Raman spectroscopic study of femtosecond laser-induced phase transformation associated with ripple formation on single-crystal SiC

Raman spectroscopy was performed to investigate microscopic structural changes associated with a ripple structure formation initiated by femtosecond laser irradiation on the surface of single-crystal silicon carbide. The amorphous phases of silicon carbide, silicon, and carbon were observed. The intensity ratio between amorphous silicon carbide and silicon changed discretely at the boundary between fine and coarse ripples. The physical processes responsible for the formation of the ripple structure are discussed.     

Asymmetric nitrile-hydration with bifunctional ruthenium catalysts bearing chiral N-sulfonyldiamine ligands

The asymmetric hydration of α-benzyl-α-methylmalononitrile was examined by using chiral bifunctional catalysts. Enantiomer discrimination of the prochiral dinitrile in the presence of water was demonstrated with a well-defined bifunctional amido-Ru complex having N-sulfonyldiamine ligands, and providing the corresponding amidato(amine) complexes diastereoselectively. Under the catalytic conditions, the (R)-cyanoamide was successfully obtained without further hydrolysis to carboxylic acids.     

Oligo-Asp tag/Zn(II) complex probe as a new pair for labeling and fluorescence imaging of proteins

To accomplish the selective labeling of a specific protein in complicated biological systems, a peptide tag incorporated into the protein and a complementary small molecular probe are required. Although a variety of peptide tag/probe pairs have been developed as molecular tools for protein analyses, the availability of pairs suitable for real-time imaging of proteins is still limited. We now report a new peptide tag/artificial probe pair composed of a genetically encodable oligo-aspartate sequence (D4 tag, (D4)n, n = 1-3) and the corresponding multinuclear Zn(II) complexes (Zn(II)-DpaTyrs). The strong binding affinity of the Zn(II)-DpaTyr probes with the D4 tag was a result of the multiple coordination bonds and the multivalent effect. It was measured quantitatively by isothermal titration calorimetry. The high affinity between the tag and the probe, indispensable for the selective protein labeling, enabled the pair to be used for the labeling and fluorescence imaging of a membrane-bound receptor protein tethering a triply repeated D4 tag ((D4)3) in an intact cell configuration without significantly affecting the receptor signal transduction.     

Electrochemical immobilization of Cs in single-crystalline SYNROC

The development of a disposal technique for the radiotoxic ¹³⁷Cs in nuclear wastes is one of the most urgent issues in nuclear fuel technology. An effective disposal method of ¹³⁷Cs is to immobilize it in a synthetic rock (SYNROC) material: cesium titanate hollandite, ¹³⁷Cs_xTi₈O₁₆ (I4/m, , ). Practical applications of ¹³⁷Cs_xTi₈O₁₆ have been restricted so far because the conventional synthetic method requires strong chemical reducers and reaction temperatures higher than 1250 °C. In this report, we present a milder preparation method of Cs_xTi₈O₁₆ by electrolysis of a mixture of Cs₂MoO₄ and TiO₂ in ambient atmosphere at 900 °C. The Cs content in the resultant single-crystalline Cs_1.35Ti₈O₁₆ is competitive with the highest value in polycrystalline Cs_1.36±0.03Ti₈O₁₆ prepared by the conventional synthetic method. The electrochemical preparation of Cs_1.35Ti₈O₁₆ is a promising way to immobilize a high quantity of ¹³⁷Cs ions in a stable form of single-crystalline SYNROC.     

Dimerization of a lattice-framework silanone into the corresponding 1,3-dioxa-2,4-disiletanes

A lattice-framework silanone, a racemate of (4R,6R)- and (4S,6S)-2,3,4,6,7,8-hexa-tert-butyl-1,5-disilatricyclo[4.2.0.0^1,4]octa-2,7-dien-5-one (4), was generated by the photoreaction of the corresponding lattice-framework disilene, a racemate of (4R,6R,4′R,6′R)- and (4S,6S,4′S,6′S)-2,3,4,6,7,8,2′,3′,4′,6′,7′,8′-dodeca-tert-butyl-[5,5′]bi{1,5-disilatricyclo[4.2.0.0^1,4]octylidene}-2,7,2′,7′-tetraene (dl-1), with mesitonitrile oxide. The silanone 4 was dimerized to produce a mixture of the corresponding dl- and meso-1,3-dioxa-2,4-disiletane derivatives 2. DFT calculations suggested that the non-selective dimerization of 4 to 2 is attributed to the irreversibility of the reaction.     

Further resolution of alpha-fetoprotein glycoforms by two-dimensional isoelectric focusing and lectin affinity electrophoresis

Human alpha-fetoprotein (AFP) from serum of patients with cirrhosis and hepatocellular carcinoma (HCC) was separated into several bands by IEF and by erythroagglutinating phytohemagglutinin (E-PHA) affinity electrophoresis. These AFP bands were directly compared in 2-D IEF and E-PHA affinity electrophoresis. IEF of serum AFP was run in 1% agarose IEF gel with 3% Pharmalyte 4.5-5.4. After IEF, a part of the gel was stained for AFP and another part of the gel corresponding to the area of separated AFP bands was cut in 1 mm x 39 mm along the focused direction and transferred to a trough in 1% agarose gel with 0.3 mg/mL E(4)-PHA for second-dimensional affinity electrophoresis. Separated 2-D AFP spots were visualized by antibody-affinity blotting and identified by combining the systems of Johnson et al.. (Johnson, P. J., Ho, S., Cheng, P., Chan, A. et al.., Cancer 1995, 75, 1663-1668) for AFP-I-+IV and of Taketa et al.. (Taketa, K., Ichikawa, E., Taga, H., Hirai, H., Electrophoresis 1985, 6, 492-497) for AFP-P1-5. AFP-P2, the major AFP glycoform, was composed of AFP-I, AFP+I, and AFP+II; AFP-P3, a nonspecific monosialo-AFP, was composed of AFP+II; AFP-P4, HCC-specific monosialo-AFP, was composed of AFP+II, AFP+III, and AFP+IV; and malignancy-related AFP-P5 was composed of AFP+I and AFP+II. Monosialo-AFP (AFP+II) was recovered in all the glycoforms of AFP-P2, -P3, -P4, and -P5; thus, AFP-P4 is more specific to HCC than monosialylated AFP+II.     

Fluorescent Diarylindoles by Palladium‐Catalyzed Direct and Decarboxylative Arylations of Carboxyindoles

Simple and brilliant : 1‐Substituted 1H‐indole‐2‐carboxylic acids efficiently undergo successive diarylation accompanied by C? H bond cleavage and decarboxylation upon treatment with aryl bromides in the presence of a palladium catalyst system to afford fluorescent 2,3‐diarylindoles. This facile synthetic method provides a highly efficient blue emitter with a quantum yield of 0.97 in the solid state (see scheme).

     

A generalized Kiepert formula for <Emphasis Type="Italic">C</Emphasis><Subscript><Emphasis Type="Italic">ab</Emphasis></Subscript> curves

Kiepert (1873) and Brioschi (1864) published algebraic equations for the n-division points of an elliptic curve, in terms of the Weierstrass ℘-function and its derivatives with respect to a uniformizing parameter, or another elliptic function, respectively. We generalize both types of formulas for a compact Riemann surface which, outside from one point, has a smooth polynomial equation in the plane, in the sense that we characterize the points whose n-th multiple in the Jacobian belongs to the theta divisor.