Self‐Template‐Directed Formation of Coordination‐Polymer Hexagonal Tubes and Rings,and their Calcination to ZnO Rings

This template will self‐destruct : A unique particle‐growth mechanism involves growth of new coordination polymers on the surface of initially formed hexagonal blocks and concomitant dissolution of the blocks to form hexagonal tubes (see scheme and scanning electron, optical, and fluorescence microscopy images). Calcination of the tubes yields ZnO particles of the same shape.

     

HPLC of fluoroquinolone antibacterials using chiral stationary phase based on enantiomeric (3,3′‐diphenyl‐1,1′‐binaphthyl)‐20‐crown‐6

A residual silanol group‐protecting chiral stationary phase (CSP) based on optically active (3,3′‐diphenyl‐1,1′‐binaphthyl)‐20‐crown‐6 was successfully applied to the resolution of fluoroquinolone compounds including gemifloxacin mesylate. The chiral recognition ability of the residual silanol group‐protecting CSP was generally greater than that of the residual silanol group‐containing CSP. From these results, it was concluded that the simple protection of the residual silanol groups of the latter CSP with lipophilic n‐octyl groups can improve its chiral recognition ability for the resolution of racemic fluoroquinolone compounds. The chromatographic resolution behaviors were investigated as a function of the content and type of organic and acidic modifiers and the ammonium acetate concentration in aqueous mobile phase and the column temperature. Especially, the addition of ammonium acetate to the mobile phase was found to be a quite effective means of reducing the enantiomer retentions without sacrificing the chiral recognition efficiency of the CSP.     

A simple formula for an analogue of conditional wiener integrals and its applications II

Let C[0, T] denote the space of real-valued continuous functions on the interval [0, T] with an analogue w _ϕ of Wiener measure and for a partition 0 = t ₀ < t ₁ < ... < t _n < t _n+1 = T of [0, T], let X _n : C[0, T] → ℝ ⁿ⁺¹ and X ⁿ⁺¹: C[0, T] → ℝ ⁿ⁺² be given by X _n (x) = (x(t ₀), x(t ₁), ..., x(t _n )) and X _n+1(x) = (x(t ₀), x(t ₁), ..., x(t _n+1)), respectively. In this paper, using a simple formula for the conditional w _ϕ-integral of functions on C[0, T] with the conditioning function X _n+1, we derive a simple formula for the conditional w _ϕ-integral of the functions with the conditioning function X _n . As applications of the formula with the function X _n , we evaluate the conditional w _ϕ-integral of the functions of the form F _m (x) = ∫₀ ^T (x(t)) ^m for x ∈ C[0, T] and for any positive integer m. Moreover, with the conditioning X _n , we evaluate the conditional w _ϕ-integral of the functions in a Banach algebra which is an analogue of the Cameron and Storvick’s Banach algebra . Finally, we derive the conditional analytic Feynman w _ϕ-integrals of the functions in .      

Peptides on GaAs surfaces: comparison between features generated by microcontact printing and dip-pen nanolithography

Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) were employed to understand the size, composition, and conformation of lithographic patterns composed of peptide molecules. GaAs surfaces were patterned by microcontact printing (microCP) and dip-pen nanolithography (DPN) using a peptide sequence composed of 15 amino acids. The detailed surface evaluation showed that the patterns have similar chemical compositions but differ in the bonding among the molecules anchored on the GaAs substrate. Both types of patterns were crystalline-like in nature. The features created by DPN exhibited interchain hydrogen bonding, while the ones generated by microCP displayed non-hydrogen bonding. The differences in the lithographic structures can be utilized in future biorecognition experiments that take advantage of the electronic properties of the GaAs substrate and the tunable behavior of the covalently anchored biomolecules on the surface.     

