Dirhodium tetracarboxylate scaffolds as reversible fluorescence-based nitric oxide sensors

We report the synthesis and characterization of dirhodium tetracarboxylate complexes [Rh(2)(mu-O(2)CR)(4)(L)(2)], with R = Me and L = dansyl-imidazole (Ds-im) or dansyl-piperazine (Ds-pip). The fluorophores coordinate to the axial sites of the dirhodium core through the imidazole or piperazine N-atom and emit only weakly when excited at 365 or 345 nm for the Ds-im and Ds-pip complexes, respectively. These fluorophore-containing complexes were investigated for their ability to elicit a fluorescence response in the presence of NO. An immediate increase in fluorescence emission of greater than 15-fold occurs when NO is admitted to solutions containing [Rh(2)(mu-O(2)CMe)(4)] and Ds-pip or Ds-im. In both systems, the fluorescence response, which arises by NO-induced displacement of the axially coordinated fluorophore, is reversible with a sensitivity of approximately 4 microM. The related dinitrosyl complexes [Rh(2)(mu-O(2)CR)(4)(NO)(2)], where R = Me, Et, or n-Pr, were prepared, structurally characterized, and found to be air-stable, losing NO upon standing in solution. Sequestration of a methylene chloride solution of the Ds-pip complex from aqueous media by a NO-permeable membrane allows for fluorescence detection of NO for potential applications in biological fluids.     

Nuclear magnetic resonance study of self-diffusion in liquid crystals

A simple and accurate pulsed-gradient nuclear magnetic resonance technique for measuring coefficients of self-diffusion in liquid crystals is described. It is based on exciting sharp response signals with long weak pulses. The method uses an extremely weak radio-frequency field, which eliminates the problem of radio-frequency heating of the sample. The temperature dependencies of coefficients of self-diffusion for two liquid crystals, 5CB (4-pentyl-4(')-cyanobiphenyl) and EBBA (N-(4-ethoxybenzylidene)-4-butylaniline), are presented.     

Angiotensin II receptor blocker attenuates overexpression of vascular endothelial growth factor in diabetic podocytes

VEGF expressed in glomerular podocytes, is known to increase vascular permeability to macromolecules. Angiotensin II can stimulate the release of VEGF, and the protective effects of angiotensin II antagonist against diabetic glomerular injury suggest that the angiotensin II-induced VEGF is an important pathogenetic mechanism in the development of proteinuria during diabetic nephropathy although this mechanism is not fully understood. In this study, the changes of VEGF expression was examined in the experimental diabetic nephropathy to determine whether these changes were modified by renoprotective intervention by blockers of angiotensin II receptors. The streptozotocin- induced diabetic rats were treated with L-158,809, a blocker of angiotensin II receptors, for 12 weeks. Age-matched rats with L-158,809 served as controls. RT-PCR and immunohistochemistry were used to assess and quantify gene and protein expression of VEGF. A progressive increase in urinary protein excretion was observed in diabetic rats. Glomerular VEGF expression was significantly higher in diabetic rats than in the control groups, with a significant reduction in glomerular VEGF expression and proteinuria in L-158,809- treated diabetic rats. VEGF mRNA was also significantly higher in diabetic kidneys than in the control groups, with a significant reduction in VEGF mRNA in L-158,809-treated diabetic kidneys. These results demonstrates that VEGF expression is significantly increased in diabetic podocytes, and angiotensin II receptor antagonist attenuated these changes in VEGF expression and prevented the development of proteinuria in vivo. Attenuation of increased VEGF expression in podocytes could contribute to the renoprotective effects of angiotensin II receptor antagonists in diabetic nephropathy.     

Universal pion freeze-out in heavy-ion collisions

Based on an evaluation of data on pion interferometry and on particle yields at midrapidity, we propose a universal condition for thermal freeze-out of pions in heavy-ion collisions. We show that freeze-out occurs when the mean free path of pions lambda(f) reaches a value of about 1 fm, which is much smaller than the spatial extent of the system at freeze-out. This critical mean free path is independent of the centrality of the collision and beam energy from the Alternating Gradient Synchrotron to the Relativistic Heavy Ion Collider.     

Dual-facing-target-sputtered amorphous CoMoN/CN compound soft-X-ray multilayers: structures and thermal stability

Amorphous CoMoN/CN compound soft-X-ray multilayers were fabricated by dual-facing-target sputtering. Their structural thermal stability has been investigated by monitoring the structural evolutions of CN and CoMoN sublayers at annealing temperatures up to 800 °C using complementary measurement techniques, and measuring the coefficient of interfacial diffusion at annealing temperatures below 300 °C. The period expansion at annealing temperatures below 600 °C, which is usually observed in annealed metal/carbon soft-X-ray multilayers, is only 5%. The enhanced sp² to sp³ bond ratio caused by the incorporation annealing effect of nitrogen [1] is thought to be responsible for the improved thermal stability of CN sublayers. Mo addition greatly suppresses the structural thermal evolution of CoMoN sublayers. XPS and TEM analyses indicate that the strong chemical bonding between N and Co atoms and Mo nitride aggregation in the grain boundary of cobalt are the main mechanisms for the high thermal stability of CoMoN sublayers. The layered structure of the CoMoN/CN multilayers still exists at the annealing temperature of 800 °C, while Co/C and CoN/CN multilayers have already been destroyed at this temperature. Compared with Co/C and CoN/CN multilayers, the smaller negative interdiffusivity measured by X-ray diffraction reveals the stable interfaces of CoMoN/CN multilayers. These results illustrate that refractory metal incorporation and strong chemical bond establishment are quite effective in obtaining thermally highly stable compound soft-X-ray optical multilayers . PACS 68.65+g; 68.55.Ln; 68.35.Fx; 68.60.Dv     

