Synthesis and characterization of original 2-(dimethylamino)ethyl methacrylate/poly(ethyleneglycol) star-copolymers

Novel synthetic transfection vectors with linear triblock and star-shaped diblock copolymer architectures have been synthesized by atom transfer radical polymerization (ATRP). Based on 2-(dimethylamino)ethyl methacrylate (DMAEMA) and copolymerization with poly(ethyleneglycol) α-methoxy, ω-methacrylate (MAPEG), the synthesis was realized using CuBr ligated with 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) as catalytic complex and either ethyl 2-bromoisobutyrate (EBⁱB) or bis(α-bromoisobutyryl) N-methyl diethanolamine (DEA) or tris(α-bromoisobutyryl) triethanolamine (TEA) as (multifunctional)initiator. The polymers were characterized by GPC and NMR. The solution properties of these homopolymers and palm-tree-like copolymers were investigated by viscometry either in pure water or in buffered aqueous solutions. Interestingly, all the synthesized polymers show polyelectrolyte effect in Millipore water (25 °C) and in Hepes (20 mM) buffer solution (pH 7.4, NaCl 155 mM, 25 °C). Fitting of these viscometric data according to either Fuoss or Fedors equation allows for calculating the intrinsic viscosity of the polymers. These results are compared with dynamic light scattering (DLS) experiments to determine absolute masses. Finally, DEA based palm-tree-like copolymer is investigated to AFM measurement and micelles were observed at pH 8.     

Integrated particle detection chip for environmental monitoring

This paper reports an integrated particle detection chip for low-cost and point-of-interest environmental monitoring; it consists of a micro virtual impactor and a micro corona discharger. With this system, airborne particles are introduced into the micro virtual impactor of the chip where they are classified according to their aerodynamic diameters. The particles are then charged and their number-concentration is detected in the micro corona discharger from the electrical current carried by the charged particles. The characteristics of each component were first analyzed, and the components were then integrated into a single chip. The micro virtual impactor was designed to have a cut-off diameter of 600 nm or 1.0 microm. Its classification characteristics were examined by classifying polydisperse particles-dioctyl sebacate particles ranging in diameter from 100 to 600 nm and carbon particles ranging in diameter from 0.6 to 10 microm. From the classification results, the cut-off diameter of the micro virtual impactor was measured to be either 550 nm or 1.1 microm. The micro corona discharger was fabricated based on a sharp silicon tip and a planar electrode and charged particles at 1.3 kV. Using the integrated particle detection chip comprising the micro virtual impactor and the micro corona discharger, the sensitivity for monodisperse particles-500 nm dioctyl sebacate in diameter-was measured to be 8 x 10(-7) pA/(particle cm(-3)).     

Structural evolution in microbial polyesters

The crystallization behavior of microbially synthesized poly(3-hydroxybutyrate) (PHB) and its copolymers [P(HB-co-HHx)] containing 2.5, 3.4, and 12 mol % 3-hydroxyhexanoate (HHx) comonomer and the melting of the resultant crystals were studied in detail using time-resolved small-angle X-ray scattering and differential scanning calorimetry. The polyesters were found to undergo primary crystallization as well as secondary crystallization. In the primary crystallization, the thicknesses of the lamellar crystals were sensitive to the crystallization temperature, but no thickening was observed throughout the entire crystallization at a given temperature. The thickness of the lamellar crystals in the PHB homopolymer was always larger than that of the amorphous layers. In the copolymers, by contrast, the randomly distributed HHx comonomer units were found to be excluded from the lamellar crystals into the amorphous regions during the isothermal crystallization process. This interrupted the crystallization of the copolymer chains, resulting in the formation of lamellar crystals with thicknesses smaller than those of the amorphous layers. The lamellar crystals in the copolymers had lower electron densities compared to those formed in the PHB homopolymer. On the other hand, secondary crystallization favorably occurred during the later stage of isothermal crystallization in competition with the continuous primary crystallization, forming secondary crystals in amorphous regions, in particular in the amorphous layers between the primarily formed lamellar crystal stacks. Compared to the primarily formed lamellar crystals, the secondary crystals had short-range-ordered structures of smaller size, a broader size distribution, and a lower electron density.     

Deracemization of unnatural amino acid: homoalanine using D-amino acid oxidase and ω-transaminase

A deracemization method was developed to generate optically pure L-homoalanine from racemic homoalanine using D-amino acid oxidase and ω-transaminase. A whole cell reaction using a biphasic system converted 500 mM racemic homoalanine to 485 mM L-homoalanine (>99% ee).     

Optimization of Culture Conditions for 1,3-Propanediol Production from Glycerol Using a Mutant Strain of <Emphasis Type="Italic">Klebsiella pneumoniae</Emphasis>

In the present work, mutant strains of Klebsiella pneumoniae with deletions of the als gene encoding acetolactate synthase involved in synthesis of 2,3-butanediol, the ldhA gene encoding lactate dehydrogenase required for lactate synthesis, or both genes, were prepared. Production of 1,3-propanediol (1,3-PD) from glycerol was enhanced in the ldhA mutant strain (ΔldhA), but lower in Δals or Δals ΔldhA mutant strains compared to the parent strain, concomitant with a reduction in the glycerol consumption rate, indicating that deletion of ldhA alone was useful to improve 1,3-PD production. Fed-batch fermentation analysis revealed that, in the ΔldhA mutant strain, 1,3-PD production was higher at low pH than at neutral pH; the reverse was true for the parent strain. Further optimization of culture conditions, by variation of aeration and glycerol feed rates, dramatically improved the production of 1,3-PD by the mutant strain. The maximum level attained was 102.7 g l⁻¹ of 1,3-PD from glycerol.     