Formation of superhydrophobic surfaces by biomimetic silicification and fluorination

The amazing water repellency of many biological surfaces, exemplified by lotus leaves, has recently received a great deal of interest. These surfaces, called superhydrophobic surfaces, exhibit water contact angles larger than 150 degrees and a low contact angle hysteresis because of both their low surface energy and heterogeneously rough structures. In this paper, we suggest a biomimetic method, "biosilicification", for generating heterogeneously rough structures and fabricating superhydrophobic surfaces. The superhydrophobic surface was prepared by a combination of the formation of heterogeneously rough, nanosphere-like silica structures through biosilicification and the formation of self-assembled monolayers of fluorosilane on the surface. The resulting surface exhibited the water contact angle of 160.1 degrees and the very low water contact angle hysteresis of only 2.3 degrees, which are definite characteristics of superhydrophobic surfaces. The superhydrophobic property of our system probably resulted from the air trapped in the rough surface. The wetting behavior on the surface was in the heterogeneous regime, which was totally supported by Cassie-Baxter equation.     

Directed evolution of ATP binding proteins from a zinc finger domain by using mRNA display

Antibodies have traditionally been used for isolating affinity reagents to new molecular targets, but alternative protein scaffolds are increasingly being used for the directed evolution of proteins with novel molecular recognition properties. We have designed a combinatorial library based on the DNA binding domain of the human retinoid-X-receptor (hRXRalpha). We chose this domain because of its small size, stable fold, and two closely juxtaposed recognition loops. We replaced the two loops with segments of random amino acids, and used mRNA display to isolate variants that specifically recognize adenosine triphosphate (ATP), demonstrating a significant alteration of the function of this protein domain from DNA binding to ATP recognition. Many novel independent sequences were recovered with moderate affinity and high specificity for ATP, validating this scaffold for the generation of functional molecules.     

Infrared spectra and density functional calculations of CH2 = MHX and CH[triple bond]MH2X complexes prepared in reactions of methyl halides with Mo and W atoms

The simple methylidene and methylidyne complexes (CH2=MHX and CH[triple bond]MH2X; X = F, Cl, Br, and I) are prepared in reactions of laser-ablated Mo and W atoms with the methyl halides and investigated by matrix infrared spectroscopy and density functional theory calculations. These complex structures are photoreversible: visible irradiation converts the methylidene complex to the methylidyne complex, and UV irradiation reverses this effect via alpha-hydrogen migration. While the higher oxidation state complexes are readily formed regardless of halogen size, the Mo methylidyne complex is relatively less favored with increasing halogen size, and the W complex shows the opposite tendency. The group 6 metal methylidenes are predicted to have the most agostically distorted structures among the early transition-metal methylidenes. The computed carbon-metal bond shortens with increasing halogen size for both the methylidene and methylidyne complexes. Harmonic and anharmonic frequencies computed by DFT converge on the experimental values and thus provide support for the identification of these new Mo and W complexes.     

Transannular distance dependence of stabilization energy of the intramolecular dimer radical cation of cyclophanes

The intramolecular dimer radical cation and charge-transfer complex of various cyclophanes were investigated by using pulse radiolysis measurements. The charge resonance band due to the dimer radical cation of cyclophanes appeared in the near-IR region, which showed a blue-shift as the distance between the two benzene rings of cyclophane decreased. The stabilization energy of the dimer radical cation, which was estimated from the peak position of the charge resonance band, was explained by the exchange interaction, while the substituent effect was small. The absorption peak of the charge-transfer complex with chlorine atom also showed the shift in accordance with the oxidation potential of cyclophanes.     

Synthesis and electrochemical properties of nonstoichiometric LiAlxMn2−xO4−δ as cathode materials for rechargeable lithium ion battery

Nonstoichiometric spinel oxides, LiAl_xMn_2−xO_4−δ (x=0.1,0.2), were synthesized under controlled partial pressure of oxygen, and their elecrochemical performances were investigated. As an Al content increases, solubility limit of the oxygen nonstoichiometry, δ, increased, while partial molar enthalpy of the formation of oxygen nonstoichiometry decreased.Cycle performance of LiAl_xMn_2−xO₄ showed significant improvement comparing with that of LiMn₂O₄ cathode. However, the decrease of theoretical capacity was accompanied with Al doping. Nonstoichiometric LiAl_xMn_2−xO_4−δ showed the increase in capacity with keeping good cycle performances as well as stoichiometric LiAl_xMn_2−xO₄. Although the introduction of oxygen nonstoichiometry leads to the increase of Mn³⁺ which is known as Jahn-Teller ion, DSC curves for LiAl_xMn_2−xO_4−δ showed no exothermic peak due to phase transition arising from Jahn-Teller distortion around room temperature.