Synthesis of end‐functionalized poly(methyl methacrylate) by ruthenium‐catalyzed living radical polymerization with functionalized initiators

A series of functionalized 2‐bromoisobutyrates and 2‐chloro‐2‐phenylacetates led to α‐end‐functionalized poly(methyl methacrylate)s in Ru(II)‐catalyzed living radical polymerization; the terminal functions included amine, hydroxyl, and amide. These initiators were effective in the presence of additives such as Al(Oi‐Pr)₃ and n‐Bu₃N. The chlorophenylacetate initiators especially coupled with the amine additive gave polymers with well‐controlled molecular weights (M_w/M_n = 1.2–1.3) and high end functionality (F_n ～ 1.0). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1937–1944, 2002     

Dynamic synovial fibroblasts are modulated by NBCn1 as a potential target in rheumatoid arthritis

Rheumatoid arthritis (RA) is an autoimmune disease characterized by aggressive fibroblast-like synoviocytes (FLSs) and pannus formation. Various therapeutic strategies have been developed against inflammatory cytokines in RA in recent decades. Based on the migratory features of FLSs, we examined whether modulation of the migratory module attenuates RA severity. In this study, inflamed synovial fluid-stimulated FLSs exhibited enhanced migration and migratory apparatus expression, and sodium bicarbonate cotransporter n1 (NBCn1) was identified in primary cultured RA-FLSs for the first time. The NBC inhibitor S0859 attenuated the migration of FLSs induced with synovial fluid from patients with RA or with TNF-α stimulation. Inhibition of NBCs with S0859 in a collagen-induced arthritis (CIA) mouse model reduced joint swelling and destruction without blood, hepatic, or renal toxicity. Primary FLSs isolated from the CIA-induced mouse model also showed reduced migration in the presence of S0859. Our results suggest that inflammatory mediators in synovial fluid, including TNF-α, recruit NBCn1 to the plasma membrane of FLSs to provide dynamic properties and that modulation of NBCn1 could be developed into a therapeutic strategy for RA.Subject terms: Chemotaxis, Bone, Ion channel signalling, Rheumatoid arthritis, Drug development     

Simplifying patterning process of ZnO nanowires by one step development and etching process

We present herein a simple protocol of growing a patterned ZnO nanowire by etching of ZnO seed layer in the tetramethyl ammonium hydroxide (TMAH) solution. The ZnO seed layer was fabricated by sol–gel method using zinc acetate solution and patterned by using photolithographic method. Patterned ZnO seed layer as etched in the TMAH solution, followed by growth of ZnO nanowires by hydrothermal method. Remarkable point of present ZnO seed layer patterning is that development of UV-exposed photoresist and etching of ZnO seed layer is subsequently processed in aqueous TMAH solution without interruption. The grown ZnO nanowires were analyzed using XRD patterns to exhibit high purity and degree of crystallinity, and showed very good pattern fidelity.     

Curvature measurement using phase shifting in-line interferometry,single shot off-axis geometry and Zernike's polynomial fitting

This paper describes the difference between phase shifting in-line interferometry, single shot off-axis geometry and Zernike's polynomial fitting methods for measuring the curvature of a spherical smooth surface by using the Michelson interferometer. In phase shifting in-line interferometry, four interferograms shifted by a piezoelectric actuator (PZT) were captured by a digital detector and corrected by using the flat fielding method. In off-axis geometry, single shot off-axis interferogram was obtained by tilting the reference and the object wave of the off-axis interferogram was reconstructed in the central region of the observation plane by using the digital reference wave concept. The demodulated phase map was obtained and unwrapped to remove the 2π ambiguity. The unwrapped phase map was converted to height and the sagittal length that used for curvature measurement was calculated accurately. The results extracted from phase shifting in-line interferometry and single shot off-axis geometry methods were compared with the results extracted from single shot Zernike's polynomial fitting method and the results were in excellent agreement. A new trial was done to overcome the fringes produced from the object interfaces. Some factors of uncertainty which affected on the measurement were estimated in the order of 6.0 × 10^?5 mm or 0.003 dioptre (▽).     

