Water cluster anions studied by the long-range corrected density functional theory

Long-range corrected density functional theory (LC-DFT) is applied to a series of small water cluster anions(n= 2-6) to compute their vertical detachment energies (VDEs). The LC scheme is shown to eliminate an unphysical overestimation of the electron-water attraction in the hybrid functional by properly accounting for the long-range exchange repulsions. It is shown that a correct correlation energy behavior for a rapidly varying density is also important for describing a spatially extent, excess electron. The one-parameter progressive (OP) correlation functional, which satisfies this condition, leads to a remarkable improvement in the calculated VDE over the conventional one. The LC-BOP method produces highly accurate VDEs with a mean absolute deviation of 13.8 meV from the reference CCSD(T) results, reducing the error of B3LYP by more than 15 times. LC-BOP is found to be more accurate than MP2 which yields an excess electron underbound by 43.6 meV. The effect of basis sets on the calculated VDE is also examined. The aug-cc-pVDZ basis set with an extra diffuse function is found to be more accurate and reliable than the extended Pople-type basis sets used in the previous works. The extrapolation of the calculated VDE of different electron binding motifs is compared with the VDEs of experimentally observed three isomers (Verlet, J. R. R.; Bragg,A. E.; Kammrath, A.; Cheshnovsky, O.; Neumark, D. M. Science 2005, 307, 93).     

Oligonucleotide analysis by nanoparticle-assisted laser desorption/ionization mass spectrometry

We analyzed oligonucleotides by nanoparticle-assisted laser desorption/ionization (nano-PALDI) mass spectrometry (MS). To this end, we prepared several kinds of nanoparticles (Cr-, Fe-, Mn-, Co-based) and optimized the nano-PALDI MS method to analyze the oligonucleotides. Iron oxide nanoparticles with diammonium hydrogen citrate were found to serve as an effective ionization-assisting reagent in MS. The mass spectra showed both [M - H](-) and [M + xMe(2+)- H](-) (Me: transition metal) peaks. The number of metal-adducted ion signals depended on the length of the oligonucleotide. This phenomenon was only observed using bivalent metal core nanoparticles, not with any other valency metal core nanoparticles. Our pilot study demonstrated that iron oxide nanoparticles could easily ionize samples such as chemical drugs and peptides as well as oligonucleotides without the aid of an oligonucleotide-specific chemical matrix (e.g., 3-hydroxypicolinic acid) used in conventional MS methods. These results suggested that iron-based nanoparticles may serve as the assisting material of ionization for genes and other biomolecules.     

Rh-catalyzed [5+1] and [4+1] cycloaddition reactions of 1,4-enyne esters with CO: a shortcut to functionalized resorcinols and cyclopentenones

We have developed novel Rh-catalyzed [n+1]-type cycloadditions of 1,4-enyne esters, which involve an acyloxy migration as a key step. The efficient preparation of functionalized resorcinols, including biaryl derivatives, from readily available 1,4-enyne esters and CO was achieved by Rh-catalyzed [5+1] cycloaddition accompanied by 1,2-acyloxy migration. When enyne esters had an internal alkyne moiety, the reaction proceeded by a [4+1]-type cycloaddition involving 1,3-acyloxy migration, leading to cyclopentenones.     

Synthesis and Structure of Two New Mycolactones Isolated from M. ulcerans subsp. shinshuense

Two new mycolactones, mycolactones S1 and S2, were isolated from culture agar of Mycobacterium ulcerans subsp. shinshuense. Their structures were established in a three-step procedure: (1) probable structures were speculated from MS analysis; (2) candidates were synthesized; (3) HPLC profiles were established for identification of the natural products. Newly isolated mycolactones correspond to the "oxidized forms" of mycolactone A/B, the causative toxin of Buruli ulcer, isolated from Mycobacterium ulcerans.     

An sp2 and sp3 hybrid nanocrystalline carbon film electrode for anodic stripping voltammetry and its application for electrochemical immunoassay

A hybridized nanocrystalline carbon film electrode consisting of sp(2) and sp(3) bonds was investigated to reveal the reduction properties of Cd(2+) and for application as a highly sensitive and reliable electrochemical immunoassay. Conductive nanocrystalline carbon film consisting of about 60% sp(2) and 40% sp(3) bonds was fabricated using electron cyclotron resonance (ECR) sputtering equipment, and then the Cd(2+) concentrations were measured with an ECR sputtered carbon (ECR nano-carbon) electrode by employing an anodic stripping voltammetry (ASV) technique. The preconcentrated Cd was analyzed with Kelvin probe force microscopy and energy dispersive X-ray spectroscopy while observing the morphology change with an atomic force microscope and a scanning electron microscope. The preconcentrated Cd on the ECR nano-carbon electrode was revealed to be a thin sheet structure, which was significantly different from the Cd on a conventional carbon material that grows with a coralloid structure. The background current during an ASV measurement maintains a low level equivalent to that found with boron-doped diamond because the surface of the ECR nano-carbon is robust and angstrom-level flat. The carbon-electrode performance for ASV was improved by controlling its structure at a nanometer scale without any metal doping or coating. Finally, the ECR nano-carbon was used for biomolecular determination by electrochemical immunoassay with a CdSe nanoparticle label. Electrochemical immunoassay results were successfully obtained with the ECR nano-carbon, and they correlated well with fluorescence results obtained for CdSe nanoparticles.     

