On-chip magnetically actuated robot with ultrasonic vibration for single cell manipulations

This paper presents an innovative driving method for an on-chip robot actuated by permanent magnets in a microfluidic chip. A piezoelectric ceramic is applied to induce ultrasonic vibration to the microfluidic chip and the high-frequency vibration reduces the effective friction on the MMT significantly. As a result, we achieved 1.1 micrometre positioning accuracy of the microrobot, which is 100 times higher accuracy than without vibration. The response speed is also improved and the microrobot can be actuated with a speed of 5.5 mm s(-1) in 3 degrees of freedom. The novelty of the ultrasonic vibration appears in the output force as well. Contrary to the reduction of friction on the microrobot, the output force increased twice as much by the ultrasonic vibration. Using this high accuracy, high speed, and high power microrobot, swine oocyte manipulations are presented in a microfluidic chip.     

Cationic Polymerization of β-Phenylvinyl Alkyl Ethers

Abstract

The cationic polymerization of β-phenylvinyl alkyl ethers (alkyl: methyl, ethyl, n-propyl, and n-butyl) was examined in toluene and in methylene chloride with boron fluoride etherate and with stannic chloride at ?78°C. Despite the fact that these monomers have bulky substituents on the α –and β-carbons, they could be homopoly-merized easily even in nonpolar sovent at ?78°C. The general features of β-phenylvinyl alkyl ethers in homopolymerization and co-polymerization with n-butyl vinyl ether suggested that β-phenylvinyl alkyl ethers behaved as derivatives of vinyl ethers, not as derivatives of styrenes. The polymerization products were white powders having a high softening point.     

Strong inclusion of inorganic anions into β-cyclodextrin immobilized to gold electrode

The inclusion of inorganic anions such as SO(4)(2-), NO(3)(-), and HPO(4)(2-) into the cavity of β-cyclodextrin monolayers on Au was examined by X-ray photoelectron spectroscopy (XPS), a quartz crystal microbalance (QCM), and chronocoulometric measurements of the competitive inclusion with ferrocene. The inclusion amounts of ferrocence in 0.2 M Na(2)SO(4), NaNO(3), and Na(2)HPO(4) solutions were less than 6% of the adsorption amount of β-cyclodextrin on Au, resulting in the apparent inhibition of the ferrocene redox reaction. The surface association constants of these anions reached about 10 on a logarithmic scale and were much higher than those for the inclusion of common organic guest compounds. A stronger anion inclusion was also demonstrated by the QCM response corresponding to the replacement of a preincluded organic guest with sulfate upon the injection of the sulfate solution. Quantitative analysis of the XPS data suggested a 1:1 association for each of these anions per surface β-cyclodextrin. There was no detectable inclusion for ClO(4)(-), Cl(-), and Br(-).     

Photorearrangements in spiro-conjoined cyclohexa-2,5-dien-1-one

The unexpected formation of cyclohexa-2,5-dien-1-one (6) spiro-conjoined with a dihydrobenzofuran framework, and the photochemical behavior of this compound in solution as well as in the solid state are described. The photoreaction of 6 in solution affords two rearranged products, one (7) accompanied by the enlargement of the oxygen heterocyclic ring and the other (8) accompanied by cyclopentadienone fragmentation. In the solid state, the former is the sole photoproduct of both solvated and desolvated crystals. The desolvated crystals were obtained as polycrystalline solids by thermal release of solvent molecules, and its structure was elucidated by ab initio determination from X-ray powder diffraction data followed by the Rietveld refinement.     

Study on the spin-crossover transition in [Fe(cis-/trans-stpy)4(X)2] (stpy: styrylpyridine, X: NCS, NCBH3) under high pressure toward ligand-driven light-induced spin change

Toward the realization of a ligand-driven light-induced spin change (LD-LISC) around room temperature, we have investigated the spin-crossover phenomenon in [Fe(stpy)₄(X)₂] (stpy = styrylpyridine, X = NCS, NCBH₃) under high pressure. The spin transition temperature increases from 110 to 220 K with increasing applied pressure up to 0.75 GPa for [Fe(trans-stpy)₄(NCS)₂], while [Fe(cis-stpy)₄(NCS)₂] shows the high-spin state in the temperature region between 2 and 300 K even at 0.75 GPa. In the case of X = NCBH₃, due to the stronger ligand field of NCBH₃, the spin transition temperature increases from 240 to 360 K with increasing applied pressure up to 0.50 GPa for [Fe(trans-stpy)₄(NCBH₃)₂]. In the case of [Fe(cis-stpy)₄(NCBH₃)₂], the spin state is the high-spin state in the temperature region between 2 and 300 K. However, the spin transition appears at 125 K under 0.5 GPa and the transition temperature increases with increasing applied pressure. In this way, we have decided the applied pressure region of 0.65-1.09 GPa where [Fe(stpy)₄(NCBH₃)₂] undergoes LD-LISC at room temperature.     

