Formation and Thermal Stability of Ordered Self-Assembled Monolayers by the Adsorption of Amide-Containing Alkanethiols on Au(111).

We examined the surface structure, binding conditions, electrochemical behavior, and thermal stability of self-assembled monolayers (SAMs) on Au(111) formed by N-(2-mercaptoethyl)heptanamide (MEHA) containing an amide group in an inner alkyl chain using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) to understand the effects of an internal amide group as a function of deposition time. The STM study clearly showed that the structural transitions of MEHA SAMs on Au(111) occurred from the liquid phase to the formation of a closely packed and well-ordered ß-phase via a loosely packed α-phase as an intermediate phase, depending on the deposition time. XPS measurements showed that the relative peak intensities of chemisorbed sulfur against Au 4f for MEHA SAMs formed after deposition for 1 min, 10 min, and 1 h were calculated to be 0.0022, 0.0068, and 0.0070, respectively. Based on the STM and XPS results, it is expected that the formation of a well-ordered ß-phase is due to an increased adsorption of chemisorbed sulfur and the structural rearrangement of molecular backbones to maximize lateral interactions resulting from a longer deposition period of 1 h. CV measurements showed a significant difference in the electrochemical behavior of MEHA and decanethiol (DT) SAMs as a result of the presence of an internal amide group in the MEHA SAMs. Herein, we report the first high-resolution STM image of well-ordered MEHA SAMs on Au(111) with a (3 × 2√3) superlattice (ß-phase). We also found that amide-containing MEHA SAMs were thermally much more stable than DT SAMs due to the formation of internal hydrogen networks in MEHA SAMs. Our molecular-scale STM results provide new insight into the growth process, surface structure, and thermal stability of amide-containing alkanethiols on Au(111).

Solvent Effect on the Formation of Octaneselenocyanate Self-Assembled Monolayers on Au(111).

Solvent effect on the formation and electrochemical behavior of octaneselenolate (C8Se) self-assembled monolayers (SAMs) on Au(111) derived from the adsorption of octaneselenocyanate (C8Se-CN) molecules in various solvents at 363 K for 1 h was examined by scanning tunneling microscopy (STM) and cyclic voltammetry (CV). STM imaging clearly revealed that the formation and structure of C8Se SAMs were markedly influenced by the polarity of solvent. C8Se SAMs formed in octane were composed of liquid-like disordered phase. In contrast, C8Se SAMs formed in DMF had ordered domains but not a uniform surface, whereas C8Se SAMs formed in ethanol had uniform surface and highly ordered domains with a (2 × 2 √13) structure. It was found that the structural quality of C8Se SAMs increased with increasing solvent polarity in the order of ethanol > DMF > octane. CV measurements also showed that blocking efficiency of C8Se SAMs for electrode reaction increased with increasing the structural quality of SAMs.

Unique ordered domains of biphenylthiol self-assembled monolayers on Au(111).

The surface structure and adsorption conditions of biphenylthiol (BPT) self-assembled monolayers (SAMs) on Au(111) were examined using scanning tunneling microscopy (STM) and X-ray photoelectron microscopy (XPS). STM imaging revealed that the structural order of BPT SAMs formed in a 0.01 mM ethanol solution at 60 degrees C decreases with increasing immersion time. Interestingly, BPT SAMs formed after 30 min have unique ordered domains containing well-ordered (square root of 3 x square root of 3)R30 degrees structures and bright rows that are connected by small aggregated domains with a periodicity of approximately 10 angstroms, results that have never been observed for other thiol SAM systems. Distances between the bright rows were 20-35 angstroms. The bright small domains contained five or six BPT molecules each, which may have originated from differences in the adsorption orientations of biphenyl groups that were induced by localized interactions between them. XPS measurements for BPT SAMs on Au(111) showed the two sulfur peaks at 161.2 and 162.2 eV, implying the formation of chemisorbed monolayers. Our results are anticipated to be useful for understanding the formation and structure of BPT SAMs on gold surfaces.