Preparation of a cellulose-based enzyme membrane using ionic liquid to lengthen the duration of enzyme stability

A novel method for preparing enzyme membranes was developed. The enzyme was attached onto the electrode surface by dropping the enzyme solution and allowing it to dry. Glucose oxidase was used for entrapment. Then, the electrode surface was coated with an ionic liquid containing cellulose, and the ionic liquid was removed by immersing the electrode into water. Enzyme activity was retained in the membrane; the enzyme electrode can be used for detecting glucose in the range of 10 μM to 1 mM, and the response time was ~10 s. The stability duration of the electrode was examined: the enzyme electrode could be used for glucose detection for 6 months. The membrane was observed by atomic force microscopy in the force modulation mode; crystalline and amorphous parts were intermingled. In conclusion, the cellulose membrane can be a suitable immobilization matrix for enzymes.     

Potassium tert-butoxide-mediated regioselective silaboration of aromatic alkenes

The regio- and diastereoselective silaboration of aromatic alkenes with a silylboron compound proceeds in the presence of a catalytic amount of potassium tert-butoxide, providing a complementary method to the corresponding transition metal-catalyzed reactions.     

Strictly diastereocontrolled photocyclodimerization of 2-anthracenecarboxylates tethered to cyclic tetrasaccharides

Photocyclodimerization of 2-anthracenecarboxylate tethered to a cyclic nigerosylnigerose scaffold gave a single chiral cyclodimer (out of two achiral and two chiral stereoisomers) in 99% optical and 96% chemical yields, achieving the ultimate stereocontrol of the supramolecular photochirogenesis in aqueous solution at 25 °C.     

Synthesis of 2RS,4RS-1-[2-phenyl-4-[2-(2-trifluromethoxy-phenoxy)-ethyl]-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole derivatives as potent inhibitors of brassinosteroid biosynthesis

Brassinosteroids are important phytohormones that affect many aspects of plant growth and development. In order to manipulate brassinosteroid levels in plant tissues by using specific biosynthesis inhibitors, we have carried out a systemic search for specific inhibitors of brassinosteroid biosynthesis. Synthesis of triazole derivatives based on the ketoconazole scaffold revealed a series of novel brassinosteroid biosynthesis inhibitors (the YCZ series). To explore the structure-activity relationships of this synthetic series, we now report the synthesis of new triazole derivatives with different aromatic structures at position 2 of 1,3-dioxolane skeleton. We found that the variation of aromatic substituent significantly affect the inhibitory potency. Structure-activity relationships studies indicated that 4-chlorophenyl analogue is the most potent inhibitor of BR biosynthesis with an IC?? value approximately 0.12 ± 0.04 μM, while a bulky biphenyl group exhibited a great negative effect on promoting the inhibitory potency with an IC?? larger than 10 μM.     

Rapid,simple, and highly sensitive analysis of drugs in biological samples using thin-layer chromatography coupled with matrix-assisted laser desorption/ionization mass spectrometry

Rapid and precise identification of toxic substances is necessary for urgent diagnosis and treatment of poisoning cases and for establishing the cause of death in postmortem examinations. However, identification of compounds in biological samples using gas chromatography and liquid chromatography coupled with mass spectrometry entails time-consuming and labor-intensive sample preparations. In this study, we examined a simple preparation and highly sensitive analysis of drugs in biological samples such as urine, plasma, and organs using thin-layer chromatography coupled with matrix-assisted laser desorption/ionization mass spectrometry (TLC/MALDI/MS). When the urine containing 3,4-methylenedioxymethamphetamine (MDMA) without sample dilution was spotted on a thin-layer chromatography (TLC) plate and was analyzed by TLC/MALDI/MS, the detection limit of the MDMA spot was 0.05 ng/spot. The value was the same as that in aqueous solution spotted on a stainless steel plate. All the 11 psychotropic compounds tested (MDMA, 4-hydroxy-3-methoxymethamphetamine, 3,4-methylenedioxyamphetamine, methamphetamine, p-hydroxymethamphetamine, amphetamine, ketamine, caffeine, chlorpromazine, triazolam, and morphine) on a TLC plate were detected at levels of 0.05 − 5 ng, and the type (layer thickness and fluorescence) of TLC plate did not affect detection sensitivity. In addition, when rat liver homogenate obtained after MDMA administration (10 mg/kg) was spotted on a TLC plate, MDMA and its main metabolites were identified using TLC/MALDI/MS, and the spots on a TLC plate were visualized by MALDI/imaging MS. The total analytical time from spotting of intact biological samples to the output of analytical results was within 30 min. TLC/MALDI/MS enabled rapid, simple, and highly sensitive analysis of drugs from intact biological samples and crude extracts. Accordingly, this method could be applied to rapid drug screening and precise identification of toxic substances in poisoning cases and postmortem examinations.