Radial transport characteristics of fast ions due to energetic-particle modes inside the last closed-flux surface in the compact helical system

The internal behavior of fast ions interacting with magnetohydrodynamic bursts excited by energetic ions has been experimentally investigated in the compact helical system. The resonant convective oscillation of fast ions was identified inside the last closed-flux surface during an energetic-particle mode (EPM) burst. The phase difference between the fast-ion oscillation and the EPM, indicating the coupling strength between them, remains a certain value during the EPM burst and drives an anomalous transport of fast ions.     

The Conversion of Superoxide to Hydroperoxide on Cobalt(III) Depends on the Structural and Electronic Properties of Azole-Based Chelating Ligands

Conversion from superoxide (O₂⁻) to hydroperoxide (OOH⁻) on the metal center of oxygenases and oxidases is recognized to be a key step to generating an active species for substrate oxidation. In this study, reactivity of cobalt(III)-superoxido complexes supported by facially-capping tridentate tris(3,5-dimethyl-4-X-pyrazolyl)hydroborate ([HB(pz^Me2,X)₃]⁻; Tp^Me2,X) and bidentate bis(1-methyl-imidazolyl)methylborate ([B(Im^N-Me)₂Me(Y)]⁻; L^Y) ligands toward H-atom donating reagent (2-hydroxy-2-azaadamantane; AZADOL) has been explored. The oxygenation of the cobalt(II) precursors give the corresponding cobalt(III)-superoxido complexes, and the following reaction with AZADOL yield the hydroperoxido species as has been characterized by spectroscopy (UV-vis, resonance Raman, EPR). The reaction of the cobalt(III)-superoxido species and a reducing reagent ([Co^II(C₅H₅)₂]; cobaltocene) with proton (trifluoroacetic acid; TFA) also yields the corresponding cobalt(III)-hydroperoxido species. Kinetic analyses of the formation rates of the cobalt(III)-hydroperoxido complexes reveal that second-order rate constants depend on the structural and electronic properties of the cobalt-supporting chelating ligands. An electron-withdrawing ligand opposite to the superoxide accelerates the hydrogen atom transfer (HAT) reaction from AZADOL due to an increase in the electrophilicity of the superoxide ligand. Shielding the cobalt center by the alkyl group on the boron center of bis(imidazolyl)borate ligands hinders the approaching of AZADOL to the superoxide, although the steric effect is insignificant.     

Access to Indole-Fused Benzannulated Medium-Sized Rings through a Gold(I)-Catalyzed Cascade Cyclization of Azido-Alkynes

Because benzannulated and indole-fused medium-sized rings are found in many bioactive compounds, combining these fragments might lead to unexplored areas of biologically relevant and uncovered chemical space. Herein is shown that α-imino gold carbene chemistry can play an important role in solving the difficulty in the formation of medium-sized rings. Namely, phenylene-tethered azido-alkynes undergo arylative cyclization through the formation of a gold carbene intermediate to afford benzannulated indole-fused medium-sized tetracycles. The reactions allow a range of different aryl substitution patterns and efficient access to these otherwise difficult-to-obtain medium-sized rings. This study also demonstrates the feasibility of the semihollow-shaped C-dtbm ligand for the construction of a nine-membered ring.     

Peptide Cyclization Mediated by Metal-Free S-Arylation: S-Protected Cysteine Sulfoxide as an Umpolung of the Cysteine Nucleophile

Covalent linking of side chains provides a method to produce cyclic or stapled peptides that are important in developing peptide-based drugs. A variety of crosslinking formats contribute to fixing the active conformer and prolonging its biological activity under physiological conditions. One format uses the cysteine thiol to participate in crosslinking through nucleophilic thiolate anions or thiyl radicals to form thioether and disulfide bonds. Removal of the S-protection from an S-protected Cys derivative generates the thiol, which functions as a nucleophile. S-Oxidation of a protected Cys allows the formation of a sulfoxide that operates as an umpolung electrophile. Herein, the applicability of S-p-methoxybenzyl Cys sulfoxide (Cys(MBzl)(O)) to the formation of a thioether linkage between tryptophan and Cys has been investigated. The reaction of peptides containing Cys(MBzl)(O) and Trp with trifluoromethanesulfonic acid (TFMSA) or methanesulfonic acid (MSA) in TFA in the presence of guanidine hydrochloride (Gn ⋅ HCl) proceeded to give cyclic or stapled peptides possessing the Cys-Trp thioether linkage. In this reaction, strong acids such as TFMSA or MSA are necessary to activate the sulfoxide. Additionally, Gn ⋅ HCl plays a critical role in producing an electrophilic Cys derivative that combines with the indole by aromatic electrophilic substitution. The findings led us to conclude that the less-electrophilic Cys(MBzl)(O) serves as an acid-activated umpolung of a Cys nucleophile and is useful for S-arylation-mediated peptide cyclization.