Synthesis and characterization of molybdenum incorporated mesoporous aluminophosphate

A synthesis of molybdenum incorporated mesoporous aluminophosphate with long-chain n-alkylamine as template material had been prepared under non-aqueous condition. These materials were extensively characterized by using X-ray diffraction (XRD), nitrogen sorption isotherms, nuclear magnetic resonance of ²⁷Al and ³¹P (NMR), inductive coupled plasma (ICP), electron spin resonance (ESR), Fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG-DTA). Morphology of the materials had been observed by using transmission electron microscope (TEM) that revealed the mesoporous materials possessed wormhole-like structures. Alkaline solvent extraction using n-butylamine/ethanol had been efficiently removed the n-alkylamine from the mesoporous samples which yielded BET surface areas around 550-730 m²/g. BJH analysis showed a narrow pore size distribution which increased with increasing of the carbon chain length of alkylamine (template). Valence state and coordination of the molybdenum in the obtained samples were investigated by using ESR and FTIR where it was found that Mo⁴⁺ and Mo⁶⁺ molybdenum species existed in the molybdenum incorporated mesoporous aluminophosphate in tetrahedral coordination.     

Simultaneous imaging of the structure and fluorescence of a supramolecular nanostructure formed by the coupling of π‐conjugated polymer chains in the intermolecular interaction

We fabricated a micrometer‐long supramolecular chain in which π‐conjugated polyrotaxane was coupled. A new experimental setup was designed and constructed, and the simultaneous direct imaging of the structure and fluorescent function was achieved. Furthermore, we identified the formation of a polymer intertwined network and observed novel fluorescence due to a long‐range interaction via this intertwined network over a distance of 5 μm or more without quenching over 15 min in the near field. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 801–809, 2006     

SUPER TOUGH GELS WITH A DOUBLE NETWORK STRUCTURE

 Living tissues work with fantastic functions in soft and wet gel-like state. Thus, hydrogels have attracted much attention as excellent soft & wet materials, suitable for making artificial organs for medical treatments.However, conventional hydrogels are mechanically too weak for practical uses. We have created double network (DN) hydrogels with extremely high mechanical strength in order to overcome this problem. DN gels are interpenetrating network (IPN) hydrogels consisting of rigid polyelectrolyte and soft neutral polymer. Their excellent mechanical properties cannot be explained by the standard fracture theories. In this paper, we discuss about the toughening mechanism of DN gels in accordance with their characteristic behavior, such as large hysteresis and necking phenomenon. We also describe the results on tissue engineering application of DN gels.     

Optical CO(2) sensor of the combination of colorimetric change of alpha-naphtholphthalein in poly(isobutyl methacrylate) and fluorescent porphyrin in polystyrene

An optical CO₂ sensor based on the overlay of the CO₂ induced absorbance change of pH indicator dye α-naphtholphthalein in poly(isobutyl methacrylate) (polyIBM) layer with the fluorescence of tetraphenylporphyrin (TPP) in polystyrene layer is developed. The observed luminescence intensity from TPP at 655 nm increased with increasing the CO₂ concentration. The ratio I₁₀₀/I₀ value of the sensing film consisting of α-naphtholphthalein in polyIBM and TPP in polystyrene layer, where I₀ and I₁₀₀ represent the detected luminescence intensities from a layer exposed to argon and CO₂ saturated conditions, respectively, that the sensitivity of the sensor, is estimated to be 192. The response and recovery times of the sensing film are less than 6.0 s for switching from argon to CO₂, and for switching from CO₂ to argon. The signal changes are fully reversible and no hysterisis is observed during the measurements. The highly sensitive optical CO₂ sensor based on fluorescence intensity changes of TPP due to the absorption change of α-naphtholphthalein in polyIBM layer with CO₂ is achieved.     

Determination of rare earth elements in seawater by on-line column preconcentration inductively coupled plasma mass spectrometry

A home made column of commercially available iminodiacetate resin, Muromac A-1 (50–100 mesh) was used to concentrate rare earth elements (REEs) (15 elements: Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in seawater. An automated low pressure flow analysis method with on-line column preconcentration/inductively coupled plasma mass spectrometry (ICP-MS) is described for the determination of REEs in seawater. Sample solutions (adjusted to pH of 3.0) passed through the column. After washing the column with water, the adsorbed elements were subsequently eluted into the plasma with 0.7 M nitric acid. Calibration curves were accomplished by means of purified artificial seawater with a sample loading time of 120 s. Detection limits (DLs) of the on-line column preconcentration/ICP-MS by eight replicate operations were between 0.040 and 0.251 pg ml⁻¹ for REEs in the artificial seawater. The precision was less than 8.9% for REEs and one sample can be processed in 7 min using a 7 ml of sample. The proposed method was applied to determine REEs in coastal seawater of Hiroshima Bay, Japan.     