A convergence study of a new partitioned fluid–structure interaction algorithm based on fictitious mass and damping

We develop, analyze and validate a new method for simulating fluid–structure interactions (FSIs), which is based on fictitious mass and fictitious damping in the structure equation. We employ a partitioned method for the fluid and structure motions in conjunction with sub-iteration and Aitken relaxation. In particular, the use of such fictitious parameters requires sub-iterations in order to reduce the induced error in addition to the local temporal truncation error. To this end, proper levels of tolerance for terminating the sub-iteration procedure have been obtained in order to recover the formal order of temporal accuracy. For the coupled FSI problem, these fictitious terms have a significant effect, leading to better convergence rate and hence substantially smaller number of sub-iterations. Through analysis we identify the proper range of these parameters, which we then verify by corresponding numerical tests. We implement the method in the context of spectral element discretization, which is more sensitive than low-order methods to numerical instabilities arising in the explicit FSI coupling. However, the method we present here is simple and general and hence applicable to FSI based on any other discretization. We demonstrate the effectiveness of the method in applications involving 2D vortex-induced vibrations (VIV) and in 3D flexible arteries with structural density close to blood density. We also present 3D results for a patient-specific aneurysmal flow under pulsatile flow conditions examining, in particular, the sensitivity of the results on different values of the fictitious parameters.     

Total synthesis of (+)-valienamine and (−)-1-epi-valienamine via a highly diastereoselective allylic amination of cyclic polybenzyl ether using chlorosulfonyl isocyanate

The total synthesis of (+)-valienamine and (−)-1-epi-valienamine was concisely accomplished from readily available d-glucose via a highly diastereoselective amination of chiral benzylic ether using chlorosulfonyl isocyanate, intramolecular olefin metathesis, and diastereoselective reduction of cyclic enone using l-Selectride as the key steps.     

Palladium-catalyzed C–S bond formation by using N-amido imidazolium salts as ligands

N-Amido imidazolium salt was employed as a ligand in the palladium-catalyzed cross-coupling reaction of aryl halides and thiols, and showed good activity in the formation of thioether. The best combination for the coupling with aryl bromides was N-amido imidazolium salt 2 and NaHMDS, and that for the coupling with aryl iodides was N-amido imidazolium salt 1 and KO^tBu. The coupling reactions were conducted in the presence of Pd(OAc)₂ (1 mol %) in DMSO at 80 °C for 12 h.     

Effects of gamma irradiation on morphological changes and biological responses in plants

This review discusses the morphological changes and biological responses of plants irradiated with gamma rays. Seedlings exposed to relatively low doses of gamma rays (1-5 Gy) developed normally, while the growth of plants irradiated with a high dose gamma ray (50 Gy) was significantly inhibited. Based on TEM observations, chloroplasts were extremely sensitive to gamma irradiation compared to other cell organelles, particularly thylakoids being heavily swollen. In addition, some portions of the mitochondria and endoplasmic reticulum were structurally altered, for example, distortion and swelling. The cerium perhydroxide deposition, as a maker for H(2)O(2) deposition, was typically manifest on the plasma membranes and cell walls of the tissues from both the control and irradiated plants. However, the intensities of cerium perhydroxide deposits (CPDs) were remarkably increased in the plasma membranes and cell walls of pumpkin tissues such as petiole, cotyledon, hypocotyl and especially leaf after gamma irradiation. These observations are in good agreement with the results of H(2)O(2) content in all tissues. The immuno-localization analysis for peroxidase (POD) on the tissues from pumpkin plant showed the same pattern between the control and irradiated plants, but the density of gold particles as indication of POD localization was significantly increased on the cell corner middle lamellae of parenchyma cells, especially in the petiole after gamma irradiation. However, accumulation and localization of H(2)O(2) and POD in vessels were not significantly different between both plants. The accumulation and localization of both H(2)O(2) and POD were differentially affected by gamma irradiation depending on the different tissue types. The deposition of both H(2)O(2) and POD in parenchyma cells appeared much higher than in vessels, suggesting that the former is more sensitive than the latter against gamma rays.