Characterization of a Novel Mannose-Binding Lectin with Antiviral Activities from Red Alga, Grateloupia chiangii.

Lectins have the ability to bind specific carbohydrates and they have potential applications as medical and pharmacological agents. The unique structure and usefulness of red algal lectin have been reported, but these lectins are limited to a few marine algal groups. In this study, a novel mannose-binding lectin from Grateloupia chiangii (G. chiangii lectin, GCL) was purified using antiviral screens and affinity chromatography. We characterized the molecular weight, agglutination activity, hemagglutination activity, and heat stability of GCL. To determine the carbohydrate specificity, a glycan microarray was performed. GCL showed strong binding affinity for Maltohexaose-ß-Sp1 and Maltoheptaose-ß-Sp1 with weak affinity for other monosaccharides and preferred binding to high-mannan structures. The N-terminal sequence and peptide sequence of GCL were determined using an Edman degradation method and LC-MS/MS, and the cDNA and peptide sequences were deduced. GCL was shown to consist of 231 amino acids (24.9 kDa) and the N-terminus methionine was eliminated after translation. GCL possessed a tandem repeat structure of six domains, similar to the other red algal lectins. The mannose binding properties and tandem repeat structure of GCL may confer it the potential to act as an antiviral agent for protection against viral infection.

Alpha- and beta-tubulin from Phytophthora capsici KACC 40483: molecular cloning, biochemical characterization, and antimicrotubule screening.

Internal fragments of alpha- and beta-tubulin genes were generated using reverse transcription polymerase chain reaction (RT-PCR), and the termini were isolated using 5'- and 3'-rapid amplification of cDNA ends. Phytophthora capsici alpha- and beta-tubulin specific primers were then used to generate full-length cDNA by RT-PCR. The recombinant alpha- and beta-tubulin genes were expressed in Escherichia coli BL21 (DE3), purified under denaturing conditions, and average yields were 3.38-4.5 mg of alpha-tubulin and 2.89-4.0 mg of beta-tubulin, each from 1-l culture. Optimum conditions were obtained for formation of microtubule-like structures. A value of 0.12 mg/ml was obtained as the critical concentration of polymerization of P. capsici tubulin. Benomyl inhibited polymerization with half-maximal inhibition (IC(50)) = 468 +/- 20 microM. Approximately 18.66 +/- 0.13 cysteine residues per tubulin dimer were accessible to 5,5'-dithiobis-(2-nitrobenzoic acid), a quantification reagent of sulfhydryl and 12.43 +/- 0.12 residues were accessible in the presence of 200 microM benomyl. The order of preference for accessibility to cysteines was benomyl > colchicine > GTP > taxol, and cysteine accessibility changes conformed that binding sites of these ligands in tubulin were folding correctly. Fluorescence resonance energy transfer technique was used for high throughput screening of chemical library in search of antimitotic agent. There was significant difference in relative fluorescence by 210-O-2 and 210-O-14 as compared to colchicine.

Cloning, purification, and polymerization of Capsicum annuum recombinant alpha and beta tubulin.

Alpha and beta tubulin genes were cloned from the Capsicum annuum leaves using rapid amplification of cDNA ends (RACE)-PCR. Nucleotide sequence analysis revealed that 1,353 bp Capsicum annuum alpha/beta-tubulin (CAnm alpha/beta-TUB) encodes a protein of 450 amino acids (aa) each. The recombinant alpha/beta tubulin was overexpressed mainly as an inclusion body in Escherichia coli BL21 (DE3), upon induction with 0.2 mM isopropyl-beta-D-thiogalactopyranoside (IPTG), and its content was as high as 50% of the total protein content. Effective fusion protein purification and refolding are described. The average yields of alpha and beta tubulin were 2.0 and 1.3 mg/l of culture respectively. The apparent molecular weight of each tubulin was estimated to be 55 kDa by SDS-polyacrylamide gel electrophoresis (PAGE). The tubulin monomers were found to be assembly competent using a standard dimerization assay, and also retained antigenicity with anti-His/T7 antibodies. The purified tubulins were polymerized to microtubule-like structures in the presence of 2 mM guanosine 5'-triphosphate (GTP).

