Scanning LLL x-ray interferometry

A new formalism is presented for the theory of scanning LLL x-ray interferometry, which takes account also of the amount of x-ray absorption and of crystal yawing. It is based on the Takagi approach to the dynamical theory of x-ray diffraction and uses, to a great extent, the formalism of quantum mechanics, in order to reduce the algebraic complexity of the Ewald-von Laue approach. The formalism presented here is an easy-to-handle tool for the study of x-ray propagation in multicrystal systems and for the investigation into deviations of the travelling-fringe period from the spacing of diffracting planes, as it explains how interference features change when moving in paramater space.     

Synthesis of Bioactive and Porous Organic-Inorganic Hybrids for Biomedical Applications

Bioactivity has been exhibited by a limited range of ceramics since the invention of Bioglass®. Recently, some bioactive polymeric organic-inorganic hybrids were introduced, including not only organically modified silicates (Ormosils) synthesized from polydimethylsiloxane (PDMS) and tetraethoxysilane but also those with gelatin and 3-glycidoxypropyl-tremethoxysilane. Preparation of the bulk and porous hybrids and their polymeric structures analyzed by Si NMR spectroscopy were presented. In vitro bioactivity or apatite deposition in a simulated body fluid of the Kokubo recipe were also described for those hybrids. Freeze-drying techniques introduced porosity (up to 90%) and pores extending in a preferred direction.     

Rotational bands in 181Ta

High-spin states in ¹⁸¹Ta have been studied via the ¹⁷⁶Yb(¹¹B,α2n) reaction at 52 MeV using the PEX array and at 57 MeV using the NORDBALL array, with α-particle detection. The previously known, K^π=(7/2)⁺ ground state band and K^π=(9/2)⁻ band have been extended to spins (29/2)⁺ and (31/2)⁻, respectively. Two new one-quasiparticle bands, the K^π=(5/2)⁺ band built on the known (5/2)⁺ isomer and a K^π=((1/2)⁻) band have been observed. Two other rotational bands with three-quasiparticle structure, K^π=(15/2)⁻ and ((19/2)⁺ with π(7/2)[404]ν²(1/2)[510](9/2)[624] and π(9/2)[514]ν²(1/2)[510](9/2)[624] configurations, respectively, have been newly observed. The half-life of the K^π=((19/2)⁺) bandhead which decays to the head of the (15/2)⁻ band has been measured to be 140(36) ns. However, transitions from the ((19/2)⁺) state to the (15/2)⁻ band have not been observed. Received: 26 August 1998     

Living anionic polymerization of N‐methoxymethyl‐N‐isopropylacrylamide: Synthesis of well‐defined poly(N‐isopropylacrylamide) having various stereoregularity

Anionic polymerization of N‐methoxymethyl‐N‐isopropylacrylamide ( 1 ) was carried out with 1,1‐diphenyl‐3‐methylpentyllithium and diphenylmethyllithium, ‐potassium, and ‐cesium in THF at ?78 °C for 2 h in the presence of Et₂Zn. The poly( 1 )s were quantitatively obtained and possessed the predicted molecular weights based on the feed molar ratios between monomer to initiators and narrow molecular weight distributions (M_w/M_n = 1.1). The living character of propagating carbanion of poly( 1 ) either at 0 or ?78 °C was confirmed by the quantitative efficiency of the sequential block copolymerization using N,N‐diethylacrylamide as a second monomer. The methoxymethyl group of the resulting poly( 1 ) was completely removed to give a well‐defined poly(N‐isopropylacrylamide), poly(NIPAM), via the acidic hydrolysis. The racemo diad contents in the poly(NIPAM)s could be widely changed from 15 to 83% by choosing the initiator systems for 1 . The poly(NIPAM)s obtained with Li⁺/Et₂Zn initiator system possessed syndiotactic‐rich configurations (r = 75–83%), while either atactic (r = 50%) or isotactic poly(NIPAM) (r = 15–22%) was generated with K⁺/Et₂Zn or Li⁺/LiCl initiator system, respectively. Atactic and syndiotactic poly(NIPAM)s (42 < r < 83%) were water‐soluble, whereas isotactic‐rich one (r < 31%) was insoluble in water. The cloud points of the aqueous solution of poly(NIPAM)s increased from 32 to 37 °C with the r‐contents. These indicated the significant effect of stereoregularity of the poly(NIPAM) on the water‐solubility and the cloud point in water © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4832–4845, 2006     

A new on-line sample preparation system for the liquid chromatography/time-of-flight mass spectrometry simultaneous analysis of pesticides in river water.

Current on-line solid-phase extraction methods combined with HPLC for shortening the clean-up operation are not suitable for simultaneously detecting compounds that have a wide variety of hydrophobicities. To solve these problems, we designed a new on-line sample preparation system. The system consists of an eluting pump, a mixing TEE connector, a 10-port 2-position valve and a solid-phase extraction precolumn. The eluate from the precolumn is diluted with a weak solvent from the HPLC at the TEE connection to load low hydrophobic compounds onto the analytical column. The proposed on-line sample preparation system was successfully applied to the simultaneous analysis of 21 pesticides in river water using LC/TOF-MS. In this method, the recoveries from river water samples were 67 to 126% (mean 83%), the reproducibility (CV%) was in the range from 1.1 to 11% (mean 5.6%), the calibration curve was linear in the range from 1 ppb to 500 ppb (r > 0.999) and the detection limits (S/N = 3) were in the range from 0.0034 ppb (daimuron) to 3.3 ppb (oxine-copper).     

Water-soluble stilbene dendrimers

The third generation of novel photo-responsive water-soluble stilbene dendrimer (trans- and cis-G3 WSD) undergoes unusual one-way trans-to-cis isomerization to give 100% of cis isomer at the photostationary state on UV irradiation in water.     

Pinacol coupling reaction of beta-halo-alpha,beta-unsaturated aldehydes promoted by TiI4

The pinacol reaction of beta-halogenated alpha,beta-unsaturated aldehydes was promoted by titanium tetraiodide to give coupling products in good yields with high dl-selectivity. Subsequent reduction with H(2)/Pd-C gave saturated vic-diols in good yields. Heck coupling reaction enabled the displacement of halogens with vinyl groups without the loss of stereochemical integrities. [reaction: see text]     

Activity of artificial mutant variants of human growth hormone deficient in a disulfide bond between Cys53 and Cys165

In order to understand the role of Cys53 and Cys165 of human growth hormone (hGH) in receptor-binding and biological activity, artificial mutant variants of hGH were prepared in Escherichia coli by in vitro mutagenesis. Variants of hGH were constructed by replacement of Cys165 with Ala ([Ala165]hGH) or Ser ([Ser165]hGH), by replacement of Cys53 with Ala ([Ala53]hGH), by replacement of Cys53 and Cys165 with Ala ([Ala53, Ala165]hGH), or by replacement of Cys53 with Ala and Cys165 with Ser ([Ala53,Ser165]hGH). All of the variants constructed as well as reduced hGH exhibited less biological activity than that of intact hGH, and the decreases in biological activity were almost equal, as measured by a sensitive biological assay for growth hormone: adipose conversion assay using 3T3-F442A cells. These variants also showed less receptor-binding activity than that of intact hGH. These results suggest that it is possible neither the residue Cys53 nor Cys165 is directly involved in the receptor binding, and that the disulfide bridge between Cys53 and Cys165 in hGH may not always be crucial for the biological activity, though necessary to express full hGH activity.