Quantitative real-time measurements of DNA hybridization with alkylated nonoxidized silicon nanowires in electrolyte solution

The quantitative, real-time detection of single-stranded oligonucleotides with silicon nanowires (SiNWs) in physiologically relevant electrolyte solution is demonstrated. Debye screening of the hybridization event is circumvented by utilizing electrostatically adsorbed primary DNA on an amine-terminated NW surface. Two surface functionalization chemistries are compared: an amine-terminated siloxane monolayer on the native SiO2 surface of the SiNW, and an amine-terminated alkyl monolayer grown directly on a hydrogen-terminated SiNW surface. The SiNWs without the native oxide exhibit improved solution-gated field-effect transistor characteristics and a significantly enhanced sensitivity to single-stranded DNA detection, with an accompanying 2 orders of magnitude improvement in the dynamic range of sensing. A model for the detection of analyte by SiNW sensors is developed and utilized to extract DNA-binding kinetic parameters. Those values are directly compared with values obtained by the standard method of surface plasmon resonance (SPR) and demonstrated to be similar. The nanowires, however, are characterized by higher detection sensitivity. The implication is that SiNWs can be utilized to quantitate the solution-phase concentration of biomolecules at low concentrations. This work also demonstrates the importance of surface chemistry for optimizing biomolecular sensing with silicon nanowires.     

Nanoimaging and spectroscopic analysis of rubber/ZnO interfaces by energy-filtering transmission electron microscopy

Energy-filtering transmission electron microscopy (EFTEM) was employed for investigating interactions between rubber and ZnO particles in the accelerated vulcanization process. Combining elemental mapping and electron energy loss spectroscopy (EELS) by EFTEM enabled the characterization of the interfaces with spatial resolutions of less than 10 nm and with high elemental detection sensitivity. We found that a sulfur- and zinc-rich compound was generated around ZnO particles, and that product was then revealed to be ZnS-generated as a byproduct in the accelerated vulcanization process. Through this study, it is indicated that the accelerated vulcanization with ZnO does not occur uniformly in the rubber matrix; it occurs locally around ZnO particles at a higher reaction rate, implying that the rubber network structure is not uniform on the nanoscale.     

Concise total syntheses of palominol, dolabellatrienone, beta-araneosene, and isoedunol via an enantioselective Diels-Alder macrobicyclization

Concise total syntheses of four members of the dolabellane family of diterpenoid natural products are reported. Key features of the developed route include the first demonstration of an enantioselective, intramolecular Type I Diels-Alder macrobicyclization, the first example of a stereoselective pi-allyl Stille coupling reaction involving a farnesyl-derived intermediate, a powerful new reagent for the formation of dithianes with acid-sensitive molecules, and a unique and highly efficient ring-contraction sequence based on a modified Wolff photochemical rearrangement.     

Histidine-tagged shiga toxin B subunit binding assay: simple and specific determination of gb3 content in mammalian cells

A two-step binding assay for globotriaosylceramide (Gb3) content was developed by histidine-tagging strategy, which is a well-established method for the purification of recombinant proteins. The complete binding of the recombinant His-tagged Shiga toxin 1B subunit (1B-His) (1 microg/ml) to the standard Gb3 adsorbed on a multi-well H type plate was observed within 30 min at 37 degrees C; and its binding could be visualized by the following applications of HisProbe-HRP (8 microg/ml) and tetramethylbenzidine (TMB) peroxidase substrate. The 1B-His binding assay was linear over the range of 1 to 100 ng of Gb3 per well. The binding of 1B-His was specific to Gb3 separated from HeLa cells, and no major cross-reactivity of other glycolipids in Folch's lower fractions extracted from HeLa cells was detected. The glycolipids in Folch's lower fractions from HeLa cells, human fibroblasts and mouse heart were suitable for this assay, but the further purification was needed for glycolipids from human plasma, thus sample preparation is critical factor for the reliable determination of Gb3 content. The 1B-His binding to Gb3 was inhibited by the addition of galactose, but not mannose. This 1B-His binding assay will be useful not only for the determination of Gb3 content, but also for screening for the compounds which inhibit the toxin-binding to Gb3. The strategy of our present method may be applicable for other binding assay, such as Cholera toxin B-subunit for ganglioside GM1.     