In-Water and Neat Batch and Continuous-Flow Direct Esterification and Transesterification by a Porous Polymeric Acid Catalyst.

A porous phenolsulphonic acid-formaldehyde resin (PAFR) was developed. The heterogeneous catalyst PAFR was applied to the esterification of carboxylic acids and alcohols, affording the carboxylic acid esters in a yield of up to 95% where water was not removed from the reaction mixture. Surprisingly, the esterification in water as a solvent proceeded to afford the desired esters in high yield. PAFR provided the corresponding esters in higher yield than other homogeneous and heterogeneous catalysts. The transesterification of alcohols and esters was also investigated by using PAFR, giving the corresponding esters. PAFR was applied to the batch-wise and continuous-flow production of biodiesel fuel FAME. The PAFR-packed flow reactor that was developed for the synthesis of carboxylic acids and FAME worked for four days without loss of its catalytic activity.

The exothermic reaction route of a self-heatable conductive ink for rapid processable printed electronics.

We report the exothermic reaction route and new capability of a self-heatable conductive ink (Ag2O and silver 2,2-dimethyloctanoate) in order to achieve both a low sintering temperature and electrical resistivity within a short sintering time for flexible printed electronics and display appliances. Unlike conventional conductive ink, which requires a costly external heating instrument for rapid sintering, self-heatable conductive ink by itself is capable of generating heat as high as 312 °C when its exothermic reaction is triggered at a temperature of 180 °C. This intensive exothermic reaction is found to result from the recursive reaction of the 2,2-dimethyloctanoate anion, which is thermally dissociated from silver 2,2-dimethyloctanoate, with silver oxide microparticles. Through this recursive reaction, a massive number of silver atoms are supplied from silver oxide microparticles, and the nucleation of silver atoms and the fusion of silver nanoparticles become the major source of heat. This exothermic reaction eventually realizes the electrical resistivity of self-heatable conductive ink as low as 27.5 µΩ cm within just 40 s by combining chemical annealing, which makes it suitable for the roll-to-roll printable electronics such as a flexible touch screen panel.

Aerobic oxygenative cleavage of electron deficient C-C triple bonds in the gold-catalyzed cyclization of 1,6-enynes.

Gold-catalyzed aerobic oxygenative cleavage of triple bonds that occurs under the ambient pressure of air and at room temperature is reported; radical inhibition tests suggest that oxygenation occurs via a gold-bound metalloradical intermediate.

Direct dehydrative esterification of alcohols and carboxylic acids with a macroporous polymeric acid catalyst.

A macroporous polymeric acid catalyst was prepared for the direct esterification of carboxylic acids and alcohols that proceeded at 50-80 °C without removal of water to give the corresponding esters with high yield. Flow esterification for the synthesis of biodiesel fuel was also achieved by using a column-packed macroporous acid catalyst under mild conditions without removal of water.

1,3-Dipolar cycloaddition of 4-platinumisochromenyliums with an olefin and tandem insertion into benzylic C-H bonds.

Isochromenylium-4-ylplatinum(II) species, generated from 1-(2-alkynylphenyl)hex-5-en-1-ones and Pt(II), reacted with a pendant olefin via [3+2] cycloaddition to form tetracyclic Pt-carbene complexes, which underwent C-H insertion with a benzyloxy group at δ or ε positions to give highly complex polycycles, which are otherwise hard to access.

Characterization of Capsicum annuum recombinant alpha- and beta-tubulin.

