Kaempferol tri- and tetraglycosides from the flowers of Clematis cultivar

A new kaempferol glycoside, kaempferol 3-O-alpha-rhamnopyranosyl-(1 --> 2)-[alpha-rhamnopyranosyl-(1 --> 6)-beta-glucopyranoside]-7-O-beta-glucopyranoside (2) was isolated from the flowers of Clematis cultivar "Jackmanii Superba", together with a known kaempferol 3-O-alpha-rhamnopyranosyl-(1 --> 6)-beta-glucopyranoside-7-O-beta-glucopyranoside (1). The chemical structures of the isolated glycosides were established by UV, LC-MS, characterization of acid hydrolysates, and 1H and 13C NMR spectroscopy.     

Mechanism of O2-accelerated sonolysis of bisphenol A

The effects of dissolved gases on the sonochemical degradation of bisphenol A (BPA) were studied at a frequency of 500 kHz. BPA degradation rate increased in the order O(2)>Ar>air>N(2). The rate constant for oxygen (2.6 h(-1)) was approximately two fold higher than that for argon (1.2 h(-1)). A primary intermediate (2,3-dihydro-2-methylbenzofuran), a typical intermediate of BPA formed during attack by OH radicals, was detected only in the presence of oxygen, revealing that a different reaction path was responsible for the enhancement of decomposition.     

Structure and reactivity of alkoxycarbonyl (ester)-terminated monolayers on silicon: sum frequency generation spectroscopy

Carboxylic acid-terminated monolayers on crystalline silicon surfaces can be readily modified with biological macromolecules for the fabrication of semiconductor-based biosensing devices. They were prepared by acid-catalyzed hydrolysis of alkoxycarbonyl (ester)-terminated monolayers and studied by vibrational sum frequency generation (SFG) spectroscopy. The C-H vibration region of the SFG spectra consists of strong methyl bands with significant contributions from methylene stretching modes, indicating that these monolayers are generally ordered but with considerable gauche defects in the alkyl chains in comparison with n-alkyl monolayers. After hydrolysis, the methylene stretching modes prevail, with "residues" of the methyl bands, indicating incomplete hydrolysis and disruption of the monolayer structure. This work demonstrates that SFG is capable of providing quantitative information on structure-reactivity correlations in organic monolayers.     

Surface Coating with a Thermoresponsive Copolymer for the Culture and Non‐Enzymatic Recovery of Mouse Embryonic Stem Cells

A thermoresponsive substrate based on a triblock copolymer, poly(N‐isopropylacrylamide)‐block‐poly[(R)‐3‐hydroxybutyrate]‐block‐poly(N‐isopropylacrylamide) (PNIPAAm‐PHB‐PNIPAAm), co‐coated with gelatin, was developed for the culture and non‐enzymatic recovery of mouse embryonic stem cells. After culture, the cells could be detached by cooling at 4 °C for 20 min without trypsin digestion. The embryonic stem cells remained undifferentiated after culture on the gelatin/copolymer‐coated surfaces, similar to standard culture techniques. Overall, the triblock copolymer coating was superior to the PNIPAAm homopolymer coating in terms of supporting better cell growth, being more stable, presenting a more homogeneous surface coating, and maintaining pluripotency of the embryonic stem cells.

     

A Class of Robust Principal Component Vectors

This paper is concerned with a study of robust estimation in principal component analysis. A class of robust estimators which are characterized as eigenvectors of weighted sample covariance matrices is proposed, where the weight functions recursively depend on the eigenvectors themselves. Also, a feasible algorithm based on iterative reweighting of the covariance matrices is suggested for obtaining these estimators in practice. Statistical properties of the proposed estimators are investigated in terms of sensitivity to outliers and relative efficiency via their influence functions, which are derived with the help of Stein's lemma. We give a simple condition on the weight functions which ensures robustness of the estimators. The class includes, as a typical example, a method by the self-organizing rule in the neural computation. A numerical experiment is conducted to confirm a rapid convergence of the suggested algorithm.     

Radical polymerization of benzyl N-(2,6-dimethylphenyl)itaconamate

The polymerization of benzyl N-(2,6-dimethylphenyl)itaconamate (BDMPI) with benzoyl peroxide (BPO) in N,N-dimethylformamide (DMF) was studied kinetically by ESR. The polymerization rate (R_p) at 70°C was given by R_p = k[BPO]^0.78[BDMPI]^1.1. The overall activation energy of polymerization was determined to be 83.7 kJ/mol. The number-average molecular weight of poly(BDMPI) was in the range of 1500–2000 by gel permeation chromatography. From the ESR study, the polymerization system was found to involve ESR-observable propagating radicals of BDMPI under practical polymerization conditions. Using the polymer radical concentration by ESR, the rate constants of propagation (k_p) and termination (k_t) were determined in the temperature range of 50–70°C. The k_p value seemed dependent on the chain-length of propagating radical. The analysis of polymers by the MALDI-TOF mass spectrometry suggested that most of the resulting polymers contain the dimethylamino terminal group. The copolymerization of BDMPI (M₁) and styrene (M₂) at 50°C in DMF gave the following copolymerization parameters; r₁ = 0.49, r₂ = 0.26, Q₁ = 1.2, and e₁ = +0.63. The thermal behavior of poly(BDMPI) was examined by dynamic thermogravimetry and differential scanning calorimetry. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1891–1900, 1997     

Quantum dynamics of a generalized Coleman-Hepp model

Studies on a generalized Coleman-Hepp model are done on the basis of a spin coherent state representation and a transformation property of the model Hamiltonian. Namely, transforming the original model Hamiltonian into a simpler form, we can determine time evolution of the whole system by successive applications of rotation operators in a spinor space. Dynamics of detector spins as well as that of an incident particle are fully discussed. Explicit numerical evaluations are also performed. Relevance of our solution to a generalized Cini model is also briefly mentioned. Received 24 August 1999     

Laryngeal closure pressure during phonation in humans.

We investigated the laryngeal closure pressure during sustained phonation in five healthy adult men with no pathological lesions in the glottis using a round pressure transducer with a diameter of 10 mm and a thickness of 1 mm. The transducer was placed between the vocal processes through the mouth. Subjects were asked to utter a sustained phonation of the vowel sound /eh/ at varying pitch and intensity in modal register. The laryngeal closure pressure ranged from 0 to 200 cmH2O. At a comfortable pitch and intensity, the pressure was below 50 cmH2O. The pressure was correlated with pitch, but not with intensity.