Surface modified microarray chip and laser induced fluorescence microscopy to detect DNA cleavage

This work describes a quantitative method to detect DNA damage in the presence of Pb and Cd ions using a surface modified microarray chip and a laser induced fluorescence microscopy (LIFM). The detection was carried out by the immobilization of a single-stranded DNA oligomer, tagged with a Cy5 fluorophore on a polydimethylsiloxane (PDMS) microarray chip followed by LIFM. Sulfosuccinimidyl-4-(N-maleimidomethyl) cyclohexane-1-carboxylate (Sulfo-SMCC) was attached as a cross-linker via the formation of covalent amide bonds. Then, the single-stranded DNA oligomer containing Cy5 as a fluorophore and thiol functional groups at both terminals, was bonded to the linker by reaction with sulfhydryl group. As the DNA oligomers were reacted with metal ions of Pb and Cd, the un-cleaved DNA oligomers were quantitatively identified by monitoring Cy5 fluorescence. Cadmium showed a quenching constant of 0.84 in the Stern–Volmer plot, whereas lead gave 0.22, indicating that cadmium ions suppress fluorescence more than lead ions. When optimized, fluorescence reductions of 23% (± 2.1) for Pb and 25% (± 1.4) for Cd were observed in air and decreased to almost < 5.0% in a radical scavenger of 5 mM. The cleaved DNA was also confirmed by MALDI-TOF-MS. In result, this experimental method using a microarray chip with surface modification provided quantitative determination of DNA oligomer damage with reproducible results, significantly reduced sample volumes and analysis times.     

Voltammetric sensing of paracetamol, dopamine and 4-aminophenol at a glassy carbon electrode coated with gold nanoparticles and an organophillic layered double hydroxide

A differential pulse voltammetric method was developed for the simultaneous determination of paracetamol, 4-aminophenol and dopamine at pH 7.0 using a glassy carbon electrode (GCE) coated with gold nanoparticles (AuNPs) and a layered double hydroxide sodium modified with dodecyl sulfate (SDS-LDH). The modified electrode displays excellent redox activity towards paracetamol, and the redox current is increased (and the corresponding over-potential decreased) compared to those of the bare GCE, the AuNPs-modified GCE, and the SDS-LDH-modified GCE. The modified electrode enables the determination of paracetamol in the concentration range from 0.5 to 400???M, with a detection limit of 0.13???M (at an S/N of 3). The sensor was successfully applied to the stimultaneous determination of paracetamol and dopamine, and of paracetamol and 4-aminophenol, respectively, in pharmaceutical tablets and in spiked human serum samples.

A new naturally derived photosensitizer and its phototoxicity on head and neck cancer cells

In our screening for photosensitizers from natural resources, 15(1)-hydroxypurpurin-7-lactone ethyl methyl diester (compound 1) was isolated for the first time from an Araceae plant. To evaluate the efficacy of compound 1 as a photosensitizer for head and neck cancers, compound 1 was studied in reference to a known photosensitizer pheophorbide-a (Pha), in terms of photophysical properties, singlet oxygen generation and in in vitro experiments (intracellular uptake and phototoxicity assays) in two oral (HSC2 and HSC3) and two nasopharyngeal (HK1 and C666-1) cancer cell lines. In this study, compound 1 exhibited higher intracellular uptake over 24 h compared with Pha in both HSC3 and HK1 cells. When activated by ≥4.8 J cm(-2) of light, compound 1 was slightly more potent as a photosensitizer than Pha by consistently having marginally lower IC(50) values across different cell lines. In flow cytometry experiments to study the mechanism of photoactivated cell death in HSC3, compound 1 was observed to induce more pronounced apoptosis compared with Pha, which may have been driven by the transient G(2)/M cell cycle block which was also observed. These promising results on compound 1 warrant its further investigation as a clinically useful photodynamic therapy agent for head and neck cancer.     

High speed injection molding of high density polyethylene �� Effects of injection speed on structure and properties

Thin wall samples of high density polyethylene (HDPE) were prepared via injection molding with different injection speeds ranging from 100 mm/s to 1200 mm/s. A significant decrease in the tensile strength and Young??s modulus was observed with increasing injection speed. In order to investigate the mechanism behind this decrease, the orientation, molecular weight, molecular weight distribution, melt flow rate, crystallinity and crystal morphology of HDPE were characterized using two-dimensional wide-angle X-ray diffraction (2D-WAXD), gel permeation chromatography (GPC), capillary rheometry and differential scanning calorimetry (DSC), respectively. It is demonstrated that the orientation, molecular weight, molecular weight distribution, melt flow rate and crystallinity have no obvious change with increasing injection speed. Nevertheless, the content of extended chain crystals or large folded chain crystals was found to decrease with increasing injection speed. Therefore, it is concluded that the decrease in tensile properties is mainly contributed by the reduced content of extended chain crystals or large folded chain crystals. This study provides industry with valuable information for the application of high speed injection molding.     