There are several conditions which might modulate polymerization to produce polymers having normal lattice structure. In the absence of 1 mM MgCl(2) the assembly was reduced by 36% in Capsicum annuum tubulin (CAnm tubulin). There was no significant difference in the final assembly formation in the presence of 5% to 10% glycerol. However, nucleation rate was slow and apparent study state was achieved lately in the presence of 10% glycerol. Taxol at 100 microM concentration increased 23% tubulin assembly. One millimolar CaCl(2), >or=1% dimethyl sulfoxide (DMSO) and physiologically low temperature reduced CAnm tubulin assembly. A value of 0.089 mg/ml was obtained as critical concentration for polymerization. Benomyl significantly reduced the number of cysteine residues accessible to 5,5'-dithiobis-(2-nitrobenzoic acid); there were 4.77 +/- 0.21 and 3.49 +/- 0.35 residues accessible per tubulin dimer in the presence of 50 and 100 microM benomyl respectively.

Improved accuracy of on-line heavy water measurement using infrared spectroscopy by investigation of signal-to-noise ratio and temperature influences.

Experimental protocols for the on-line measurement of heavy water concentration in nuclear power plants have been established, and important parameters, such as the temperature and signal-to-noise ratio, which govern the accuracy of measurement, have been studied. The temperature of a sample should be controlled tightly because the temperature variation introduces non-linear baseline variations and leads to an increase of the partial least squares calibration error. Furthermore, the variation in the signal-to-noise ratio of spectra sensitively influences the calibration. For reliable prediction, it is critical to maintain the signal-to-noise ratio at a certain level. When the sample spectra were collected at a higher temperature, it was possible to acquire spectra with an improved signal-to-noise ratio and better calibration. In addition, a single beam spectrum of water shifts to a lower frequency, and the maximum transmission intensity at around 2500 cm(-1)(the heavy water band location) increases at an elevated temperature. Overall, an on-line infrared spectroscopic scheme is presented for measuring heavy water. The scheme can be applied to an actual process without practical difficulties. If the spectra could be collected at elevated temperature over 2 min with the use of a high throughput light source, the prediction error could reach to 1.0 ppm.

Rhodium-catalyzed asymmetric 1,4-addition of aryltitanium reagents generating chiral titanium enolates: isolation as silyl enol ethers.

The addition of aryltitanium triisopropoxide (ArTi(OPr-i )3) to alpha,beta-unsaturated ketones proceeded with high enantioselectivity (94-99.8% ee) in the presence of 3 mol % of [Rh(OH)((S )-binap)]2 in THF at 20 degrees C to give high yields of the titanium enolates as 1,4-addition products. The titanium enolates were converted into silyl enol ethers by treatment with chlorotrimethylsilane and lithium isopropoxide.

Syntheses of regioisomerically pure 5- or 6-halogenated fluoresceins.

Three routes to regioisomerically pure 5- and 6-iodofluoresceins or 5- and 6-bromofluoresceins are described. The first, shown in Scheme 1, involves diazotization/iodination of the corresponding aminofluoresceins. In the second approach (Scheme 2) a mixture of regioisomeric fluoresceins was prepared, and the 5-bromo isomers were isolated as the ring closed diacetates 9b and 11 by fractional crystallization. Scheme 3 shows an approach to sulfonic acid derivatives 3 and 4 of 5-iodofluorescein. This is the most convenient procedure of the three, and it is particularly useful as sulfofluoresceins have more favorable water solubility characteristics than fluoresceins that lack the sulfonic acid group.

Asymmetric synthesis of 1-aryl-1,2-ethanediols from arylacetylenes by palladium-catalyzed asymmetric hydrosilylation as a key step.

Double hydrosilylation of arylacetylenes with trichlorosilane catalyzed first by platinum and second by a chiral monophosphine-palladium complex generated the corresponding 1,2-bis(silyl)-1-arylethanes, the oxidation of which with hydrogen peroxide gave 1-aryl-1,2-diols of high enantiomeric purity (94-98% ee) in high yields.