Direct determination of acylcarnitines in amniotic fluid by column-switching liquid chromatography with electrospray tandem mass spectrometry

A direct, simple, and simultaneous determination of acylcarnitines in amniotic fluid was developed using column-switching liquid chromatography/tandem mass spectrometry (LC/MS/MS). The analytes can be assayed within 20 min without any sample preparation process, and we monitored separated acylcarnitines with positive electrospray ionization (ESI)-MS/MS. The calibration ranges of acylcarnitines were 1 to 100 nmol/L. The linearity of the method was 0.992 to 0.999, and the limits of detection at a signal-to-noise ratio of 3 were 1 nmol/L. The coefficients of variation were in the range of 5.2 to 13.3% for within-day variation and 6.7 to 11.9% for day-to-day, respectively. We detected acylcarnitines in the amniotic fluid of 22 women in the early stages of their pregnancies in the range of 2.2 to 17.2 nmol/L. The proposed method could be applied to diagnosis, monitoring, and biomedical investigations of inborn errors of the organic acid and fatty acid metabolism of the embryo.     

Fully flexible unit cell simulation with recursive thermostat chains

The recursive thermostat chained fully flexible cell molecular dynamic simulation (NsigmaT ensemble) is performed. The ensemble is based on the metric tensor, whose components are used as extended variables. These variables are combined with Nosé-Poincaré recursive thermostat chains. This extended Hamiltonian approach preserves Hamiltonian in structure, and the partition function satisfies the NsigmaT ensemble state in phase space. In the present study, the generalized leap frog method was employed for time integration. The resulting molecular dynamics simulation was performed for bulk and thin film solid materials in the face-centered-cubic crystal structure. Uniaxial tension test and simple shear test are performed to predict the behaviors of a solid material in the bulk state and nanoscale thin film state. The proposed flexible cell method should serve as a powerful tool for the prediction of mechanical and thermal properties of solid materials including nanoscale behavior.     

Catalytic one-pot synthesis of cyclic amidines by virtue of tandem reactions involving intramolecular hydroamination under mild conditions

A new synthetic methodology for the generation of cyclic amidines has been developed by the reaction of 1,n-aminoalkynes with electron-deficient azides using a ruthenium catalyst at ambient temperature. The reaction proceeds most likely via a tandem sequence of intramolecular hydroamination of aminoalkynes, cycloaddition of azides with the resulting enamines, and rearrangement of triazoline intermediates. It demonstrates, as the proof-of-principle, that an equilibria cascade sequence can be favorably driven by an irreversible step, thus enabling a facile one-pot synthetic route to deliver molecular complexity under unprecedented mild conditions without relying on the traditional linear approaches.     

Conducting block copolymer for simple micro- to nanopatterns

To use conducting polymers as substitutes for metals and conventional semiconductors in device fabrication, a cost-effective process for the reproducible deposition of the conducting polymers is needed. In this letter, we report a simple solution casting method for the fabrication of micro- to nanopatterns using the conducting block copolymer, poly(thiophene-block-ethyleneoxide), which shows rectifying characteristics dependent on the pattern width.     

Self-assembly of a diblock copolymer on a patterned surface with low-energy electron beam

A pattern was generated by 500 eV electron beam irradiation on benzaldimine monolayer through a grid and subsequent hydrolysis of nonirradiated regions. While we tried to assemble a block copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), on the pattern, we observed that the polarity difference between the two different regions was not right for discriminating the wetting behavior of two blocks of the polymer. Among various modifications of the retrieved amine, it was found that tribromoacetaldehyde was suitable for this end. Surprisingly, treatment of the aldehyde gave a surface preferring the polystyrene block to poly(4-vinylpyridine) block, while the irradiated section favored the latter block. As a result, island morphology was observed on the tribromoacetaldimine region and hole morphology on the irradiated region when the film thickness was 1.3Lo. Contact angle data were consistent with the observed symmetric wetting on the former region and the asymmetric one on the latter.     