Determination of the propylene oxide-hemoglobin adduct by gas chromatography-electron impact ionization mass spectrometry

A gas chromatography-mass spectrometry method was developed for the determination of the propylene oxide (PO)-hemoglobin adduct. The adduct was identified as hydroxy propyl valine (HPV), and released from globin by the modified Edman degradation and extracted with ethyl ether. HPV and deuterated HPV (d6-HPV) were synthesized for identification and quality control. d6-HPV was used as an internal reference standard. The dried extract was completely derivatized with N-methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA). The method detection limit (MDL) of the assay was 10 pmole/g for HPV, based on assayed hemoglobin of 0.1 g. The method was applied to the determination of the PO-hemoglobin adduct formed in young female Sprague-Dawley rats after treatment for 4 and 5 weeks with 5 and 10 mM PO via drinking water. HPV was detected by the proposed procedure. After 4 weeks, the concentration of HPV was 6.75 nmole/g hemoglobin during treatment with 5 mM, and 80.26 nmole/g hemoglobin during treatment with 10 mM. The adduct level in 5 weeks increased up to about 51.47 nmole/g during treatment with 5 mM PO in the drinking water and up to about 120.27 nmole/g during treatment with 10 mM PO. This method was also applied to determine the concentrations of HPV in the blood of 20 persons living near the Ulsan petroleum industrial complex in Korea. As a result, HPV-hemoglobin adduct was detected in the concentration range 0-1100 pmol/g in the human blood samples.     

Tandem nucleophilic addition/fragmentation reactions and synthetic versatility of vinylogous acyl triflates

A thorough analysis of the chemistry of vinylogous acyl triflates provides insight into important chemical processes and opens new directions in synthetic technology. Tandem nucleophilic addition/C-C bond cleaving fragmentation reactions of cyclic vinylogous acyl triflates 1 yield a variety of acyclic acetylenic compounds. Full details are disclosed herein. A wide array of nucleophiles, such as organolithium and Grignard reagents, lithium enolates and their analogues, hydride reagents, and lithium amides, are applied. The respective reactions produce ketones 2, 1,3-diketones and their analogues 3, alcohols 4, and amides 5. The present reactions are proposed to proceed through a 1,2-addition of the nucleophile to the carbonyl group of starting triflates 1 to form tetrahedral alkoxide intermediates C, followed by Grob-type fragmentation, which effects C-C bond cleavage to yield acyclic acetylenic compounds 2-5 and 7. The potent nucleofugacity of the triflate moiety is channeled through the sigma-bond framework of 1, providing direct access to the fragmentation pathway without denying other typical reactions of cyclic vinylogous esters. The synthetic versatility of vinylogous acyl triflates, including functionalization reactions of the cyclic enone core (1 --> 6 or 8), is also illustrated.     

Characteristics of the series resonant-frequency shift of a quartz crystal microbalance in electrolyte solutions

We report the novel characteristics of the series resonant-frequency shift, DeltaF, of a one-face sealed quartz crystal microbalance (QCM) in solutions of monovalent electrolytes and divalent electrolytes. In the present study, we used NaCl, KCl, LiCl, NaNO3 and CH3COONa as monovalent electrolytes, and MgCl2, CaCl2, MgSO4 and Na2SO4 as divalent electrolytes. These experiments reveal that, in all the solutions, the DeltaF values vary linearly with an increase in the square root of the density-viscosity product of the solutions, and the immersion angle dependence of DeltaF appears. Moreover, we have found that the intercept values of DeltaF are dependent only on the cation species, and that the slope values of DeltaF with the viscosity and density of the solutions are related only to the valence of ions. We also suggest that the DeltaF values are independent of anion species, conductivity and permittivity of the solutions.     

Diiron amido-imido complex [(CpFe)2(mu2-NHPh)(mu2-NPh)]: synthesis and a net hydrogen atom abstraction reaction to form a bis(imido) complex

A reaction between [CpFeCl]x and LiNHPh (1 equiv to Fe) produces a new paramagnetic Fe(II)-Fe(III) mu2-amido-mu2-imido complex [(CpFe)2(mu2-NHPh)(mu2-NPh)] (1), which, upon interaction with 2,2'-azobis(2,4-dimethylvaleronitrile), undergoes a net N-H hydrogen atom abstraction reaction to give a diamagnetic Fe(III)-Fe(III) mu2-imido dimer [CpFe(mu2-NPh)]2 (2). The molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction.     

Facile approach for diblock codendrimers by fusion between Fréchet dendrons and PAMAM dendrons

For the first time, a simple and facile approach for the synthesis of diblock codendrimers by fusion between the azide focal point functionalized Fréchet-type polyether and the propargyl focal point functionalized Tomalia-type PAMAM dendrons has been described based on click chemistry, i.e., the copper-catalyzed cycloaddition reaction between alkyne and azide.     

Coaxial holographic data storage without recording the dc components

A technique of recovering the data pages from Fourier holograms recorded without the dc components is demonstrated theoretically and experimentally by use of a coaxial holographic storage system. A reconstructed image is obtained by adding a phase-modulated dc component of the signal beam on reading. The bit error rate of the reconstructed image is comparable with that for the hologram recorded with the dc component as well. Since high intensities of the dc components are not recorded in this technique, the dynamic range of the recording media can be saved, which potentially contributes to increasing the number of multiplexed holograms.