Excited states of phosphorescent platinum(II) complexes containing N wedge C wedge N-coordinating tridentate ligands: spectroscopic investigations and time-dependent density functional theory calculations

The absorption and emission spectra of the Pt(II) complexes containing N wedge C wedge N-coordinating tridentate ligands, platinum(II) 1,3-di(2-pyridyl)benzene chloride [Pt(dpb)Cl] and platinum(II) 3,5-di(2-pyridyl)toluene chloride [Pt(dpt)Cl], together with their corresponding free ligands, 1,3-di(2-pyridyl)benzene (dpbH) and 3,5-di(2-pyridyl)toluene (dptH), have been analyzed by density functional theory (DFT) for the ground state and time-dependent DFT (TDDFT) for the excited states. T(1)(A(1)) and S(1)(B(2)) of the complexes (in C(2)(v) symmetry) were assigned on the basis of the calculated excitation energies as well as comparison of the experimental spectroscopic properties and the calculated states' characteristics. The calculated excitation energies for T(1) and S(1) of the complexes as well as those for T(1) of the free ligands were in good agreement with their observed values within 600 cm(-1). The d-pi* characters of the excited states were evaluated from the change in electron densities between the ground and excited states by Mulliken population analysis; values of 25% for T(1) and 32% for S(1) were obtained for both complexes. The calculated values of d-pi* character were found to be consistent with the reported emission lifetimes as well as the observed emission energy shifts from the corresponding free ligands. Most spectroscopic properties of the complexes and the free ligands, which include solvatochromic shift, Stokes shifts, methyl substitution shifts, and emission spectra profiles, were well explained from the calculation results.     

Highly active, immobilized ruthenium catalysts for oxidation of alcohols to aldehydes and ketones. Preparation and use in both batch and flow systems

A novel, highly active immobilized ruthenium catalyst, which can be successfully used in oxidation of alcohols to aldehydes and ketones, has been developed. In contrast to most immobilized catalysts, the Ru catalyst has activity that is higher than that of the original non-immobilized catalyst. In a batch system, the Ru catalyst was recovered and reused several times without loss of activity. The catalyst was also applied to a flow system, in which excellent conversions and yields were demonstrated. No leaching of Ru was observed in both cases.     

Development of a stable isotope dilution UPLC‐MS/MS method for quantification of dexmedetomidine in a small amount of human plasma

Dexmedetomidine (Dex) is a selective central α2‐agonist with anesthetic properties and has been used in clinical practice for sedation in the intensive care unit (ICU) after operations. In this study, an analytical assay for the determination of Dex in a small amount of plasma was developed for the application to pediatric ICU trials. The quantification of Dex was constructed using the original stable isotope Dex‐d₃ for electrospray ionization‐tandem mass spectrometry (ESI‐MS/MS) in the selected reaction monitoring mode. A rapid ultra‐performance liquid chromatography technique was adopted using ESI‐MS/MS with a runtime of 3 min. Efficacious concentration levels (50 pg/mL to 5 ng/mL) could be evaluated using a very small amount of plasma (10 μL) from patients. The lower limit of the quantification was 5 pg/mL in the plasma (100 µL). For sample preparation, a solid‐phase extraction was used along with the OASIS‐HLB cartridge type. Recovery values ranged from 98.8 to 100.3% for the intra‐ [relative standard deviation (RSD), 0.9–1.3%] and inter‐ (RSD, 0.9–1.5%) day assays. A stable test had recovery values that ranged from 97.8 to 99.7% with an RSD of 1.0–1.9% for the process/wet extract, bench‐top, freeze–thaw and long‐term tests. This method was used to measure the Dex levels in plasma from pediatric ICU patients. In the clinical ICU trial, the small amount of blood (approximate plasma volume, 200 μL) remaining from blood gas analysis was reused and targeted for the clinical analysis of Dex in plasma. Copyright © 2013 John Wiley & Sons, Ltd.