Doped colloidal photonic crystal structure with refractive index chirping to the [111] crystallographic axis

A three-dimensionally ordered array of close-packed colloidal spheres, a photonic crystal structure in which the refractive index of the medium interstitial lattice in a colloidal crystal spatially changes in the [111] crystallographic axis, is demonstrated. The colloidal photonic crystal structure with refractive index chirping was produced by infiltration of a monomer and organic dopants with a high refractive index into a silica opal, followed by interfacial gel polymerization. The resulting photonic crystal structure has a gradually varying stop band at each different (111) plane in the face-centered cubic (fcc) crystal structure at a normal incidence. This novel structure exhibited optical characteristics that have band-gap broadening by the superposition of stop bands at each plane of the crystal with different dielectric functions. Moreover, the refractive index perturbation in the [111] fcc opal also showed a defect state within a pseudo-photonic band gap. This new type of photonic crystal structure should be useful for the band-gap engineering of photonic-band-gap materials.     

ADAAPT: Amgen's data access, analysis, and prediction tools

The Amgenȁ9s Data Access Analysis Prediction Tools (ADAAPT) system is a desktop decision support tool developed to provide flexible access and analysis of chemical and biological data. The system is platform independent, adaptable, easily deployed, and scalable. It consists of four main modules: access, analysis, prediction, and tools. The access module contains numerous user interfaces designed to retrieve data easily. The analysis module provides standard computational tools to perform property calculation, QSAR/QSPR, and statistical analyses. The prediction module contains in-house models to calculate a drug-likeness score and absorption index. Finally, the tools module provides a wide array of features that are of general interest to our scientists.     

Modulating the pattern quality of micropatterned multilayer films prepared by layer-by-layer self-assembly

Patterned multilayer films composed of poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate) (PSS) were prepared using dip and spin self-assembly (SA) methods. A silicon substrate was patterned with a photoresist thin film using conventional photolithography, and PAH/PSS multilayers were then deposited onto the substrate surface using dip or spin SA. For spin SA, the photoresist on the substrate was retained, despite the high centrifugal forces involved in depositing the polyelectrolytes (PEs). The patterned multilayer films were formed by immersing the PE-coated substrates in acetone for 10 min. The effect of ionic strength on the pattern quality in dip and spin multilayer patterns (line-edge definition and surface roughness of the patterned region) was investigated by increasing the salt concentration in the PE solution (range 0-1 M). In dip multilayer patterns, the presence of salt increased the film surface roughness and pattern thickness without any deformation of pattern shape. The spin multilayer patterns formed without salt induced a height profile of about 130 nm at the pattern edge, whereas the patterns formed with high salt content (1 M) were extensively washed off the substrates. Well-defined pattern shapes of spin SA multilayers were obtained at an ionic strength of 0.4 M NaCl. Multilayer patterns prepared using spin SA and lift-off methods at the same ionic strength had a surface roughness of about 2 nm, and those prepared using the dip SA and lift-off method had a surface roughness of about 5 nm. The same process was used to prepare well-defined patterns of organic/metallic multilayer films consisting of PE and gold nanoparticles. The spin SA process yielded patterned multilayer films with various lengths and shapes.     

Drop formation via breakup of a liquid bridge in an AC electric field

Experimental results are presented for the study of drop formation mechanism in a newly proposed electrohydrodynamic (EHD) method of drop generation in an AC electric field. In the method, a small drop is generated in two stages. A pendant drop is elongated with large oscillation by an electric force in the first stage. Then, it undergoes formation and breakup of a liquid bridge between the upper nozzle and the insulator-coated lower flat plate in the second stage. It is found that there exists a resonant frequency for maximum oscillation, which leads to an efficient drop formation in the latter stage. It is also found that breakup of liquid bridge is accelerated by the electrowetting tension acting on the drop perimeter contacting the insulator-coated flat plate. Thus the whole procedure of drop formation depends heavily on the frequency of AC field and the properties of the insulator such as hydrophilicity, thickness, and the dielectric constant. It is demonstrated that a wide range of drop size, from picoliter to nanoliter, can be obtained by controlling such key parameters without changing the nozzle diameter.