Self-assembled monolayers made of 6-(5-((6-((5-hexylthiophen-2-yl)ethynyl)-9,10-bis(phenylethynyl)anthracen-2-yl)ethynyl)thiophen-2-yl)hexyl 3-(triethoxysilyl)propylcarbamate for ultrathin film transistors

A new functionalized triethoxysilane bearing an X-shaped, anthracene-based semiconducting molecule on one arm was designed and synthesized as a precursor for the preparation of a self-assembled monolayer (SAM) on a SiO(2) substrate. 3-Isocyanatopropyl triethoxysilane was reacted with a monohydroxyl-terminated X-shaped, anthracene-based semiconducting molecule in the presence of tin catalyst. The 6-(5-((6-((5-hexylthiophen-2-yl)ethynyl)-9,10-bis(phenylethynyl)anthracen-2-yl)ethynyl)thiophen-2-yl)hexyl 3-(triethoxysilyl)propylcarbamate (BATHT-TEOS) was found to be stable and sufficiently reactive to form organic monolayers on hydroxylated SiO(2) surfaces. The structures and properties of these SAMs were investigated using X-ray photoelectron spectroscopy, UV-vis absorption spectroscopy, photoluminescence (PL) spectroscopy, laser scanning confocal microscopy-PL spectrometry, and spectroscopic ellipsometry. In this work, BATHT-SAM was employed as an interfacial layer on SiO(2) to fabricate ultrathin film transistors (UTFTs, active layer thickness ～ 16.09 nm). The device UTFT-I, made of 0.06 wt % 5,5'-(9,10-bis(phenylethynyl)anthracene-2,6-diyl)bis(ethyne-2,1-diyl)bis(2-hexylthiophene) (BATHT) solution on an n-octyltrichlorosilane-SAM/SiO(2) layer, showed no gate effect for the carrier transport behavior; however, the device UTFT-II, fabricated on BATHT-SAM/SiO(2), exhibited field effect mobilities of 0.04 cm(2) V(-1) s(-1) (I(on/off) ～ 6.3 × 10(3) to 1.0 × 10(4)). This can be attributed to the effect of BATHT-SAM inducing uniform coverage and ordering of BATHT molecules as an upper layer.     

Quencher-free linear beacon systems containing 2-ethynylfluorenone-labeled 2′-deoxyuridine units

In this study we synthesized the 2-ethynylfluorenone-containing deoxyuridine derivative U^FO and incorporated it at the central positions of oligodeoxynucleotides (ODNs) in an attempt to develop a new type of quencher-free linear beacon probe and to understand the effect of functionalization of the fluorene scaffold on the photophysical properties of the fluorescent ODNs. Herein, we describe our photophysical studies of U^FO DNA probes and their application to single-nucleotide polymorphism typing.     

Influence of silver nanoclusters on formation of PbS quantum dots in glasses

Heat-treatment was used to precipitate PbS quantum dots (QDs) in silicate glasses doped with different amounts of Ag₂O, and the influence of Ag₂O on QDs was investigated. Under given heat-treatment conditions, the absorption coefficients and photoluminescence intensities of PbS QDs increased with the addition of Ag₂O. Ag clusters formed by thermal treatment nucleated formation of PbS QDs in glasses.     

Preparation and third-order optical nonlinearity of glass ceramics based on GeS2–Ga2S3–CsCl pseudo-ternary system

Chalcohalide glass-ceramics based on GeS₂–Ga₂S₃–CsCl pseudo-ternary system were prepared by heat treatment method. X-ray diffraction and scanning electron microscope studies confirmed the formations of Ga₂S₃ and GeS₂ phase grains with sizes of 2–5 and 80 nm, respectively. Z-scan technology was employed to investigate the third-order nonlinear optical characteristics of both precursor glass and its glass ceramics at 800 nm. The results show that nonlinear refractive index n₂ as well as nonlinear absorption coefficient β increase after heat treatment, which is due to quantum effects, and the largest n₂ of the glass ceramics is 4.3 × 10^? 11 esu which is 4 times larger than that of the host.     

Hybridization of DNA to bead-immobilized probes confined within a microfluidic channel

We report the factors influencing the capture of DNA by DNA-modified microbeads confined within a microfluidic channel. Quantitative correlation of target capture efficiency to probe surface concentration, solution flow rate, and target concentration are discussed. The results indicate that the microfluidic system exhibits a limit of detection of approximately 10(-10) M (approximately 10(-16) mol) DNA and a selectivity factor of approximately 8 x 10(3). Typical hybridization times are on the order of minutes.