 days (i.e., 7, 10, 13, and 16 days after immunization) by in vivo sonoporation significantly reduced paw swelling on days 20–23 after immunization. Radiographic scores in the siTNF group were 56% of those in the CIA group and 61% of those in the siNeg group. Histological examination showed that the number of TNF-α positive cells was significantly lower in areas of pannus invasion into the ankle joints of siTNF- than of siNeg-treated rats. These results indicate that transduction of siTNF into articular synovium using sonoporation may be an effective local therapy for arthritis.     

No-wash protein labeling with designed fluorogenic probes and application to real-time pulse-chase analysis

Small molecule labeling techniques for cellular proteins under physiological conditions are very promising for revealing new biological functions. We developed a no-wash fluorogenic labeling system by exploiting fluorescence resonance energy transfer (FRET)-based fluorescein-cephalosporin-azopyridinium probes and a mutant β-lactamase tag. Fast quencher elimination, hydrophilicity, and high resistance against autodegradation were achieved by rational refinement of the structure. By applying the probe to real-time pulse-chase analysis, the trafficking of epidermal growth factor receptors between cell surface and intracellular region was imaged. In addition, membrane-permeable derivatization of the probe enabled no-wash fluorogenic labeling of intracellular proteins.     

Improvement of mechanical and oxygen barrier properties of cellulose films by controlling drying conditions of regenerated cellulose hydrogels

Mechanical, thermal and oxygen barrier properties of regenerated cellulose films prepared from aqueous cellulose/alkali/urea solutions can be markedly improved by controlling the drying conditions of the films. By pre-pressing followed by vacuum drying under compression, the tensile strength, Young’s modulus, coefficient of thermal expansion and oxygen permeability of the dried films reached 263 MPa, 7.3 GPa, 10.3 ppm K⁻¹ and 0.0007 ml μm m⁻² day⁻¹ kPa⁻¹, respectively. Thus, films produced in this way show the highest performance of regenerated cellulose films with no orientation of cellulose chains reported to date. These improved properties are accompanied by a clear increase in cellulose II crystallinity from 50 to 62% during pre-pressing/press-vacuum drying process. At the same time, the film density increased from 1.45 to 1.57 g cm⁻³, and the moisture content under equilibrium conditions decreased from 14.1 to 9.8%. Hence, the aqueous alkali/urea solvent system has potential applications in producing new and environmentally friendly cellulose films with high performances through control of the drying conditions.     

Experimental Study on Powder Flowability Using Vibration Shear Tube Method

The flowability of powders with different mass median diameters ranging from micrometers to nanometers was measured using the vibration shear tube method. In the measurement system used in this study, the powder was discharged through a narrow gap between a vibrating tube edge and a flat bottom surface, where each particle could experience high shear forces to overcome the adhesion and friction forces. The vibration amplitude was increased during the measurement, and the mass of particles discharged was measured at constant time intervals. From the relationship between the mass flow rate and the vibration acceleration, static and dynamic properties of the powders were evaluated using the critical vibration acceleration, characteristic mass flow rate, and gradient of mass flow rate. The correlation between the static and dynamic properties was studied in detail.     

Polypyrrole-palladium nanocomposite coating of micrometer-sized polymer particles toward a recyclable catalyst

A range of near-monodisperse, multimicrometer-sized polymer particles has been coated with ultrathin overlayers of polypyrrole-palladium (PPy-Pd) nanocomposite by chemical oxidative polymerization of pyrrole using PdCl(2) as an oxidant in aqueous media. Good control over the targeted PPy-Pd nanocomposite loading is achieved for 5.2 μm diameter polystyrene (PS) particles, and PS particles of up to 84 μm diameter can also be efficiently coated with the PPy-Pd nanocomposite. The seed polymer particles and resulting composite particles were extensively characterized with respect to particle size and size distribution, morphology, surface/bulk chemical compositions, and conductivity. Laser diffraction studies of dilute aqueous suspensions indicate that the polymer particles disperse stably before and after nanocoating with the PPy-Pd nanocomposite. The Fourier transform infrared (FT-IR) spectrum of the PS particles coated with the PPy-Pd nanocomposite overlayer is dominated by the underlying particle, since this is the major component (>96% by mass). Thermogravimetric and elemental analysis indicated that PPy-Pd nanocomposite loadings were below 6 wt %. The conductivity of pressed pellets prepared with the nanocomposite-coated particles increased with a decrease of particle diameter because of higher PPy-Pd nanocomposite loading. "Flattened ball" morphologies were observed by scanning/transmission electron microscopy after extraction of the PS component from the composite particles, which confirmed a PS core and a PPy-Pd nanocomposite shell morphology. X-ray diffraction confirmed the production of elemental Pd and X-ray photoelectron spectroscopy studies indicated the existence of elemental Pd on the surface of the composite particles. Transmission electron microscopy confirmed that nanometer-sized Pd particles were distributed in the shell. Near-monodisperse poly(methyl methacrylate) particles with diameters ranging between 10 and 19 μm have been also successfully coated with PPy-Pd nanocomposite, and stable aqueous dispersions were obtained. The nanocomposite particles functioned as an efficient catalyst for the aerobic oxidative homocoupling reaction of 4-carboxyphenylboronic acid in aqueous media for the formation of carbon-carbon bonds. The composite particles sediment in a short time (相似文献