Creep strain recovery of Fe-Ni-B amorphous metallic ribbon

Creep strain recovery and structural relaxation of the amorphous metallic glass Fe₄₀Ni₄₁B₁₉ after longtime loading at different annealing temperatures below the glass transition temperature have been studied using anisothermal differential scanning calorimetry (DSC) and dilatometry (TMA). It has been demonstrated that structural relaxation effects depend on the stress-annealing temperature of the amorphous ribbon. The structural relaxation states of the amorphous ribbon annealed at different temperatures under and without applied stress have been compared. The activation energy spectra were calculated from the anisothermal dilatometric measurements using the modern method based on the Fourier transformation technique. The influence of the annealing temperature on the shape of creep strain recovery spectra has been analyzed.      

Effect of Pretreatment of TaN Substrates on Atomic Layer Deposition Growth of Ru Thin Films

The polycrystalline ruthenium films are grown on TaN substrates by atomic layer deposition （ALD） using bis（cyclopentadienyl） ruthenium [RuCp2] and oxygen as ruthenium precursor and reactant respectively at a deposition temperature of 330℃. The low-energy Ar ion bombardment and Ru pre-deposition are performed to the underlying TaN substrates before ALD process in order to improve the Ru nucleation. X-ray diffraction, x-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy are carried out to characterize the properties of ALD Ru films. The results show that the nucleation density of Ru films with Ar^＋ bombardment to the underlying TaN substrates is much higher than that of the ones without any pretreatment. The possible reasons are discussed.     

Phase Transfer Catalyzed Anomeric Nucleophilic Substitutions with D-Xylopyranosyl Halides

Abstract

Anomeric pairs of per-O-acetylated-D-xylopyranosyl halides were individually treated with a wide variety of nucleophiles under mild PTC conditions. Thus, 2,3,4-tri-O-acetyl-α-D-xylopyranosyl bromide 1 provided exclusively the β-D-xylopyranosyl anomers 2-11 in good to excellent yields (65-95%). Alternatively, under the same PTC conditions, 2,3,4-tri-O-acetyl-β-D-xylopyranosyl chloride 13 afforded solely the inverted α-D-anomers 15 (82%) and 16 (67%) upon treatment with thiophenol and sodium azide, respectively. Similarly, 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl chloride 19 provided the analogous products 20 (63%) and 21 (31%) upon treatment with thiophenol and sodium azide. In the presence of tetrabutylammonium chloride as PTC catalyst, β-xylopyranosyl chloride 13 was shown to slowly equilibrate to the α-chloride 14. Therefore, care must be taken to avoid PTC catalyst for which counter anions can cause anomerization of the starting glycosyl halides.     

Synthesis and nonlinear optical properties of novel Y‐type polyester containing tricyanovinylthiazolylazoresorcinoxy group with enhanced thermal stability of dipole alignment

Novel Y‐type polyester 4 containing 5‐methyl‐4‐{5‐(1,2,2‐tricyanovinyl)‐2‐thiazolylazo}resorcinoxy groups as nonlinear optical (NLO) chromophores, which are parts of the polymer backbone, was prepared, and its NLO properties were investigated. Polyester 4 is soluble in common organic solvents such as N,N‐dimethylformamide and dimethylsulfoxide. Polymer 4 shows a thermal stability up to 250 °C from thermogravimetric analysis with glass‐transition temperature obtained from differential scanning calorimetry of approximately 94 °C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer film at 1560‐nm fundamental wavelength is 8.12 × 10^?9 esu. The dipole alignment exhibits a thermal stability even at 6 °C higher than glass‐transition temperature (T_g), and no significant SHG decay is observed below 100 °C due to the partial main‐chain character of polymer structure, which is acceptable for NLO device applications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

芴2,7位取代的9,9’-二芳基螺芴类化合物的合成及性能

设计并合成了一系列以三苯胺为核,芴衍生物为外围基团的有机蓝光小分子,该合成通过Suzuki反应在9-芳基芴的2位和(或)7位引入相同或不同取代基作为模块,并利用Friedel-Crafts反应将4-甲基三苯胺与这一系列模块结合.用NMR,MS和元素分析进行结构表征.荧光测试结果表明该类化合物溶液的荧光发射波长范围在442～466 nm之间,属蓝光发射.电化学测试显示该类材料的HOMO能级位于-5.15～-5.19 eV之间.差示扫描量热仪与热重分析得出化合物的玻璃化转变温度在166℃以上,热分解温度高于398℃,表明该类材料具有良好的热稳定性.