Biosynthesis of Ribostamycin Derivatives by Reconstitution and Heterologous Expression of Required Gene Sets

Ribostamycin is a 4,5-disubstituted 2-deoxystreptamine (DOS)-containing aminoglycoside antibiotics and naturally produced by Streptomyces ribosidificus ATCC 21294. It is also an intermediate in the biosynthesis of butirosin and neomycin. In the biosynthesis of ribostamycin, DOS is glycosylated to generate paromamine which is converted to neamine by successive dehydrogenation followed by amination, and finally ribosylation of neamine gives ribostamycin. Here, we report the biosynthesis of 6′-deamino-6′-hydroxyribostamycin (a ribostamycin derivative or pseudoribostamycin) in Streptomyces venezuelae YJ003 by reconstructing gene cassettes for direct ribosylation of paromamine. A trace amount of pseudoribostamycin was detected with ribostamycin in the isolates of ribostamycin cosmid heterologously expressed in Streptomyces lividans TK24. It has also indicated that the ribosyltransferase can accept both neamine and paromamine. Thus, the present in vivo modification of ribostamycin could be useful for the production of hybrid compounds to defend against bacterial resistance to aminoglycosides.     

Cycloaddition reactions: a controlled approach for carbon nanotube functionalization

Controlled functionalization of carbon nanotubes (CNTs) through the use of cycloaddition reactions is described. By employing various cycloaddition reactions, a wide range of molecules could be coupled onto CNTs without disruption of the structural integrity as well as with a statistical distribution of functional groups onto the surface of the CNTs. The cycloaddition reactions represent an effective and tailored approach for preparing CNT-based advanced hybrid materials that would be useful for a wide range of applications from nanobiotechnology to nanoelectronics.     

微波辐射法制备水溶性CdTe/ZnS量子点及其与司帕沙星的作用

以巯基乙酸为稳定剂,通过微波加热在水溶液中制备了CdTe/znS量子点.研究了pH值、反应时间、反应温度和cdTe/s<'2->浓度比等合成条件对cdTe量子点荧光光谱的影响.以CdTe/ZnS量子点为探针,探讨了喹诺酮类抗生素司帕沙星与量子点的荧光猝灭作用,结果表明,在最佳实验条件下,其线性范围为0.05～3.00μg/mL,线性相关系数为0.9954,检出限为0.01μg/mL,可将CdTe/ZnS量子点荧光探针用于司帕沙星的测定.     

2,5-Bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione-based donor-acceptor alternating copolymer bearing 5,5'-di(thiophen-2-yl)-2,2'-biselenophene exhibiting 1.5 cm2·V(-1)·s(-1) hole mobility in thin-film transistors

A novel diketopyrrolopyrrole-based π-conjugated copolymer P(DPP-alt-DTBSe), 5, and a known copolymer P(DPP-alt-QT), 4, have been synthesized in 80-90% yield using the Stille coupling reaction. The molecular weights of 4 and 5 are 58,781 and 19,271 g/mol, respectively, with polydispersity values of 3.25-3.35. A relatively small band gap of 1.32-1.39 eV and excellent solubility in organic solvents were achieved in the two polymers. Thin-film transistors made of 5 exhibit outstanding performance (e.g., μ > 1.0-1.5 cm(2)·V(-1)·s(-1), I(on)/I(off) > 10(5)-10(6)) with a conventional n-octyltrichlorosilane-SiO(2) gate dielectric.     

Core-Clickable PEG-Branch-Azide Bivalent-Bottle-Brush Polymers by ROMP: Grafting-Through and Clicking-To

The combination of highly efficient polymerizations with modular "click" coupling reactions has enabled the synthesis of a wide variety of novel nanoscopic structures. Here we demonstrate the facile synthesis of a new class of clickable, branched nanostructures, polyethylene glycol (PEG)-branch-azide bivalent-brush polymers, facilitated by "graft-through" ring-opening metathesis polymerization of a branched norbornene-PEG-chloride macromonomer followed by halide-azide exchange. The resulting bivalent-brush polymers possess azide groups at the core near a polynorbornene backbone with PEG chains extended into solution; the structure resembles a unimolecular micelle. We demonstrate copper-catalyzed azide-alkyne cycloaddition (CuAAC) "click-to" coupling of a photocleavable doxorubicin (DOX)-alkyne derivative to the azide core. The CuAAC coupling was quantitative across a wide range of nanoscopic sizes (～6-～50 nm); UV photolysis of the resulting DOX-loaded materials yielded free DOX that was therapeutically effective against human cancer cells.